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2(UNO-)](O2. 2-. )(SbF6). UV-vis absorption spectra were recorded on a Hewlett Packard 8453 spectrophotometer and Shimadzu UV-3100PC attached with a ...

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Peroxo and Superoxo Moieties Bound to Copper Ion: Electron-Transfer Equilibrium with a Small Reorganization Energy Rui Cao,† Claudio Saracini,†,# Jake W. Ginsbach,‡,|| Matthew T. Kieber-Emmons,‡,⊥ Maxime A. Siegler,† Edward I. Solomon,*,‡ Shunichi Fukuzumi,*,§,# and Kenneth D. Karlin,*,† †

Department of Chemistry, Johns Hopkins University, Baltimore, MD 21218, USA



Department of Chemistry, Stanford University, Stanford, CA 94305, USA

§

Faculty of Science and Engineering, ALCA, SENTAN, Japan Science and Technology Agency (JST),

Meijo University, Nagoya, Aichi 468-0073, Japan #

Department of Chemistry and Nano Science, Ewha Womans University, Seoul 120-750, Korea

*

To whom correspondence should be addressed

[email protected] [email protected] [email protected]

Present Addresses ⊥ ||

Department of Chemistry, University of Utah, 315 S 1400 E, Salt Lake City, UT, 84112-0850 ZS Associates, Inc. 400 South El Camino Real, Suite 1500, San Mateo, CA, 94402

Table of Contents 1. Materials and instrumentation 2. Synthesis and characterization of [CuI2(UNO-)](SbF6)(CH3CN) and [CuII2(UNO)(OH)](SbF6)2 3. Synthesis and characterization of [CuICuII(UNO-)(DMF)](SbF6)2 and [CuIICuII(NO2UN-O–)(Cl)](SbF6)• (CH2Cl2)2

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  4. Synthesis and characterization of ferrocenium hexafluoroantimonate and its derivatives 5. Cyclic Voltammetry (CV) 6. Drawings of the ligands described in main text Table 1 • Figure S1 7. Single Crystal X-ray Crystallography • Figure S2, Figure S3 8. Bond Valence Sum (BVSA) analysis for [CuICuII(UNO-)(DMF)](SbF6)2 • Table S1 9. Eyring plot of [CuII2(UNO-)](O2-)(SbF6)2 formation and kinetics • Figure S4, Table S2 10. Titration experiments for [CuII2(UNO-)](O22-)(SbF6) and [CuII2(UNO-)](O2-)(SbF6)2 interconversion • Figure S5 11. Step by step deduction of reduction potential of [CuII2(UNO-)](O2-)(SbF6)2 12. Stopped-flow kinetics of [CuII2(UNO-)](O2-)(SbF6)2 formation 13. Step by step deduction of the reorganization energy of the electron transfer process 14. rRaman experiments for [CuII2(UNO-)](O22-)(SbF6) and [CuII2(UNO-)](O2-)(SbF6)2 15. Low temperature (-80 ºC) 1H-NMR spectroscopy experiment for [CuII2(UNO-)](O22)(SbF6). • Figure S6 16. DFT details of the ligand conformations for [CuII2(UNO-)](O22-)(SbF6) and [CuII2(UNO-)](O2-)(SbF6)2 structure analysis • Figure S7 - S10, Table S3 - S15 17. DFT calculation of reorganization energy • Table S16 – S17 18. Mullikan population analysis • Table S18 19. References 1. Materials and instrumentation All materials purchased were of highest purity available from Sigma-Aldrich Chemicals, Strem Chemicals, or Tokyo Chemical Industries (TCI) and used as received, unless specified otherwise. Dichloromethane (CH2Cl2), acetonitrile (CH3CN) and diethyl ether (CH3CH2OCH2CH3, Et2O) were used after passing them through a 60 cm long column of activated alumina (Innovative Technologies, Inc.) under argon. Dioxygen was dried by passing through a short column of supported P4O10 (Aquasorb, Mallinkrodt). Preparation and handling of air sensitive complex were performed in an MBraun Labmaster 130 nitrogen atmosphere drybox S2  

  or under argon atmosphere using standard Schlenk techniques. Solvent deoxygenation was achieved by bubbling with argon for about 40 minutes through addition funnel connected to a receiving Schlenk flask. Elemental analyses were conducted by Columbia Analytical Services and air-sensitive samples were prepared in the glovebox and flame sealed outside using standard Schlenk techniques. UV-vis spectra were recorded with a Cary-50 Bio spectrophotometer equipped with a fiber optic coupler (Varian) and a fiber optic dip probe (Hellma: 661.202-QXUV-1cm-for-low-temperature) and/or UnispeKs CoolSpeK N40P103410 cryostat controller and cell holder kit by Unisoku Scientific Instruments. NMR spectroscopy was performed on Bruker 300 and/or 400 MHz instruments with spectra calibrated to either internal tetramethylsilane (TMS) standard or to residual protio solvent. EPR measurements were performed on an X-Band Bruker EMX-plus spectrophotometer equipped with a dual mode cavity (ER 4116DM) or Bruker EMX CW EPR controlled with a Bruker ER 041 XG microwave bridge operating at the X band (~9 GHz). X-ray diffraction was performed at the X-ray diffraction facility at the Johns Hopkins University. The X-ray intensity data were measured on an Oxford Diffraction Xcalibur3 system equipped with a graphite monochromator and an Enhance (Mo) X-ray Source (λ = 0.71073Å) operated at 2 kW power (50 kV, 40 mA) and a CCD detector. The frames were integrated, scaled and corrected for absorption using the Oxford Diffraction CrysAlisPRO software package. Resonance Raman spectra were collected with a triple monochromator (Spex 1877 CP with 1200, 1800, and 2400 groves/mm holographic spectropgraph gratings) and a CCD (Andor Newton). Laser excitation (20 mW at the sample) was provided by an argon ion laser (Innova Sabre 25/7) and a krypton ion laser (Coherent I90C-K). The 18O2 (99 atom %) gas was purchased from Icon Isotopes as a 1 L tank. The mixed-isotope O2 gas was purchased from Icon Isotopes as a 25 ml glass bulb containing a statistical mixture of 1:2:1 of 16O-16O : 16O-18O : 18O-18O with 97% atom percentage. Stopped-flow kinetics measurements were performed on a Unisoku RSP601 stopped-flow spectrometer equipped with a MOS-type highly sensitive photodiode array or a Hewlett-Packard 8453 photodiode-array spectrophotometer using a 10 mm quartz cuvette (10 mm path length) and a Unisoku thermostatted cell holder. The rates were determined through monitoring the decrease in spectral intensity at 510 nm corresponding to [CuII2(UNO-)](O22)(SbF6). UV-vis absorption spectra were recorded on a Hewlett Packard 8453 spectrophotometer and Shimadzu UV-3100PC attached with a UNISOKU thermostat cell holder. DFT calculations were performed with the B3LYP functional with TZVP on copper, oxygen, and nitrogen atoms and SV on carbon and hydrogen with an ultrafine integration grid in dichloromethane as modeled by a Polarizable Continuum Model as implemented in Gaussian 091. Analytical frequency calculations were performed on all stationary points to verify that a local minimum (or transition state) had been found and for comparison to rR data. 2. Synthesis and characterization of [CuI2(UNO-)](SbF6)(CH3CN) and [CuII2(UNO)(OH)](SbF6)2 2.1 Synthesis of complex [CuI2(UNO-)](SbF6)(CH3CN) The complex [CuI2(UNO-)](PF6)(CH3CN) was previously synthesized and characterized.2 The method employed here is to use CuI(CH3CN)4(SbF6) instead of the CuI(CH3CN)4(PF6) salt while other conditions are kept the same. The final product [CuI2(UNO-)](SbF6)(CH3CN) was recrystallized with DCM/Et2O to give a 65% yield of light yellow air sensitive crystals. The purity of the complex was determined by elemental analysis and NMR spectroscopy. Mw =

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  961.6. Anal. Calcd for (C37H40Cu2F6N7OSb): C, 46.21; H, 4.19; N, 10.20. Found: C, 46.05; H, 4.02; N, 9.93. 1H-NMR (CD3NO2; 400 MHz): 2.05 (s,3H), 2.45-2.71 (m, 8H), 2.85-2.95 (m,4H), 3.25-3.35 (m, 4H), 3.75 (s, 2H), 6.55 (t(d-d), 1H), 6.89 (d, 1H), 7.05 (t(d-d), 2H), 7.21 (t(d-d), 4H), 7.31 (d,1H), 7.41 (t(d-d), 2H), 7.71 (t(d-d), 2H), 7.79 (t(d-d), 2H), 7.95 (s, br,2H), 9.05 (d, 2H). 2.2 Synthesis of complex [CuII2(UNO-)(OH)](SbF6)2 The complex [CuII2(UNO-)(OH)](PF6)2 was previously synthesized and characterized.2 The method employed here was to use CuI(CH3CN)4(SbF6) instead of the CuI(CH3CN)4(PF6) salt while other conditions were kept the same for the synthesis. The final product [CuII2(UNO)(OH)](SbF6)2 was recrystallized with DCM/Et2O to give a 45% yield of green crystals. The purity of the complex was determined by elemental analysis and further examined by X-ray crystallography. Mw = 1132.3 Anal. Calcd for (C35H38Cu2F12N6O2Sb2): C, 35.8; H, 3.3; N, 7.2. Found: C, 36.1; H, 3.2; N, 7.4. 3. Synthesis and characterization of [CuICuII(UNO-)(DMF)](SbF6)2 (1) and [CuIICuII(NO2UN-O–)(Cl)](SbF6)• (CH2Cl2)2: 3.1 Synthesis of complex [CuICuII(UNO-)(DMF)](SbF6)2 (1) 110 mg (0.114 mmol) of the [CuI2(UNO-)](SbF6)(CH3CN) complex charged in a clean vial inside a glovebox. 48 mg (0.114 mmol) of [(Cp)2Fe]SbF6 was dissolved using 3 ml of degassed DMF solvent in the glovebox to obtain a dark blue solution. The [(Cp)2Fe]SbF6 solution was added dropwise to the vial charged with [CuI2(UNO-)](SbF6)(CH3CN) complex. The light yellow crystals gradually dissolved and the solution turned to a brownish green color, whereupon this solution was left to stir for an hour under a nitrogen atmosphere. Then, the contents of the vial was transferred to a wide neck bottle filled with 15 ml of degassed Et2O and these were left to slowly diffuse and mix with the [CuICuII(UNO-)](SbF6)2 solution. After two days, brownish green crystals of [CuICuII(UNO-)(DMF)](SbF6)2 were obtained and the remaining solution turned yellow. Yield; ~70% (95 mg) after washing and drying under nitrogen. Mw = 1229.6. Anal. Calcd for (C38H44Cu2F12N7O2Sb2): C, 37.12; H, 3.61; N, 7.98. Found: C, 37.26; H, 3.73; N, 7.68. 3.2 Synthesis of complex [CuIICuII(NO2UN-O–)(Cl)](SbF6)2(CH2Cl2)2 20 mg (0.021 mmol) of [CuICuII(UNO-)(DMF)](SbF6)2 was dissolved in 10 ml of dichloromethane (DCM) solvent and charged into a 50 ml Schlenk flask. The flask was chilled in a dry-ice/acetone bath (-80 °C) under argon using standard Schlenk techniques. The solution was bubbled with excess O2 for a few seconds and left to react for 1 hr. Then O2 was removed by applying vaccum/purge (with Ar) cycles. The resulting solution was bubbled with excess NO(g) and let react for 20 mins. With slow warmup of the solution, crystals of [CuIICuII(NO2UN-O– )(Cl)](SbF6)2(CH2Cl2)2 were directly obtained (Figure S2). Details of this reaction chemistry will be reported later as a separate project. 4. Synthesis and characterization of ferrocenium hexafluoroantimonate and its derivatives The complex ferrocenium hexafluoroantimonate (FcSbF6) and its derivatives were synthesized via a revised literature procedure.3 4.1 Synthesis and characterization of ferrocenium hexafluoroantimonate (FcSbF6)

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  0.55g (1.6 mmol) of silver hexafluoroantimonate (AgSbF6) was charged in a 20 ml vial wrapped with aluminum foil. Ferrocene (Fc. 0.30 g (1.6 mmol)), dissolved with 10 ml of diethyl ether, was placed in another 20 ml vial and this solution was gradually added to the vial containing AgSbF6., whereupon the solution color changed to green. After stirring for 30 min, a dark green/blue precipitate formed on the bottom of the vial and the solution changed to a yellow color. This supernatant solution was removed with a Pasteur pipette and the solid remaining was redissolved using 10 ml of acetone. This solution was passed through a medium glass-fritted funnel layered with a short Celite column (1 inch) and 30 ml more of acetone was used as eluent to collect all the remaining compound in a round bottom flask (100 ml). This solution was concentrated by rotory evaporation, to about a total of 10 ml and then transferred to a 20 ml vial. This vial was placed into a wide neck bottle containing about 30 ml of Et2O at the bottom, and it was allowed to slowly diffuse to the vial with product complex. Royal blue crystals were formed after ~ 12 hours giving 0.4 g (~ 60 % yield). Anal. Calcd for (C10H10FeSbF6): C, 28.5; H, 2.4. Found: C, 28.3; H, 2.5. 4.2 Synthesis and characterization of acetyl-ferrocenium hexafluoroantimonate (AcFcSbF6) 0.55 g (1.6 mmol) of silver hexafluoroantimonate (AgSbF6) was charged in a 50 ml with a 14/20 joint Schlenk flask with a glass stopcock. The flask was sealed with a rubber septum and wrapped with aluminum foil. 0.36 g (1.6 mmol) of acetyl-ferrocene was dissolved into 20 ml of Et2O in a 100 ml addition funnel. Deoxygenation was carried on the Et2O solution by rigorously bubbling argon for 20 min. Gradually add the acetyl-ferrocene solution to react with AgSbF6 for 30 mins. The solution gradually turned yellow accompanied by formation of a dark blue precipitate. The yellow supernatant solution was decanted and under Ar, the precipitate was dissolved using degassed DCM (Note: O2 was removed by bubbling the solvent with Ar gas for 20 mins) and the resulting solution filtered through Celite using a medium glass-fritted Schlenk funnel under Ar and passed into a receiving 100 ml Schlenk flask. Degassed Et2O (80 ml) was added to this solution and blue crystals were obtained then next day, a 40% yield after isolation and drying. The blue crystals are relatively stable in the air. Anal. Calcd for (C12H12FeOSbF6): C, 31.1; H, 2.6. Found: C, 30.8; H, 2.7. 4.3 Synthesis and (Me2FcSbF6)

characterization

of

Dimethylferrocenium

hexafluoroantimonate

0.55 g (1.6 mmol) of silver hexafluoroantimonate (AgSbF6) was charged into a 20 ml vial and wrapped with aluminum foil. Dimethyl ferrocene (Me2Fc) (0.34 g, 1.6 mmol) was dissolved in 10 ml of diethyl ether in a 20 ml vial and the ferrocene solution was gradually added to the vial containing AgSbF6 whereupon the solution turned into a greenish blue color. After stirring for 30 min, a dark green/blue precipitate was formed on the bottom of the vial and the supernatant solution changed to a yellow color. The supernatant was removed using a glass pipette and the remaining solid redissolved using 10 ml of acetone. This solution was passed through a medium glass-fritted funnel layered with short Celite column (1 inch) and 30 ml more of acetone was used as eluent to collect all the remaining compound in a round bottom flask (100 ml). The solution was concentrated to a ~ 10 ml volume using rotory evaporation, and then transferred to a 20 ml vial. This vial was placed in a wide neck bottle containing about 30 ml of diethyl ether at

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  the bottom and it was allowed to slowly diffuse to the vial. Royal blue crystals were formed overnight and after drying giving 0.42 g of product (60% yield). Anal. Calcd for (C12H16FeSbF6): C, 32.0; H, 3.1. Found: C, 32.2; H, 3.3. 4.4 Synthesis and characterization of diphenyl amine ferrocene (Ph2NFc) and diphenyl amine ferrocenium hexafluroantimonate (Ph2NFcSbF6). The synthesis of the diphenylamine ferrocene was derived from a literature modified method: Özçubukçu, S.; Schmitt, E.; Leifert, A.; Bolm, C. Synthesis 2007 (3), 389-392. Bromoferrocene (0.53 g, 2 mmol), CuI (0.40 g, 2.1 mmol), K2CO3 (0.55 g, 4 mmol) and diphenylamine (Ph2NH) (0.37 g, 2.2 mmol) were measured out and used for the following procedure. A 10 ml Schlenk flask was charged with a magnetic stir-bar and 4 ml of DMSO solvent, which had been degassed by several freeze (LN2)/thaw (under Ar) cycles. While keeping an Ar flow, the reagents (as above) bromoferrocene, CuI, K2CO3 and diphenylamine were added into the flask which was then sealed with a 14/20 rubber septum (and secured with copper wire). The resulting solution was heated to 90 ºC under argon using a sand bath while stirring for 24 hours. Working up the product using a ½ inch by 8 inch column packed with silica gel and using pure hexane as eluent, the diphenyl amine ferrocene (Ph2NFc) containing solution was collected and obtained a yield of 35% after drying. Anal. Calcd for (C22H19FeN): C, 74.8; H, 5.4. Found: C, 74.5; H, 5.6. The diphenyl amine ferrocenium hexafluroantimonate (Ph2NFcSbF6) was synthesized using the following procedure: 0.1 g (0.3 mmol) of silver hexafluoroantimonate (AgSbF6) was charged into a 20 ml vial wrapped with aluminum foil and dissolve with 5 ml of a 90:10 dichloromethane: acetonitrile mixture. 0.11 g (0.3 mmol) of diphenyl amine ferrocene (Ph2NFc) was charged into a vial and the AgSbF6 solution was slowly added. The resulting solution was filtered and recrystallized using DCM/pentane to obtain red needle-like crystals. Anal. Calcd for (C22H19F6FeNSb): C, 44.9; H, 3.2. Found: C, 44.6; H, 3.3. The UV-Vis absorption spectrum using various concentration for analysis of the 1014 nm absorption; The observed absorptions for solutions of the following concentrations, 0.19 mM, 0.095 mM, 0.048 mM and 0.019 mM at -80 ºC, were found to be 0.56, 0.31, 0.18 and 0.01. Therefore, the extinction coefficient at 1014 is is calculated to be 2680 M-1 cm-1. 5. Cyclic Voltammetry (CV) Reduction potentials of the ferrocenes and derivatives were measured using a BAS-100B potentiostat linked to a computer. The ferrocene and derivatives were each prepared as 10 mM solutions in DCM under a nitrogen atmosphere in a round bottom Schlenk flask equipped with 3 side arms sealed with 14/20 rubber septa. CVs were recorded at 25 ºC using a 100 mV/s scan rate. nBu4NPF6 (0.1 M) was employed as the supporting electrolyte. In a typical experiment, a standard three-electrode cell was used containing a glassy carbon working electrode, a platinum wire counter electrode, and a reference electrode consisting of a 10 mM solution of Ag/AgCl. The ferroceninum/ferrocene (Fc+/Fc) couple was employed as external standard to calculate the reduction potentials for the ferrocenium derivatives, and the calculated reduction potentials versus Fc+/Fc were further calibrated versus SCE and listed in Figure 4a of the main text.

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6. Drawings of the ligands in the main text Table 1

Figure S1. Drawings of the ligands listed in main text, Table 1. UN-OH = 2-(bis(2-(pyridin-2yl)ethyl)amino)-6-((bis(2-(pyridin-2-yl)ethyl)amino)met-hyl)phenol; XYL-OH = 2,6-bis((bis(2(pyridin-2-yl)ethyl)amino)methyl)phenol; TMPA = tris(2-methylpyridyl)amine; PV-TMPA = bis(pyrid-2-ylmethyl){[6-(pivalamido)pyrid-2-yl]-methyl}amine; TMG3tren = 1,1,1-tris{2-[N2(1,1,3,3-tetramethylguanidino)]ethyl}amine); Me6tren = tris(2-dimethylaminoethyl)amine; HIPT3tren = tris(hexaisopropylterphenyl) amine; LiPr = 1-isopropyl-5-[2-(2-pyridyl)ethyl]-1,5diazacyclooctane; HMe2LiPr2 = pentane-2,4-diylbis((2,6-diisopropylphenyl)-l2-azane), hydrogen salt.

7. Single Crystal X-ray Crystallography All reflection intensities were measured at 110(2) K using a KM4/Xcalibur (detector: Sapphire3) with enhance graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) under the program CrysAlisPro (Versions 1.171.34.44/ 1.171.35.11 Oxford Diffraction Ltd., 2010). The same program was used to refine the cell dimensions and for data reduction. The structure was

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  solved with the program SHELXS-2014/7 (Sheldrick, 2008) and was refined on F2 with SHELXL-2014/7 (Sheldrick, 2008). Analytical numeric absorption corrections based on a multifaceted crystal model were applied using CrysAlisPro. The temperature of the data collection was controlled using the system Cryojet (manufactured by Oxford Instruments). The H atoms were placed at calculated positions using the instructions AFIX 23, AFIX 43 or AFIX 137 with isotropic displacement parameters having values 1.2 or 1.5 times Ueq of the attached C atoms. For the structure of [CuIICuII(UN-O–)(OH)](SbF6)2, the H atom of the coordinated hydroxide was found from difference Fourier map, and the O−H distance was set to be refined to 0.84(3) Å using one DFIX restraint. [CuICuII(UNO-)(DMF)](SbF6)2 (1): Fw = 1229.38, yellow-green lath, 0.47 × 0.17 × 0.04 mm3, triclinic, P-1 (no. 2), a = 10.81274(18), b = 11.4439(2), c = 19.1353(3) Å, α = 78.4517(14), β = 78.6462(14), γ = 73.1423(15)°, V = 2195.72(6) Å3, Z = 2, Dx = 1.859 g cm−3, µ = 2.267 mm−1, abs. corr. range: 0.499−0.926. 30479 Reflections were measured up to a resolution of (sin θ/λ)max = 0.62 Å−1. 8625 Reflections were unique (Rint = 0.0549), of which 7365 were observed [I > 2σ(I)]. 634 Parameters were refined with 321 restraints. R1/wR2 [I > 2σ(I)]: 0.0276/0.0658. R1/wR2 [all refl.]: 0.0351/0.0682. S = 1.055. Residual electron density found between −0.62 and 0.57 e Å−3. The asymmetric unit contains one molecule of Cu(I)−Cu(II) complex and two SbF6



counterions. The structure is mostly ordered, except for one of the two counterions that is found to be disordered over two orientations [occupancy factor of the major component: 0.697(4)]. [CuIICuII(NO2UN-O–)(Cl)](SbF6)2• (CH2Cl2)2: Fw = 1401.64, yellow plate, 0.42 × 0.33 × 0.05 mm3, triclinic, P-1 (no. 2), a = 9.5t5(2), b = 13.8420(3), c = 20.1911(5) Å, α = 106.146(2), β = 93.216(2), γ = 107.792(2)°, V = 2402.75(9) Å3, Z = 2, Dx = 1.937 g cm−3, µ = 2.354 mm−1, abs. corr. range: 0.440−0.893. 29451 Reflections were measured up to a resolution of (sin θ/λ)max = 0.62 Å−1. 9714 Reflections were unique (Rint = 0.0352), of which 8386 were observed [I > 2σ(I)]. 678 Parameters were refined using 207 restraints. R1/wR2 [I > 2σ(I)]: 0.0264/0.0636. R1/wR2 [all refl.]: 0.0339/0.0665. S = 1.048. Residual electron density found between −0.78 and 1.19 e Å−3. The structure is mostly ordered, except for one of the two counteanions that is found to be disordered over two orientations [occupancy factor of the major component: 0.530(13)]. The crystal is a phase mixture, for which the major component has the nitrato group attached to

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  C17 with an occupancy of 0.886(4). The minor component being that for which one H atom is attached to C17 (which was initially the expected ligand). After tackling the phase mixture problem, the refinement turned out to be problem free.

Figure. S2 Displacement ellipsoid plot (50% probability level) of [CuII2(NO2UNO)(Cl)]2+ Lattice solvent and counter-anions (and proton) are omitted for clarity. Selected bond lengths (Å) and angles (deg): Cu1-O1, 1.956(2); Cu1-N1, 2.011(2); Cu1-N2, 2.025(2); Cu1-N3, 2.182(2); Cu2-O1, 1.954(2); Cu2-N4, 2.082(2); Cu2-N5, 1.986(3); Cu2-N6, 2.173(2). Cl1-Cu1-O1, 80.14(6); Cl1-Cu1-N1, 97.98(7); Cl1-Cu1-N2, 156.55(6); Cl1-Cu1-N3, 101.39(6); O1-Cu1-N1, 166.47(9); O1-Cu1-N2, 84.53(8); O1-Cu1-N3, 98.50(8); N1-Cu1-N2, 92.79(9); N1-Cu1-N3, 95.01(8); N2-Cu1-N3, 98.33(8); Cl1-Cu2-O1, 78.18(6); Cl1-Cu2-N4, 165.81(6); Cl1-Cu2-N5, 88.68(7); Cl1-Cu2-N6, 95.70(6); O1-Cu2-N4, 92.46(8); O1-Cu2-N5, 151.40(9); O1-Cu2-N6, 101.59(8); N4-Cu2-N5, 94.89(9); N4-Cu2-N6, 96.62(8); N5-Cu2-N6, 104.94(9).

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  [CuIICuII(UN-O–)(OH)](SbF6)2:

Fw = 1173.29, green lath, 0.58 × 0.16 × 0.10 mm3,

monoclinic, P21/n (no. 14), a = 13.5404(4), b = 11.2264(4), c = 26.4611(11) Å, β = 90.054(3), V = 4022.3(3) Å3, Z = 4, Dx = 1.937 g cm−3, µ = 2.469 mm−1, abs. corr. range: 0.399−0.840. 20865 Reflections were measured up to a resolution of (sin θ/λ)max = 0.59 Å−1. 6974 Reflections were unique (Rint = 0.0307), of which 6579 were observed [I > 2σ(I)]. 536 Parameters were refined using 1 restraint. R1/wR2 [I > 2σ(I)]: 0.0377/0.0892. R1/wR2 [all refl.]: 0.0410/0.0908. S = 1.040. Residual electron density found between −0.65 and 1.03 e Å−3. The structure is ordered. The crystal was found to be twinned pseudo-merohedrally, and the twin relationship corresponds to a twofold axis found along the c direction. The twin law is described by the matrix: (-1 0 0 / 0 -1 0 / 0 0 1). The batch scale factor refines to 0.4973(9).

Figure. S3 Displacement ellipsoid plot (50% probability level) of [CuIICuII(UN-O–)(OH)]2+ Lattice solvent and counter-anions are omitted for clarity. Selected bond lengths (Å) and angles (deg): Cu1-N1, 2.015(5); Cu1-N2, 2.060(6); Cu1-N3, 2.147(6); Cu1-O1, 1.968(4); Cu1-O2, 1.934(4); Cu2-N4, 2.057(7); Cu2-N5, 2.068(6); Cu2-N6, 2.091(5); Cu2-O1, 2.026(4); Cu2-O2, 1.944(4). N1-Cu1-N2, 95.5(2); N1-Cu1-N3, 105.5(2); N1-Cu1-O1, 142.7(2); N1-Cu1-O2, 94.3(2); N2-Cu1-N3, 98.3(2); N2-Cu1-O1, 84.2(2); N2-Cu1-O2, 158.9(2); N3-Cu1-O1, S10  

  111.4(2); N3-Cu1-O2, 97.1(2); O1-Cu1-O2, 76.8(2); N4-Cu2-N5, 96.4(3); N4-Cu2-N6, 93.8(3); N4-Cu2-O1, 90.4(2); N4-Cu2-O2, 165.3(2); N5-Cu2-N6, 118.0(2); N5-Cu2-O1, 119.1(2); N5Cu2-O2, 93.2(2); N6-Cu2-O1, 121.9(2); N6-Cu2-O2, 91.6(2); O1-Cu2-O2, 75.2(2). 8. Bond Valence Sum (BVSA) analysis for [CuII2(UNO-)(DMF)](SbF6)2 BVSA was first proposed by Thorp,4 according to the equation s = exp[(r0-r)/B] where s represents bond valences; r0 and B (=0.37) are empirically determined values listed in Table S1. The r values are determined through the bond distances in the crystal structure (Figure 2 (a)). Employing s = exp[(r0-r)/B] and values in Table S1, s(Cu1) = 1.12 and s(Cu2) = 2.16. Table S1: r and r0 values used to calculate the bond valences (s) bond r0 , Å 4 bond r, Å bond 2+ Cu -N 1.751 Cu1-N1 1.964 Cu2-N4 Cu2+-O 1.679 Cu1-N2 2.129 Cu2-N5 Cu+-N 1.595 Cu1-N3 1.989 Cu2-N6 + Cu -O 1.523 Cu1-O1 2.169 Cu2-O1 Cu2-O2

r, Å 2.048 2.024 2.180 1.942 1.991

9. Eyring plot of [CuII2(UNO-)](O2-)(SbF6)2 formation and kinetics

Table S2: Kinetics data for [CuII2(UNO-)](O2-)(SbF6)2 formation at various temperature ln(k/T) 1/T (K-1) -8.52 0.00546 -8.08 0.00532 -7.66 0.00518 -7.06 0.00505 -6.50 0.00492 -6.16 0.00481

S11  

 

E quatio y  =  a  +  b*x

-­‐6

Adj.  R -­‐S 0.992

ln(k/T )

Value

-­‐7

S tandar

A

Interc 11.822 0.72181

A

S lope

-­‐3738. 140.752

-­‐8

0 .0 0 4 8

0 .0 0 5 0

1/T   ( K

0 .0 0 5 2

-­‐1

0 .0 0 5 4

)

Figure S4. Eyring plot for kinetic results obtained on [CuII2(UNO-)](O2-)(SbF6)2

ln

k k ΔH ≠ 1 ΔS ≠ =− ⋅ + ln B + T R T h R

Calculated value of the activation enthalpy and entropy ΔH ≠ = 31.1 ± 1.1kJ / mol , ΔS ≠ = −99.4 ± 6.0 J / K ⋅ mol 10. Titration experiments for [CuII2(UNO-)](O22-)(SbF6) and [CuII2(UNO-)](O2-)(SbF6)2 interconversion [CuI2(UNO-)](SbF6)(CH3CN) (5.5 mg) was used to prepare a 25 ml stock solution using a 25 ml volumetric flask. From here, 10 ml (0.00231mmol) were transferred to a Schlenk flask and charged with a magnetic stir-bar in the inert-atmosphere box. The Schlenk flask was sealed using a septum and brought out of the glove-box and put into a Dewar filled with acetone/dry and allowed to equilibrate for 10 min. In the meantime, the side-arm of the Schlenk flask was attached to the Schlenk line under an Ar atmosphere. The top septum was removed and a UV-vis Dip-Probe was put into the Schlenk flask while keeping an Ar flow.. After ~5 min, a spectrum was recorded for this complex [CuI2(UNO-)](SbF6), as shown in Figure S5(a) (yellow line spectrum). Dioxygen gas was slowly bubbleed into the solution for ~ 1 second which allowed for the full formation of [CuII2(UNO-)](O22-)(SbF6) in Figure S5(a) (purple line spectrum), as evidenced by having no further increase in the intensity of the purple line spectrum after additional O2-injection. Separately, [(Cp)2Fe]SbF6 (24 mg) was used to prepare a 5 ml stock solution and 200 µl put into a 1 ml Hamilton gas-tight syringe. Initially, ¼ equiv (50 µl) of the S12  

  [(Cp)2Fe]SbF6 solution was injected which led to the the first red line spectrum Figure S5(a), that below the purple line spectrum. Further additions of half and then three-quarter equiv resulted in two more red line spectra, Figure S5(a), with isosbestic conversion to the green line spectrum, which corresponds to a fully formed solution of [CuII2(UNO-)](O2-)(SbF6)2, as evidenced by by the observation that additional one more equiv from the [(Cp)2Fe]SbF6 solution led to no change from the the green spectrum. The experiment was repeated several times using varying amounts of [CuI2(UNO)](SbF6)(CH3CN). With 4.4 mg of the [CuI2(UNO-)](SbF6)(CH3CN) complex, similar steps were repeated as given by the procedures written just above (Figure S5(b)) where the purple line spectrum represents the fully formed [CuII2(UNO-)](O22-)(SbF6) complex and the green line spectrum was the fully formed superoxide complex [CuII2(UNO-)](O2-)(SbF6)2 . Addition of one equivalent of (Cp*)2Fe (decamethylferrocene) resulted in near complete ~ 90% regeneration of the [CuII2(UNO-)](O22-)(SbF6) which is the black line spectrum (Figure S5(b). The diphenylamine ferrocenium complex (see above), made according to literature modified procedures (see above, Sect. 4.4), was used and led to the generation of Figure S5(c) where the ferrocenium and the superoxide complex reached an equilibrium state and the redox potential could be calculated using Nernst equation, see below. The final spectrum is the red line spectrum where one equiv of Ph2NFcSbF6 had been added to the peroxide [CuII2(UNO-)](O22-)(SbF6) complex.

S13  

 

Figure S5. [CuII2(UNO-)](O22-)(SbF6) and [CuII2(UNO-)](O2-)(SbF6)2 interconversion

S14  

  11. Step by step deduction of reduction potential of [CuII2(UNO-)](O2-)(SbF6)2 In the inert-atmosphere box, [CuI2(UNO-)](SbF6)(CH3CN) (4.5 mg) was dissolved with 25 ml of DCM solvent in a 25 ml volumetric flask to obtain a 0.189 mM solution. From that solution, 10 ml was transferred to a Schlenk flask which was sealed with a rubber septum before bringing it out of the glovebox. The titration experiment was performed the same way as described above in Section 10. The amount of starting [CuI2(UNO-)](SbF6)(CH3CN) and Ph2FcSbF6 were both 1.89 x 10-6 mol. [CuII2(UNO-)](O22-)(SbF6) + Ph2NFcSbF6 → [CuII2(UNO-)](O2-)(SbF6)2 + Ph2NFc Start

1.89

1.89

0

0

Equilibrium

0.57

0.57

1.32

1.32

In the equilibrium state, the unreacted (i.e., remaining) amount of Ph2NFcSbF6 was calculated based on measurement of the absorption difference observed and measured at 1014 nm (ε = 2680 M-1cm-1 at -80 ºC, see above). It was found that this ΔA = 0.15, so that concentration of unreacted Ph2NFcSbF6 was c = A/ε = 5.6 x 10-5 mol/L in a total amount of 10.2 ml of solution which is equal to 0.57 x 10-6 mol. Thus, the [CuII2(UNO-)](O2-)(SbF6)2 generated was 1.32 x 10-6 mol. Therefore, Ket = (1.32 x 1.32) / (0.57 x 0.57) = 5.36. According to Nernst equation at equilibrium state: !"

0 = 𝐸°!" − !" 𝑙𝑛𝐾!" , 𝐸°!" = 𝐸° 0 = 0.16𝑉 − 𝐸°

!"#$%&'(!" !"#$%&'"



!"!!!" !

!"!!"! !.!"#×!"# !"#

%$− 𝐸°

!"#$%&'()$ !"#$%&'" !"#$%&'()$

×𝑙𝑛5.36, 𝐸°

!"#$%&'"

= 0.13𝑉  𝑣𝑠  𝑆𝐶𝐸

12. Stopped-flow kinetics of [CuII2(UNO-)](O2-)(SbF6)2 formation 60 mM solutions of [CuI2(UN-O–)](SbF6)(CH3CN) (1.4 mg in 25 mL) and of 60 mM dimethyl ferrocenium hexafluoroantimonate (Me2FcSbF6) (53.9 mg in 2 mL) in O2-free 1,2dichloroethane were prepared, separately, in a glove box and were placed into 50 mL Schlenk flasks equipped with rubber septa. In a typical experiment, the [CuII2(UN-O–)(O22–)]+ complex was formed by direct O2 bubbling through a 24-inch needle (19-gauge) for 5 minutes into 1 mL of the 60 mM solution of [CuI2(UN-O–)]+, previously transferred in the stopped-flow pre-loading cell, equipped with a rubber septum (and previously flashed with argon gas), through a 2 mL Hamilton syringe equipped with a three-way high-pressure stopcock that allowed syringe flashing with argon gas. After transferring 1 mL of the 60 mM dimethyl ferrocenium in a separate pre-loading stopped-flow cell using the same procedure as used for [CuI2(UN-O–)]+, mixing of [CuII2(UN-O–)(O22–)]+ and dimethyl ferrocenium was allowed and UV-visible spectra were collected at various temperature ranging from -55 °C to -80 °C.

S15  

 

13. Step by step deduction of reorganization energy of the electron transfer process

From the Eyring plot: ΔH‡ (kET) = 4.1 ± 0.7 (kcal mol-1) = 17.1 ± 2.9 (kJ mol-1) ΔS‡ (kET) = -3.8 ± 3.6 (cal K mol-1) = -0.016 ± 0.015 (J K-1 mol-1) ΔG‡ = ΔH‡ -T ΔS‡ = (17.1 ± 2.9) – 193.15 (-0.016 ± 0.015) = 20.2 ± 4.1 (kJ mol-1) Also, from Marcus theory ΔG‡ = (λET + ΔG0)2/ 4λET ΔG0 = - nF [E0Red (Me2Fc+/Me2Fc) - E0red (Superoxide/Peroxide)] = - F [0.26 - 0.13] = -12.5 kJ mol-1 Therefore, λET = 1.1 ± 0.2 eV

14. Resonance Raman Spectrocopy for [CuII2(UNO-)](O22-)(SbF6) and [CuII2(UNO-)](O2)(SbF6)2. A 2 mM stock solution of [CuI2(UNO-)](SbF6)(CH3CN) in DCM was prepared in the dry box using similar procedures as described above in section 10. Each tube for the Resonance Raman was charged with 500 µl of the stock solution and sealed with septum and parafilm. The tubes were immediately put into acetone/dry ice bath after bringing outside the glove box. A gas tight syringe with a three-way stopper was used for oxygenation. Firstly, the syringe was flushed with argon gas for several cycles, then pure oxygen 16O2 from a septum and electrical/parafilm tape sealed Schlenk flask was used to oxygenate some of the same tubes of dicopper(I) complex. Afterwards, the samples in the tubes were frozen under LN2 and flame sealed under an active vacuum. The above steps were repeated in order to generate complexes with 18O2. A similar procedure was used to introduce the mixed isotope 16O-18O gas to form the partially labelled sample tubes for rRaman spectroscopy. {NOTES: The O2 containing Schlenk flask was prepared by vacuum/Ar purge for three cycles followed by a final application of vacuum, with the rubber septum cap sealed using electrical/parafilm tapes. Then, dry O2 was introduced from a tank of molecular oxygen. For the other sample, the mixed-isotope oxygen bulb was connected to a glass S16  

  adapter sealed with a rubber septum. The adapter and a gas tight three-way syringe were put under vacuum/Ar purge cycles (3) to remove O2. A metal bar which had been placed inside the adapter was used to break the bulb allowing gas transfer to the Schlenk flask, whereupon the mixed-isotope oxygen gas could be loaded into the gas-tight syringe for transfer to the tube containing the dicopper(I) starting complex.} Resonance Raman spectra were collected with a triple monochromator (Spex 1877 CP with 1200, 1800, and 2400 groves/mm holographic spectropgraph gratings) and a CCD (Andor Newton). Laser excitation (20 mW at the sample) was provided by an argon ion laser (Innova Sabre 25/7) and a krypton ion laser (Coherent I90C-K). Samples in NMR tubes were placed in a liquid nitrogen finger dewar (Wilmad) in a ~135° backscattering configuration and spectra were collected for 5 minutes. The average spectra were baseline corrected with Peakfit Version 4 and individual transitions were fit with Gaussian bands.

15. Low temperature (-80 ºC) 1H-NMR spectroscopy experiment for [CuII2(UNO-)](O22)(SbF6). The low temperature 1H-NMR spectroscopy on [CuII2(UNO-)](O22-)(SbF6) was collected on a Bruker 300 MHz device with CD2Cl2 as solvent at -80 ºC. The chemical shifts compared to [CuI2(UNO-)](SbF6)(CH3CN) suggest that two unpaired electrons of [CuII2(UNO-)](O22-)(SbF6) are ferromagnetically coupled resulting in a S = 1 ground state compound. 5

S17  

 

Figure. S6 The low temperature 1H-NMR experiment of [CuII2(UNO-)](O22-)(SbF6)

16. Density Functional Theory Calculations. DFT calculations of (2) and (3) were performed with the B3LYP functional with TZVP on copper, oxygen, and nitrogen atoms and SV on carbon and hydrogen with an ultrafine integration grid in dichloromethane as modeled by a Polarizable Continuum Model as implemented in Gaussian 09. Analytical frequency calculations were performed on all stationary points to verify that a local minimum (or transition state) had been found and for comparison to rR data. For all of the computed isomers of (2) the S =1/2 wave function was predicted to be lower in energy than the S = 3/2, in agreement with EPR spectroscopy (Figure 2(c)). For (3), the S = 1 state was lower in energy than the S = 0, in agreement with the temperature dependent NMR data (vide infra). The Gibbs free energy of the various isomers was computed at -80 °C and contributions of spin contamination to the energy of the broken symmetry wave function (BSE) of (2) was removed by computing the S = 3/2 energy (4E) at the same molecular geometry to obtain the spin purified S = 1/2 energy (2E).

S18  

 

2

E=

(

3 ( BS−2 E ) − S 2

BS 2

3.75 − S

)

− 0.75 4 E

(1)

BS

While the structures of (2) and (3) supported by 8 potential isomers of the UN-O- ligand were computed, only isomers that are within 5 kcal/mol are reported. The reorganization energy of the various UN-O- isomers of the µ-1,2 superoxo and µ-1,2 peroxo structures can be computed as determined previously. The energy of reorganization energy of the oxidized state (λox) was determined from the energy difference of the oxidized state at the oxidized and reduced geometries. The reorganization energy of the reduced state (λred) was determined in a similar fashion to compute the overall reorganization energy (𝜆).   (2) λ = 1/ 2(λox + λred )

S19  

 

Figure S7. Resonance Raman spectra of (2) with 407 nm excitation; 16O2 (blue), 18O2 (red), mixed isotope (a 1:2:1 mixture of 16O2:16,18O2:18O2 green), and ¼(16O2 + 18O2) (orange) and Gaussian fits (individual transitions are grey for 16O2 and 18O2 and black for mixed isotope while the Gaussian sum for each spectrum is shown as a dashed curve). Attempts to fit the mixed isotope spectrum (green) with an intermediate Cu–O stretch at ~ 467 cm-1 yield a spectral shape (dashed green curve) that is in poor agreement with the experimental data.

S20  

  Figure S8: Overlays (A) and the individual structures (B) of the seven low energy ligand confirmations of the µ-1,2-peroxo isomers of [(UN-O)Cu2O2]1+. µ-1,2-PC1 in grey, µ-1,2-PC3 in red, µ-1,2-PC4 in green, µ-1,2-PC5 in yellow, µ-1,2-PC6 in magenta, µ-1,2-PC7 in teal, and µ-1,2PC8 in orange.

S21  

  Table S3: Computational details for the lowest energy µ-1,1-superoxo isomers of [CuII2(UNO-)](O2-)(SbF6)2

Functional Basis Set Charge Multiplicity Point Group Solvation Integral Grid SCF Energy (a.u.) S2 ΔG (kcal, -80° C) νO-O (cm-1) CuN•••CuMe (Å) O–O (Å) CuN–O (Å) CuMe–O (Å) CuN–OPhO- (Å) CuMe–OPhO- (Å) CuN–N (Å) CuMe–N (Å) CuN CuM O2

µ-1,1-SC1 µ-1,1-SC4 UB3LYP UB3LYP TZVP (Cu, O, N) TZVP (Cu, O, N) SV (C, H) SV (C, H) 2 2 2 2 C1 C1 PCM in dichloromethane PCM in dichloromethane Ultrafine Ultrafine -5189.84381744 -5189.84585763 1.6426 1.6307 4.8 2.4 1206 1211 Selected Metrical Parameters 3.286 3.272 1.292 1.292 2.116 2.075 2.072 2.145 1.964 1.990 2.095 1.996 2.013, 2.109, 2.203 2.028, 2.123, 2.188 2.110, 2.121, 2.131 2.026, 2.111, 2.249 Selected Spin Densities -0.57 0.53 0.51 -0.56 0.44, 0.69 0.42, 0.67

S22  

µ-1,1-SC5 UB3LYP TZVP (Cu, O, N) SV (C, H) 2 2 C1 PCM in dichloromethane Ultrafine -5189.84391736 1.6476 4.6 1210 3.283 1.295 2.101 2.149 1.991 1.975 2.053, 2.086, 2.217 2.013, 2.113, 2.242 0.53 -0.57 0.42, 0.66

  Table S4: Computational details for the lowest energy µ-1,2-superoxo isomers of [CuII2(UNO-)](O2-)(SbF6)2

Functional Basis Set Charge Multiplicity Point Group Solvation Integral Grid SCF Energy (a.u.) S2 ΔG (kcal, -80° C) νO-O (cm-1) CuN•••CuMe (Å) O–O (Å) CuN–O (Å) CuMe–O (Å) CuN–OPhO- (Å) CuMe–OPhO- (Å) CuN–N (Å) CuMe–N (Å) ∠CuN–O–O–CuM (°) CuN CuM O2

µ-1,2-SC1 µ-1,2-SC3 UB3LYP UB3LYP TZVP (Cu, O, N) TZVP (Cu, O, N) SV (C, H) SV (C, H) 2 2 2 2 C1 C1 PCM in dichloromethane PCM in dichloromethane Ultrafine Ultrafine -5189.84854879 -5189.84658507 1.6667 1.6734 1.7 3.0 1238 1235 Selected Metrical Parameters 3.486 3.460 1.292 1.295 2.019 2.026 2.040 2.035 2.003 2.002 2.068 2.044 2.078, 2.102, 2.216 2.074, 2.101, 2.222 2.080, 2.132, 2.175 2.055, 2.083, 2.242 -14.4 -8.7 Selected Spin Densities 0.55 0.53 -0.57 -0.56 0.43, 0.61 0.42, 0.66

S23  

µ-1,2-SC4 UB3LYP TZVP (Cu, O, N) SV (C, H) 2 2 C1 PCM in dichloromethane Ultrafine -5189.85132448 1.6679 0.0 1231 3.473 1.293 2.013 2.080 2.020 2.013 2.091, 2.100, 2.192 2.066, 2.101, 2.247 8.4 0.54 -0.57 0.46, 0.62

  Table S5: Computational details for the lowest energy µ-1,2-superoxo isomers of [CuII2(UNO)](O2-)(SbF6)2

Functional Basis Set Charge Multiplicity Point Group Solvation Integral Grid SCF Energy (a.u.) S2 ΔG (kcal, -80° C) νO-O (cm-1) CuN•••CuMe (Å) O–O (Å) CuN–O (Å) CuMe–O (Å) CuN–OPhO- (Å) CuMe–OPhO- (Å) CuN–N (Å) CuMe–N (Å) ∠CuN–O–O–CuM (°) CuN CuM O2

µ-1,2-SC5 µ-1,2-SC6 UB3LYP UB3LYP TZVP (Cu, O, N) TZVP (Cu, O, N) SV (C, H) SV (C, H) 2 2 2 2 C1 C1 PCM in dichloromethane PCM in dichloromethane Ultrafine Ultrafine -5189.84560258 -5189.84577736 1.6855 1.6818 4.0 4.3 1232 1231 Selected Metrical Parameters 3.485 3.499 1.296 1.295 2.024 2.023 2.034 2.047 1.989 2.002 2.050 2.031 2.080, 2.101, 2.217 2.094, 2.104, 2.212 2.009, 2.180 2.207 2.048, 2.100, 2.253 0.7 4.3 Selected Spin Densities 0.55 0.55 -0.58 -0.58 0.44, 0.62 0.45, 0.61

S24  

  Table S6: Computational details for the lowest energy µ-1,2-superoxo isomers of [CuII2(UNO)](O2-)(SbF6)2

Functional Basis Set Charge Multiplicity Point Group Solvation Integral Grid SCF Energy (a.u.) S2 ΔG (kcal, -80° C) νO-O (cm-1) CuN•••CuMe (Å) O–O (Å) CuN–O (Å) CuMe–O (Å) CuN–OPhO- (Å) CuMe–OPhO- (Å) CuN–N (Å) CuMe–N (Å) ∠CuN–O–O–CuM (°) CuN CuM O2

µ-1,2-SC7 µ-1,2-SC8 UB3LYP UB3LYP TZVP (Cu, O, N) TZVP (Cu, O, N) SV (C, H) SV (C, H) 2 2 2 2 C1 C1 PCM in dichloromethane PCM in dichloromethane Ultrafine Ultrafine -5189.84610235 -5189.84712413 1.6787 1.6783 3.3 2.9 1232 1238 Selected Metrical Parameters 3.452 3.500 1.294 1.293 2.023 2.029 2.045 2.036 2.008 1.987 2.033 2.061 2.105, 2.110, 2.172 2.041, 2.092, 2.262 2.051, 2.088, 2.206 2.096, 2.122, 2.171 7.6 7.6 Selected Spin Densities 0.55 -0.58 -0.58 0.54 0.45, 0.62 0.45, 0.63

S25  

  Table S7. Select vibrations for µ-1,1-SC4 and their predicted isotope shift (cm-1). 16

νO–O Sym νCu–O Antisym νCu–O

O–16O 1211 466 280

16

O–18O 1177, 1175 464, 431 280, 249

18

O–18O 1144 430 247

Table S8. Select vibrations for µ-1,2-SC4 and their predicted isotope shift (cm-1). 16

νO–O Sym νCu–O Antisym νCu–O

O–16O 1230 469 321

16

O–18O 1197, 1197 455, 452 317, 314

18

O–18O 1161 443 312

Table S9: Computational details for the interconversion of µ-1,1-SC4 and µ-1,2-SC4.

TS-SC4 Functional UB3LYP TZVP (Cu, O, N) Basis Set SV (C, H) Charge 2 Multiplicity 2 Point Group C1 Solvation PCM in dichloromethane Integral Grid Ultrafine SCF Energy (a.u.) -5189.83473963 S2 1.7378 ΔG (kcal, -80° C) 9.8 Imaginary Frequencies 1 Selected Metrical Parameters CuN•••CuMe (Å) 3.514 O–O (Å) 1.288 CuN–O (Å) 2.679, 2.827 CuMe–O (Å) 2.034, 2.845 CuN–OPhO- (Å) 1.923 CuMe–OPhO- (Å) 2.243 CuN–N (Å) 1.984, 2.103, 2.109 CuMe–N (Å) 2.100, 2.145, 2.153 92.7 ∠CuN–O–O–CuM (°) Selected Spin Densities CuN -0.59 CuM 0.44 O2 0.65, 0.73

S26  

 

Figure S9. Resonance Raman spectra of [(UN-O)Cu2O2]1+ 16O2 (blue), 18O2 (red), difference (black), and Gaussian fits (individual transitions are grey while the sum and difference are shown as a dashed curve). 530 nm excitation (A, B) and 568 nm excitation (C, D) for samples in CH2Cl2 (A, C) and CD2Cl2 (B, D).

Figure S10. Resonance Raman spectra of (3) with 530 nm excitation; 16O2 (blue), 18O2 (red), mixed isotope (a 1:2:1 mixture of 16O2:16,18O2:18O2 green), and ½(16O2 + 18O2) (orange) with 530 nm excitation. Fitting the mixed isotope data with equal contributions of the 16O2 and 18O2 spectra poorly reproduce the mixed isotope spectrum indicating the presence of intermediate Cu– O stretches.

S27  

  Table S10: Computational details for the lowest energy µ-1,2-peroxo isomers of [(UNO)Cu2O2]1+.

Functional Basis Set Charge Multiplicity Point Group Solvation Integral Grid SCF Energy (a.u.) S2 ΔG (kcal, -80° C) νO-O (cm-1) CuN•••CuMe (Å) O–O (Å) CuN–O (Å) CuMe–O (Å) CuN–OPhO- (Å) CuMe–OPhO- (Å) CuN–N (Å) CuMe–N (Å) ∠CuN–O–O–CuM (°) CuN CuM O2

µ-1,2-PC1 µ-1,2-PC3 UB3LYP UB3LYP TZVP (Cu, O, N) TZVP (Cu, O, N) SV (C, H) SV (C, H) 1 1 3 3 C1 C1 PCM in dichloromethane PCM in dichloromethane Ultrafine Ultrafine -5190.02630026 -5190.02415405 2.0096 2.0094 0.7 1.8 938 934 Selected Metrical Parameters 3.441 3.443 1.360 1.362 1.973 1.968 1.988 1.982 2.076 2.079 2.110 2.117 2.141, 2.147, 2.213 2.142, 2.148, 2.209 2.153, 2.171, 2.217 2.160, 2.195, 2.200 71.9 73.0 Selected Spin Densities 0.44 0.44 0.41 0.42 0.46, 0.46 0.45, 0.46

S28  

µ-1,2-PC4 UB3LYP TZVP (Cu, O, N) SV (C, H) 1 3 C1 PCM in dichloromethane Ultrafine -5190.02711184 2.0098 0.0 941 3.449 1.356 1.972 1.998 2.079 2.111 2.144, 2.149, 2.205 2.137, 2.219, 2.231 72.6 0.43 0.40 0.47, 0.47

  Table S11: Computational details for the lowest energy µ-1,2-peroxo isomers of [(UNO)Cu2O2]1+.

Functional Basis Set Charge Multiplicity Point Group Solvation Integral Grid SCF Energy (a.u.) S2 ΔG (kcal, -80° C) νO-O (cm-1) CuN•••CuMe (Å) O–O (Å) CuN–O (Å) CuMe–O (Å) CuN–OPhO- (Å) CuMe–OPhO- (Å) CuN–N (Å) CuMe–N (Å) ∠CuN–O–O–CuM (°) CuN CuM O2

µ-1,2-PC5 µ-1,2-PC6 UB3LYP UB3LYP TZVP (Cu, O, N) TZVP (Cu, O, N) SV (C, H) SV (C, H) 1 1 3 3 C1 C1 PCM in dichloromethane PCM in dichloromethane Ultrafine Ultrafine -5190.02304723 -5190.02338503 2.0086 2.0090 2.9 2.6 918 923 Selected Metrical Parameters 3.451 3.461 1.376 1.371 1.957 1.964 1.950 1.972 2.073 2.061 2.110 2.110 2.154, 2.159, 2.207 2.156, 2.178, 2.200 2.107, 2.221, 2.246 2.131, 2.169, 2.265 -68.6 -69.3 Selected Spin Densities 0.45 0.45 0.47 0.44 0.39, 0.42 0.42, 0.43

S29  

  Table S12: Computational details for the lowest energy µ-1,2-peroxo isomers of [(UNO)Cu2O2]1+.

Functional Basis Set Charge Multiplicity Point Group Solvation Integral Grid SCF Energy (a.u.) S2 ΔG (kcal, -80° C) νO-O (cm-1) CuN•••CuMe (Å) O–O (Å) CuN–O (Å) CuMe–O (Å) CuN–OPhO- (Å) CuMe–OPhO- (Å) CuN–N (Å) CuMe–N (Å) ∠CuN–O–O–CuM (°) CuN CuM O2

µ-1,2-PC7 µ-1,2-PC8 UB3LYP UB3LYP TZVP (Cu, O, N) TZVP (Cu, O, N) SV (C, H) SV (C, H) 1 1 3 3 C1 C1 PCM in dichloromethane PCM in dichloromethane Ultrafine Ultrafine -5190.02304661 -5190.02545227 2.0091 2.0094 2.4 1.3 913 928 Selected Metrical Parameters 3.422 3.444 1.374 1.366 1.960 1.965 1.959 1.981 2.089 2.085 2.085 2.111 2.152, 2.154, 2.209 2.152, 2.165, 2.207 2.130, 2.167, 2.229 2.149, 2.172, 2.209 -66.7 -70.3 Selected Spin Densities 0.44 0.44 0.46 0.43 0.41, 0.42 0.44, 0.44

S30  

  Table S13: Computational details for the lowest energy mixed valent µ-1,1-superoxo and η1superoxo isomers of [(UN-O)Cu2O2]1+.

Functional Basis Set Charge Multiplicity Point Group Solvation Integral Grid SCF Energy (a.u.) S2 ΔG (kcal, -80° C) νO-O (cm-1) CuN•••CuMe (Å) O–O (Å) CuN–O (Å) CuMe–O (Å) CuN–OPhO- (Å) CuMe–OPhO- (Å) CuN–N (Å) CuMe–N (Å) CuN CuM O2

µ-1,1-MV-SC1 η1-MV-SC4 UB3LYP UB3LYP TZVP (Cu, O, N) TZVP (Cu, O, N) SV (C, H) SV (C, H) 1 1 3 3 C1 C1 PCM in dichloromethane PCM in dichloromethane Ultrafine Ultrafine -5190.01713136 -5190.01908120 2.0135 2.0111 5.9 3.7 1131 1189 Selected Metrical Parameters 3.319 3.538 1.298 1.288 2.151 2.045 2.187 2.728 2.057 2.031 2.110 2.164 2.072, 2.181, 2.225 2.097, 2.182, 2.206 2.128, 2.143, 2.216 2.042, 2.087, 2.189 Selected Spin Densities 0.29 0.42 0.25 0.03 0.65, 0.63 0.67, 0.71

η1-MV-SC5 UB3LYP TZVP (Cu, O, N) SV (C, H) 1 3 C1 PCM in dichloromethane Ultrafine -5190.01789552 2.0111 4.5 1206 3.693 1.281 2.054 3.574 2.024 2.152 2.098, 2.213, 2.233 2.026, 2.063, 2.200 0.42 0.00 0.70, 0.72

Table S14. Select vibrations for µ-1,2-PC4 and their predicted isotope shift (cm-1). 16

νO–O Sym νCu–O Antisym νCu–O

O–16O 941 415 383

16

O–18O 919, 918 412, 402 374, 365

S31  

18

O–18O 892 395 363

  Table S15: DFT computed electronic inner sphere reorganization energies for the µ-1,2-peroxo and µ-1,2-superoxo isomers. Confirmation C1 C3 C4 C5 C6 C7 C8

Reorganization Energy (eV) 0.37 0.42 0.38 0.44 0.43 0.39 0.44

17. DFT calculations of ferrocenium/ferrocene bond (inner sphere) and solvent (outer sphere) reorganization energy The radii of ferrocene and the UN-O isomers (a1 and a2) for use in the Marcus-Sutin outer sphere electron transfer equation were approximated by averaging the distances between most distant protons plus van der Walls radii along each cartesian axis and dividing in half. The distance between redox centers (r) was taken as the sum of the individual radii (a1 + a2). Ferrocene structure is calculated by DFT (b3lyp/tzvp,sv int=ultrafine as per manuscript) and λinner is calculated using equation (2) and Table S16 Table S16. DFT calculated energy for the ferrocene moiety Neutral optimization -1650.448056 Cation at neutral geom -1650.210707 Cation optimization -1650.214804 Neutral at cation geom -1650.444644 λox 0.00409735 λred 0.00341206 Average 0.102170776

Hartree Hartree Hartree Hartree Hartree Hartree eV

Marcus and Sutin6 described the outer sphere reorganization as a function of molecular radii, distance and amount of charge transferred, and polarity of the solvent as follows: 𝜆!"#$% = ∆𝑒

!

! !!!

+

! !!!



!

!

!

!!"#$%&'



! !!"#"

%$(3)

where λouter is the outer sphere reorganization energy, ∆e is the change in charge, a1 and a2 are the molecular radii, r is the distance, Doptical is the dynamic dielectric constant (frequently approximated as the square of the refractive index), Dstatic is the normal dielectric constant of the solvent.

S32  

  a1 = a2 (ferrocene radius) = 0.406 nm (this was found by taking the optimized structure farthest two protons, adding the VDW radii of the protons (1.2Å) and dividing in half) Doptical (acetonitrile) = 1.806 Dstatic (acetonitrile) = 37.5 Δe = √(1.4399764 MeV•fm) λouter is 0.934 eV in acetonitrile By this method, λ = λinner + λouter = 1.036 eV. This compares well to 1.06 eV measured experimentally in acetonitrile.7 In DCM solvent, λouter for the following reaction can be calculated in similar fashion:

radii of peroxo 0.6775 nm radii of dimethylferrocene –use the radius of ferrocene as an approximation (0.406 nm) Doptical (DCM) = 2.03 Dstatic (DCM) = 9.08 peroxide particularly strongly donating much greater pi* donation which lowers reorganization energy scale that down by the distortion squared, distributing that over mode centers, since it goes as the distortion squared, it dramatically lowers the reorganization energy λouter to be 0.574 eV As comparison to Table S15 Inner sphere reorganization (λinner) energy of free superoxide/peroxide is also calculated as follows using equation 2 and data in Table S17. The calculated λinner is hence 0.76eV. Table S17. DFT calculated energy for free superoxide/peroxide moieties peroxo opt -150.0925648 peroxo at superoxo geom -150.0658226 superoxo opt -150.3926457 superoxo at peroxo opt -150.3633128 λox 0.02674217 hartrees λred 0.02933291 hartrees Average 0.762940688 eV

S33  

  18. Mullikan population analysis Mulliken populations were tabulated using QMForge. [Tenderholt, A. L. QMForge, Version 2.1; Stanford University: Stanford, CA, 2007] Table S18. Mullikan population analysis Peroxo C4 orbital 186α 186β

level CuA d – O2 π* CuB d – O2 π*

occ E(eV) 0 -4.279 0 -4.344 charge spin density

Cu 45.5 41.9 0.49, 0.53 -0.43, 0.39

O2 42.2 44.9 -0.30, -0.27 0.10, -0.19

rest 12.3 13.2

O2 34.4 11.1 78.1 -0.16, -0.15 0.46, 0.62

rest 19.4 29.1 7.6

Peroxo Mayer B.O. CuA-O2 0.766 (0.624 + 0.142) Peroxo Mayer B.O. CuB-O2 0.734 (0.148 + 0.586) Peroxo Mayer B.O. O-O 0.921 Selected Metrical Parameters CuN•••CuMe (Å) 3.449 O–O (Å) 1.356 CuN–O (Å) 1.972 CuMe–O (Å) 1.998 CuN–OPhO- (Å) 2.079 CuMe–OPhO- (Å) 2.111 CuN–N (Å) 2.144, 2.149, 2.205 CuMe–N (Å) 2.137, 2.219, 2.231 CuN–O–O–CuM (°) 72.6

Cu-O-O: 113.0°, 104.8° Superoxo C4 orbital 185β 186α 186β

level CuA d – O2 π* CuB d – O2 π* O 2 π*

occ E(eV) 0 -4.068 0 -4.251 0 -3.961 charge spin density

Cu 46.2 59.7 14.3 0.47, 0.56 0.54, -0.57

Superoxo Mayer B.O. CuA-O2 0.579 (0.500 + 0.079) Superoxo Mayer B.O. CuB-O2 0.455 (0.054 + 0.401) Superoxo Mayer B.O. O-O 1.24 Selected Metrical Parameters CuN•••CuMe (Å) 3.473 O–O (Å) 1.293 CuN–O (Å) 2.013 CuMe–O (Å) 2.080 CuN–OPhO- (Å) 2.020 CuMe–OPhO- (Å) 2.013 CuN–N (Å) 2.091, 2.100, 2.192 CuMe–N (Å) 2.066, 2.101, 2.247 CuN–O–O–CuM (°) 8.4

Cu-O-O: 123.9°, 120.1° à 11% reduction in overlap from sin θ S34  

 

Cartesian Coordinates µ-1,1-MV-SC1 Cu Cu O N N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H O O

1.48007100 -1.82418800 -0.07604600 2.57084200 -2.96958700 -2.22735000 -0.84267100 -0.54093100 0.76566800 1.78724900 1.51415800 0.19154600 2.25311800 2.35514600 2.91151100 3.38517800 3.28346600 2.71235300 2.61369500 3.38164100 2.44076400 1.81600000 2.29068400 3.46971000 4.12005900 3.58723900 4.29129500 3.45113000 -2.04615400 -2.17610900 -2.46777700 -2.63693600 -2.50199300 -2.20231500 -2.05235400 -3.14191300 -3.27650700 -2.90793100 -3.82352800 -5.19285300 -5.58134100 -4.60371300 -4.99734200 -4.31848500 -2.16135800 -2.84792000 1.55222500 3.01310600 4.29197600 3.71881000 4.66418100 5.18660000 2.79421100 4.13346000 -1.05471800 -2.10465000 -4.11968300 -3.18475600 -4.76659700 -6.09109100 -4.97576400 -4.18866900 -2.02296000 -2.55737500 -2.86727100 -2.62322200 -1.83566100 -3.46546000 -5.94261200 -6.63787000 5.04091700 3.87522800 1.74586000 0.90071200 2.80587700 0.98670200 -1.34191100 1.95566800 2.96645900 3.82621800 3.64337500 -0.26921100 -0.35173500

η1-MV-SC4 0.24834900 -0.01537900 0.11939200 -0.69905500 -0.84414100 -0.45489000 -1.03284600 -1.86578400 -2.33541700 -1.96272500 -1.14157900 -0.66021000 -0.92407800 -0.42710600 -1.14797000 -2.44513800 -2.96173600 -2.18203400 -2.70382500 -1.84710300 2.20255300 3.28144800 4.59092100 4.79941800 3.68789900 2.39742800 1.18409900 0.32080600 -1.72706600 -1.58936900 -2.66060500 -3.93555000 -4.08237600 -2.96082100 -3.08024900 -2.33462700 1.46940100 2.62544200 3.58020100 3.33082300 2.14312500 1.22902600 -0.03945900 -0.18849100 0.64755800 -0.73773800 -2.77088200 -3.73100700 -1.43836900 -2.48665400 0.55760300 1.52931200 0.96999600 -0.19874100 -2.72112000 -4.14742700 -2.54269700 -2.75293300 -0.92093900 -0.03834400 -0.76411200 0.81090100 -0.58059100 -2.49396000 -4.79921600 -5.06026800 2.77906300 4.49327900 4.04790400 1.91864000 3.81066000 5.80540900 5.42124400 3.07393200 -2.31755600 -2.97703500 -2.14186600 0.57716000 -0.69859900 -3.04297300 -3.96719300 0.90472000 1.06428300

-0.30544300 -0.14006800 1.03291300 1.38703300 1.56637500 2.82468800 2.99855000 4.08816600 4.30956700 3.42194700 2.31451100 2.08636000 -1.82829000 -3.08480500 -4.14756100 -3.90162100 -2.60237200 -1.57949600 -0.16262600 0.86987800 -0.18740000 -0.71648000 -0.57822900 0.15264600 0.70536100 0.51716500 1.08795500 2.05974200 -1.38405600 -2.72473500 -3.57777400 -3.01675100 -1.62892700 -0.83209300 0.66827900 1.47581500 -0.66967800 -1.27266600 -1.72984200 -1.55708400 -0.92259600 -0.48624600 0.24081100 1.62146000 2.79915400 3.70018500 0.14570300 -0.13759500 0.40131700 1.70787100 0.25586000 1.63181600 2.66149400 2.76423800 0.97357900 0.94410200 1.00916000 2.50174200 -0.38743100 0.38135200 2.30612800 2.06906200 -3.11573300 -4.65335500 -3.64632900 -1.15685400 -1.39140100 -2.21003900 -1.90177300 -0.75834100 1.28047000 0.28970000 -1.03253200 -1.27374100 3.60260200 5.16668000 4.78248300 -3.23409700 -5.14125700 -4.70360700 -2.37239500 -1.37145800 -2.65740400

Cu Cu O N N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H O O

S35  

1.53854000 -1.97565100 -0.01337600 2.56235800 -2.99147800 -2.01863600 -0.74699600 -0.46781700 0.76478400 1.75153500 1.49840600 0.23243400 2.47238400 2.77917800 3.32675400 3.56338800 3.25666600 2.71426900 2.43989200 3.24136900 2.60874100 2.02829100 2.62340900 3.88064100 4.48316100 3.82463900 4.44310700 3.57494500 -2.19316500 -1.32281400 -1.33667000 -2.29535100 -3.19927700 -3.13358600 -4.12386900 -3.50362100 -3.03008600 -3.07843700 -3.97100300 -4.86391800 -4.81579800 -3.88775800 -3.80107400 -4.12713000 -1.75102700 -2.53640400 1.35983700 2.70956600 4.22958200 3.42576100 4.67635100 5.40953800 3.01613300 4.23007500 -4.82331700 -4.73399700 -4.25940600 -2.65938000 -4.50811600 -2.79235200 -4.97084800 -4.46871200 -0.59567500 -0.61342700 -2.34162200 -3.96271800 -2.36115200 -3.95969300 -5.57883400 -5.48992200 5.45893700 4.38139800 2.10948800 1.05240700 2.72945800 0.96330400 -1.22829700 2.55731300 3.55580300 3.98519300 3.43892300 0.06069300 0.30169800

0.47764500 0.31601000 0.23246700 -0.84688600 -0.28955800 -0.18817800 -0.99976800 -2.00102900 -2.67495400 -2.31702500 -1.33202400 -0.67721100 -0.30192000 0.48783000 -0.01160000 -1.39074300 -2.20875500 -1.63883700 -2.46692000 -1.97104600 2.32612500 3.53556800 4.73872400 4.68898000 3.43856600 2.27091200 0.90524200 -0.06328800 -1.44063700 -1.74821700 -2.96742600 -3.92669300 -3.61574600 -2.36384000 -2.00272000 -1.68643900 1.98413900 2.37494300 3.34073000 3.93549900 3.54062400 2.56636800 2.14253700 0.65343800 0.87896200 -0.47467200 -2.46009700 -3.51588300 -1.61374300 -2.81128100 0.44998800 1.03441100 0.50255200 -0.77814900 -2.84650900 -1.14377600 -1.87886300 -2.37096600 2.75495900 2.38124300 0.35039700 0.54352100 -0.97224100 -3.15378400 -4.89378700 -4.33544100 1.89602000 3.61739000 4.69308000 3.98572900 3.35939200 5.60391200 5.68641800 3.53105900 -2.80454900 -3.44778500 -2.24176700 1.54969800 0.66849100 -1.82151200 -3.28517700 1.31671600 2.15845500

-0.28456500 0.09315600 1.00250000 1.11480800 1.93493400 3.07465500 2.95041000 3.89660300 3.91809000 2.98810300 2.01920200 1.95652900 -1.99289900 -3.04866700 -4.23594600 -4.33670000 -3.23973200 -2.07390900 -0.83886500 0.38437800 0.26521800 0.08502000 0.48326200 1.10326700 1.29952200 0.86966800 1.08121500 1.91936800 -1.01238400 -2.00605400 -2.69280500 -2.33258700 -1.30769600 -0.66523100 0.42298400 1.80601900 -0.43237100 -1.73159500 -2.20955500 -1.30522700 0.03892600 0.45318900 1.90364200 2.17814600 3.16128900 4.01506300 -0.59522900 -1.04366200 0.05140900 1.07738400 0.10025900 1.59630000 2.68191800 2.45571300 0.54838000 0.08411700 2.59859000 1.99088100 2.48824000 2.28857600 1.53598500 3.23070900 -2.25426000 -3.48975600 -2.84029700 -1.00268100 -2.39990100 -3.26603000 -1.63708100 0.77468200 1.78456800 1.43090000 0.30939800 -0.40295500 3.03435000 4.66525300 4.64745800 -2.93167600 -5.05878200 -5.24856100 -3.27660600 -1.42221500 -2.36634500

  η1-MV-SC5 Cu Cu O N N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H O O

µ-1,2-PC1 1.18190300 -1.22015100 -0.15908000 2.45268300 -2.56474500 -2.23960600 -0.78262800 -0.37774600 0.95326500 1.88809900 1.50785900 0.18149700 1.94369900 2.06666800 2.48692600 2.79018300 2.67690100 2.25508400 2.19821700 3.11933300 2.30743300 1.70046200 2.30333100 3.60072200 4.23401500 3.56638300 4.24527700 3.48070700 -2.52597900 -2.22322600 -3.15405500 -4.47167100 -4.79342500 -3.80412400 -4.12542100 -3.96515600 -0.15962200 1.11849400 1.89545100 1.32776400 0.00748400 -0.72018600 -2.15289800 -2.39549700 -2.86341500 -2.54189800 1.16110100 2.50645800 4.01852500 3.46722900 4.44496600 5.23365100 2.95254300 4.20810000 -3.49276500 -5.16971100 -4.30519200 -4.63115300 -2.81398600 -2.45629400 -3.28964900 -1.53563800 -1.18904900 -2.84851200 -5.23177900 -5.80818200 1.52143200 2.91786200 1.89841100 -0.46951800 5.24436200 4.10957600 1.76507700 0.69516900 2.91824000 1.25336600 -1.12445600 1.79907800 2.56720300 3.11524500 2.91566300 -0.45516400 -0.32415700

0.34982200 2.35854900 0.54163200 -0.41714700 1.34685900 -0.11998700 -0.45611900 -1.14182300 -1.55858900 -1.31938900 -0.65183300 -0.16051500 -0.96237200 -0.58501300 -1.45789000 -2.78356600 -3.17299200 -2.24118100 -2.59655800 -1.69656700 2.25681300 3.31047500 4.56577200 4.74566300 3.66081000 2.42436800 1.23950100 0.60986700 3.19077500 4.32446400 5.03250600 4.55342300 3.38629000 2.71863600 1.44983600 1.54886600 3.53528900 3.91964400 4.64016600 4.98151100 4.59012100 3.87201300 3.45557700 1.92563300 -0.62905700 -0.51089800 -2.52541200 -3.64732500 -1.43914400 -2.25098900 0.46923800 1.56509000 1.39349600 0.13950400 0.62942000 1.16865700 2.54435800 0.80344400 3.93231800 3.85448700 1.69438800 1.42500200 4.66671400 5.93555200 5.07561000 2.98223100 3.63735100 4.92466600 5.54211200 4.84038100 3.76223000 5.70898200 5.37616900 3.12991700 -1.66338800 -2.08110900 -1.36729900 0.44860200 -1.10199300 -3.49937900 -4.19343700 0.78784500 1.25179900

-0.66248600 1.29498500 0.84180100 0.97947000 2.71292400 2.71816100 2.94893000 4.10601400 4.28538100 3.26680200 2.09003800 1.93369700 -2.11141700 -3.40570400 -4.41556900 -4.07181900 -2.72984900 -1.76447500 -0.29602600 0.55808500 -0.95005700 -1.54693300 -1.69282800 -1.19089700 -0.56934700 -0.46425800 0.18977000 1.37784100 -0.01208700 -0.69428000 -1.46106000 -1.52401100 -0.81803700 -0.07104100 0.68967400 2.22905500 2.61639400 2.37273700 3.28588100 4.52297400 4.78251800 3.81357600 4.07560500 4.07819200 3.48338000 1.73192700 0.08503800 -0.17084600 -0.02449900 1.44814800 -0.57869900 0.55472000 1.94480900 2.06989400 0.30340500 0.47304000 2.56171800 2.71537700 3.32686500 5.05826100 4.69651100 4.55309600 -0.61621200 -1.99382000 -2.11094200 -0.84414800 1.39856100 3.02826600 5.26798700 5.73310800 -0.16629800 -1.28104000 -2.18877400 -1.92972300 3.39696000 5.19751900 4.87533500 -3.62973300 -5.44464300 -4.83137000 -2.42204300 -1.82302900 -3.01037400

Cu Cu O N N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H O O

S36  

1.55325800 -1.83349600 -0.10117100 2.57440100 -2.99926200 -2.21731300 -0.85534600 -0.55690500 0.75063600 1.77591300 1.50451300 0.17642900 2.38537400 2.50689100 2.94469000 3.26568800 3.14073100 2.69673300 2.57160900 3.35401700 2.54606200 1.94146400 2.48108600 3.70168500 4.32701500 3.72853500 4.38498100 3.49768200 -2.30384200 -2.43993600 -2.69036500 -2.80026900 -2.65708000 -2.40639200 -2.25635800 -3.29276400 -3.21620300 -2.76271800 -3.61185500 -4.99442000 -5.46583000 -4.55300900 -5.02053000 -4.30232000 -2.09882600 -2.83966600 1.50539300 2.94115300 4.27712300 3.66580700 4.73402800 5.29187400 2.86677300 4.14758600 -1.23507400 -2.37795600 -4.27438700 -3.39510800 -4.88498800 -6.10444000 -4.96904200 -4.09029700 -2.33352900 -2.79279800 -2.99447200 -2.73582600 -1.68050100 -3.19375200 -5.69186200 -6.53439800 5.27625400 4.15698800 1.95273700 0.99211900 2.79666700 0.97199100 -1.35570000 2.22673300 3.02596100 3.60900100 3.38465100 -0.64281000 0.24493300

0.47161900 -0.13891600 0.06337300 -0.65844300 -0.79645400 -0.41043500 -1.03642600 -1.85272500 -2.32027400 -1.94507000 -1.13324100 -0.68470800 -0.70156300 -0.14072800 -0.85100300 -2.20878900 -2.79264500 -2.01423100 -2.59776700 -1.80716700 2.34433200 3.47880800 4.75392600 4.86317300 3.69172300 2.44123500 1.15991500 0.26259700 -1.95541000 -1.90489100 -3.03783300 -4.28205500 -4.33754400 -3.15527600 -3.16043800 -2.27421200 1.42441200 2.50927500 3.50287000 3.36658100 2.24820600 1.29095200 0.09228600 -0.04588300 0.68610400 -0.63886300 -2.65001200 -3.63635600 -1.40214800 -2.48734300 0.58857800 1.42027700 0.89101200 -0.34472600 -2.84582100 -4.19406600 -2.42884200 -2.61275900 -0.83139300 0.18769800 -0.54763000 0.95997600 -0.91700900 -2.94261500 -5.19189500 -5.28811000 2.56561900 4.35919100 4.11829100 2.11178900 3.73678700 5.84014400 5.63571800 3.33976700 -2.28716700 -2.95384400 -2.11198500 0.91176200 -0.34951100 -2.80136900 -3.84603300 0.32411000 1.30792300

-0.27050200 -0.27213000 0.91502700 1.33442300 1.49478000 2.73257400 2.90680200 4.00864900 4.23370100 3.35084200 2.23582500 1.98494000 -1.85665400 -3.08224300 -4.20580000 -4.05494300 -2.78672000 -1.70112800 -0.31067800 0.75825900 0.07323000 -0.35364700 -0.15033200 0.53271800 0.98086700 0.73507900 1.20040700 2.09399800 -1.36445500 -2.70961800 -3.49312900 -2.85317800 -1.45954700 -0.73748600 0.76705700 1.49340200 -0.80264800 -1.47547000 -1.97731500 -1.78123200 -1.08009100 -0.59904800 0.19769300 1.55727200 2.67329800 3.62166100 -0.01438100 -0.32665000 0.31202500 1.57344300 0.31943800 1.77134000 2.74335400 2.75555800 1.04524800 1.13343800 1.01491600 2.54397300 -0.39695900 0.37659700 2.28814900 1.95539500 -3.16191400 -4.57618300 -3.42752000 -0.92666900 -1.60856000 -2.51072800 -2.16051600 -0.89801300 1.51981000 0.71544700 -0.51886100 -0.87507000 3.54487000 5.09665100 4.71211300 -3.15168600 -5.17244700 -4.90716900 -2.63015100 -1.79542300 -1.48728300

  µ-1,2-PC3 Cu Cu O N N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H O O

µ-1,2-PC4 1.71194700 -1.70491700 0.05047800 2.69177100 -2.86524900 -2.07486700 -0.74099600 -0.47451100 0.81230300 1.84853600 1.60753200 0.30019400 2.47827100 2.60842200 2.99835800 3.25878400 3.12475100 2.73199200 2.60156900 3.42345500 2.78450700 2.22526700 2.82019000 4.04934800 4.62732100 3.97396200 4.57722500 3.65399500 -2.39112100 -2.63521800 -2.99380000 -3.09881800 -2.84413900 -2.48872500 -2.22135200 -3.18168100 -2.94077600 -2.76323400 -3.54098700 -4.55893000 -4.74565800 -3.91901000 -4.09035500 -4.17307700 -1.89610500 -2.70888400 1.53746300 2.93434300 4.35373700 3.72256300 4.90455400 5.49314400 3.05075500 4.27845900 -1.17545100 -2.33673100 -4.20284700 -3.19509300 -5.02587600 -3.28470600 -4.77542900 -4.70909000 -2.52932900 -3.18120500 -3.37452900 -2.91639600 -1.95600200 -3.34869700 -5.19357900 -5.52680300 5.58138100 4.54723000 2.32705100 1.26735900 2.85380300 1.00955400 -1.28048800 2.37503600 3.08971700 3.56311900 3.32283400 -0.49748500 0.43749800

0.55599400 0.13626800 0.18230300 -0.69126800 -0.59245900 -0.31182900 -1.00803300 -1.90497100 -2.44249900 -2.05929000 -1.16957200 -0.64498600 -0.57693000 0.03539900 -0.63970700 -2.01622800 -2.65328900 -1.90802800 -2.55069000 -1.83784700 2.36718400 3.54444100 4.78487100 4.81089300 3.59474100 2.38334800 1.05542200 0.15258600 -1.49878400 -1.31336900 -2.35597900 -3.65259900 -3.84806500 -2.75015000 -2.90017100 -2.06753600 1.91450700 2.54501800 3.63057500 4.09123300 3.44624400 2.36261400 1.69058300 0.15133500 0.77540900 -0.57188200 -2.58051700 -3.59951100 -1.44355200 -2.56521300 0.51344000 1.25118700 0.77393400 -0.51396300 -2.62471900 -3.96108500 -2.17859400 -2.48587400 2.06213500 2.02975300 -0.16589700 -0.18223600 -0.29090600 -2.15221100 -4.49575800 -4.84314000 2.15023200 4.09842900 4.93351300 3.77560400 3.57501000 5.75835000 5.70424500 3.46933900 -2.45782700 -3.13760500 -2.17307000 1.10134100 -0.09687600 -2.58264600 -3.72270500 0.57424100 1.50458300

-0.11247300 -0.10232800 1.07940400 1.42442100 1.61929700 2.87800100 3.00302100 4.04872300 4.23426900 3.36799000 2.30669100 2.09665600 -1.76070300 -2.96054500 -4.12275300 -4.04080300 -2.79944600 -1.67172600 -0.30810600 0.78534000 0.31556600 -0.05353100 0.20339100 0.87928800 1.26816900 0.97153900 1.37428000 2.22485800 -1.33650100 -2.65369600 -3.51648500 -2.98998600 -1.62508600 -0.81926800 0.66097400 1.53870800 -0.46275800 -1.65074900 -2.06867900 -1.22078800 0.00839100 0.36640800 1.71089900 1.69303100 2.90133900 3.74994500 -0.00077900 -0.37676700 0.34478400 1.56361400 0.46674500 1.95657400 2.90653900 2.85313300 0.88651700 0.94112700 1.13743400 2.56369800 2.16227600 2.38842000 0.82477300 2.60688100 -3.02030700 -4.57284100 -3.62903300 -1.17978500 -2.26942200 -3.03659300 -1.50903400 0.69760100 1.80009600 1.10206300 -0.11928000 -0.57233700 3.53252700 5.05463900 4.74052000 -2.97637100 -5.06588900 -4.92503800 -2.69588000 -1.61208300 -1.27409500

Cu Cu O N N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H O O

S37  

1.69018800 -1.74776500 0.02193200 2.60308800 -2.94839800 -2.07574400 -0.81742700 -0.60513400 0.63225500 1.68050300 1.49269900 0.22551400 2.40572600 2.56865700 2.95740000 3.18324500 3.01523500 2.62407900 2.45257600 3.29056600 2.85862400 2.36514100 3.01754000 4.23539900 4.74549400 4.03740500 4.57032200 3.59408100 -2.15679900 -1.29492600 -1.43583300 -2.52040600 -3.41421700 -3.21026800 -4.16617100 -3.49728500 -3.08694400 -3.17311000 -4.00886800 -4.78748400 -4.70062300 -3.84143200 -3.73938500 -4.08871500 -1.79687100 -2.69551400 1.38512400 2.74171700 4.24464000 3.54554300 4.88807500 5.48468800 3.01182000 4.17791400 -4.90693100 -4.74011600 -4.23050200 -2.66270600 -4.43010700 -2.72294200 -4.91266800 -4.46250500 -0.47358600 -0.71035000 -2.66777500 -4.27013200 -2.53165000 -4.04037700 -5.45019000 -5.29266400 5.68887400 4.77655400 2.57643300 1.41242900 2.65391000 0.78646800 -1.41391100 2.36352600 3.07520700 3.48703300 3.18644900 -0.52768100 0.45023400

0.71677100 0.44072100 0.31301600 -0.76812400 -0.22357800 -0.21649400 -1.04845500 -2.10487400 -2.77014600 -2.34964300 -1.30341800 -0.65913400 -0.21929000 0.54341800 0.01850300 -1.36306500 -2.15583700 -1.55714700 -2.37287400 -1.85208700 2.40342000 3.64445300 4.81178100 4.69103800 3.40811400 2.27741800 0.88088700 -0.07829500 -1.41943700 -1.74811800 -2.89488200 -3.74943600 -3.41567500 -2.24167800 -1.85541900 -1.60701100 2.01480400 2.38086600 3.41010700 4.10012200 3.72400300 2.67517700 2.21666200 0.72350400 0.83694700 -0.54458100 -2.39796600 -3.41605100 -1.44764500 -2.69100100 0.44389600 0.95639100 0.47884200 -0.84961000 -2.66353000 -0.96207300 -1.80785600 -2.31443500 2.81587800 2.42258200 0.46457000 0.55440400 -1.04511000 -3.10678600 -4.65686500 -4.05633200 1.83008900 3.66360900 4.91325000 4.23503000 3.27445200 5.57692800 5.78800300 3.68392700 -2.84181700 -3.58976800 -2.39682300 1.60808600 0.67912800 -1.81461800 -3.23422400 1.01921000 1.85941400

-0.07184300 -0.04327600 1.10120300 1.27890400 1.70031500 2.93621500 2.88568500 3.78594500 3.84774700 3.01338000 2.09424200 1.99300000 -1.86264200 -2.96893300 -4.20675400 -4.30596400 -3.16194300 -1.94921400 -0.68649300 0.49892900 0.56621200 0.33978600 0.75244400 1.43838900 1.67975100 1.22952900 1.46663200 2.18631500 -1.20590200 -2.19746800 -2.98859500 -2.74136300 -1.71489800 -0.96410900 0.14226100 1.51073600 -0.58808500 -1.88929200 -2.33761300 -1.39620700 -0.04878400 0.32830300 1.76433800 1.95172500 3.10971800 3.79546200 -0.39165300 -0.89563000 0.12359400 1.17356500 0.50084500 2.07891200 2.93811900 2.72799200 0.26315700 -0.16981500 2.32033300 1.64592000 2.38035700 2.14906100 1.26776400 2.98265500 -2.35135900 -3.77702300 -3.33323400 -1.48973300 -2.57820000 -3.39933400 -1.70414200 0.71399500 2.21419100 1.78121700 0.54038000 -0.19239500 3.09388700 4.55455100 4.46481900 -2.84499400 -5.06824000 -5.25417600 -3.19942600 -1.51627400 -1.09516100

  µ-1,2-PC5 Cu Cu O N N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H O O

µ-1,2-PC6 1.78791400 -1.00815700 0.17230000 2.64808200 -2.04415200 -1.95869900 -0.57685500 -0.28666000 0.96760000 1.93455800 1.67063800 0.41886900 1.85111300 1.90531400 1.77272700 1.56881300 1.51228800 1.65488800 1.61342700 2.81782900 3.44868000 3.23708400 4.25392100 5.55190900 5.77277100 4.70370000 4.92485600 3.98055700 -2.82093400 -2.62622400 -3.65764600 -4.96272400 -5.17040500 -4.08058500 -4.32427300 -3.48356300 -0.89294400 -0.52490800 -0.37837600 -0.61003800 -0.98508500 -1.12808200 -1.59837100 -1.37617900 -2.63372800 -2.34312300 0.67571300 1.58468400 3.72097800 3.00306200 4.84340300 5.96326200 3.78190600 4.48532400 -4.24093600 -5.38024700 -3.50945000 -3.96977300 -2.66666400 -1.07979300 -1.73430800 -0.29787600 -1.59537800 -3.43786400 -5.80050700 -6.17249500 -0.33566500 -0.08560900 -0.49972100 -1.17288100 6.76761600 6.37411700 4.02552900 2.20757800 2.90010400 1.18328800 -1.05805400 2.05273200 1.82571300 1.45876700 1.35846100 0.19349700 0.61066300

0.82101300 2.27531300 0.53193200 -0.77406300 1.48815900 -0.02180200 -0.60021800 -1.47157900 -2.10036900 -1.86860100 -0.99723100 -0.32510900 -0.33722800 0.30683400 -0.34945200 -1.73802100 -2.40764600 -1.68086000 -2.36743700 -2.03725100 2.18175500 3.50513700 4.46342700 4.03999800 2.67468000 1.76487700 0.28743200 -0.35331900 2.38224400 2.90251600 3.09154000 2.73250100 2.19839800 2.02771100 1.39963400 1.91143400 4.26958800 5.29263500 6.61216900 6.90094100 5.85388400 4.54531500 3.45910600 1.98966100 -0.41587900 -0.35168400 -2.10737700 -3.45797200 -1.92507900 -2.87924300 -0.25005700 0.13974300 0.35994200 -1.23401500 0.29999000 1.58032800 3.01252400 1.56927600 3.63787100 3.60809400 1.38011800 1.78818500 3.16821600 3.51217100 2.86796300 1.90975600 5.01632500 7.39033500 7.91781500 6.03469400 2.30492400 4.75630000 5.51630800 3.78554600 -2.37831500 -2.77552800 -1.67296600 1.38739900 0.21745800 -2.29002900 -3.48851500 3.01174800 2.10548100

-0.30943600 1.09625400 0.95656600 0.94994000 2.75292300 2.74114500 2.93371500 3.99467700 4.09566500 3.10443800 2.03377700 1.95089800 -2.12475200 -3.31391900 -4.54291100 -4.53971900 -3.30951500 -2.11234800 -0.76348600 0.14143100 -0.07830100 -0.28492900 -0.19899300 0.12141600 0.34535200 0.23638700 0.46946200 1.51049600 -0.18237900 -1.42088500 -2.34622300 -1.97663300 -0.69976900 0.17932000 1.53824800 2.72023100 2.12212000 1.30581800 1.74018900 3.09472900 3.94104200 3.42915000 4.37801200 4.00484300 3.52751000 1.76196300 -0.23515700 -0.92406900 -0.48049000 0.83575200 -0.49440900 0.81027500 2.32682200 1.95471100 1.44630400 1.80636500 2.71293000 3.65864600 4.60891300 5.34363300 4.86087000 3.89481300 -1.65718200 -3.32982200 -2.66593700 -0.37320300 0.26747200 1.03209000 3.48081500 5.00244000 0.60430100 0.20034200 -0.37772000 -0.51006800 3.17056600 4.92791900 4.74592900 -3.26420800 -5.47471900 -5.47698300 -3.26842100 -0.25204100 -1.19988000

Cu Cu O N N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H O O

S38  

1.55981900 -1.06073400 0.01958000 2.42723400 -2.16324300 -2.11664000 -0.75749000 -0.48921900 0.73606100 1.69803100 1.45667400 0.23737800 1.50952000 1.50350900 1.35323800 1.19922200 1.20557600 1.36015100 1.37923300 2.60548700 3.32548600 3.17225300 4.22027400 5.49142800 5.65554400 4.55810200 4.74661300 3.74786100 -2.81542500 -2.78305500 -3.89767600 -5.09392800 -5.12702800 -3.96891900 -3.95258600 -3.61935800 -0.39586600 0.35250100 0.82510500 0.52257200 -0.23981700 -0.69282600 -1.55037500 -1.49494700 -2.78904300 -2.54528400 0.45445700 1.36544900 3.48463200 2.83163700 4.73656800 5.75978500 3.52677600 4.22494800 -4.94817300 -3.23837800 -3.98148400 -4.18771900 -2.59821000 -1.23492900 -1.96572100 -0.44408800 -1.82427200 -3.82323200 -5.98519900 -6.04023200 0.57493800 1.41893200 0.87627200 -0.49091400 6.62977000 6.33654100 4.03631300 2.16538200 2.63993800 0.93276300 -1.25772400 1.61697900 1.35572800 1.07899900 1.09153400 0.39131300 0.10394800

1.13044500 2.66931100 0.88329600 -0.51743200 1.76769200 0.25915200 -0.38931400 -1.36714800 -2.05734300 -1.77909300 -0.80352300 -0.07031900 0.04396900 0.73855000 0.12989000 -1.26419200 -1.98606700 -1.30520000 -2.04955600 -1.73544900 2.40389400 3.70921500 4.63638900 4.20192500 2.85556500 1.97409600 0.50891300 -0.10110700 3.06199400 2.95903800 3.22585000 3.62090500 3.72732500 3.44083000 3.51719300 2.16519900 4.38141400 5.32146300 6.48125500 6.68748600 5.72066900 4.57810700 3.57458400 2.10922900 -0.19588100 0.06379700 -1.83260500 -3.13234600 -1.57235500 -2.60705200 -0.06996300 0.37713000 0.62553300 -0.98119400 3.83497900 4.29648000 2.16905200 1.37811500 3.93351100 3.59008200 1.49851700 1.78622200 2.65578800 3.12772500 3.84085700 4.03114700 5.11085800 7.20017700 7.57723800 5.83775800 2.47664700 4.89431300 5.67377800 4.00280400 -2.33542400 -2.81514500 -1.60320700 1.82060500 0.73673100 -1.78035100 -3.07264100 2.51274000 3.39778200

-0.26273300 1.39435600 1.08387900 0.90884800 3.02995400 2.85574600 2.96113200 3.93236800 3.95215700 2.96763300 1.98584800 1.99055100 -2.12385200 -3.28549200 -4.53685400 -4.58686000 -3.38521100 -2.16262500 -0.84412300 0.03827800 -0.20681200 -0.54283300 -0.51746500 -0.11499000 0.23410300 0.17209900 0.49738200 1.50208800 0.25155400 -1.09765600 -1.90224200 -1.28409200 0.11372300 0.85934200 2.36915000 3.04262000 2.71981700 2.08590600 2.70661900 4.06128400 4.72433700 4.03035000 4.77584800 4.33024400 3.61063800 1.85625600 -0.27477900 -1.05159500 -0.60543000 0.68192700 -0.44566900 0.91310100 2.30117400 1.97755500 2.72293500 2.68808900 4.08970200 2.51980900 4.79547200 5.83474600 5.12979000 4.25064500 -1.52548400 -2.98732900 -1.87788100 0.63078700 1.03855800 2.13810200 4.58903400 5.78149700 0.55172400 -0.07393500 -0.80499300 -0.83694000 2.96971600 4.71508500 4.67643300 -3.19343700 -5.44472100 -5.54309800 -3.38600700 -1.02621400 -0.01997700

  µ-1,2-PC7 Cu Cu O N N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H O O

µ-1,2-PC8 1.91718100 -0.79252700 0.27495700 2.67849000 -1.83992000 -1.84964500 -0.49480000 -0.22563100 0.99323100 1.94805900 1.70774400 0.49101300 1.89551100 1.99593000 1.81386600 1.50794900 1.40307300 1.59994700 1.51075000 2.74278700 3.63638700 3.49641100 4.56901000 5.84704300 5.99336900 4.87100400 5.00446500 4.05035800 -2.60349900 -2.38681200 -3.41909200 -4.74540600 -4.97402200 -3.88299800 -4.15592900 -3.25132800 -0.86865200 -1.26053700 -1.37293000 -1.06792600 -0.65690200 -0.56025200 -0.10859200 -1.20217100 -2.52201300 -2.28201900 0.59894600 1.39681000 3.64736400 2.86856800 4.85671900 6.04071300 3.92317900 4.50899900 -4.20692500 -5.17728100 -3.18524300 -3.76016900 0.27467400 0.73518200 -1.99024500 -0.73346700 -1.33923800 -3.18387800 -5.58346200 -5.99284900 -1.48410600 -1.69030800 -1.14482100 -0.40369200 6.97051500 6.71110800 4.39835400 2.47937300 2.88698700 1.19040600 -0.98983800 2.22277700 1.90793600 1.35699600 1.17031200 0.44020400 0.83117700

0.83700000 2.29748900 0.52242900 -0.90439700 1.48991400 -0.01631500 -0.67767800 -1.62780800 -2.32773700 -2.08562000 -1.13833000 -0.39715900 -0.18142300 0.54315400 -0.00894600 -1.37518800 -2.12805300 -1.50405400 -2.28247900 -2.11244700 2.07746400 3.42520500 4.30971700 3.78144900 2.38934300 1.55849700 0.05422500 -0.62621800 2.30173800 2.69819300 2.96827900 2.83485700 2.41963900 2.14800300 1.60256100 2.02044200 4.21538700 5.33121200 6.57587200 6.66217300 5.50397700 4.28994700 3.00251800 1.91810300 -0.43596100 -0.24779500 -1.98972800 -3.35287900 -2.02202000 -3.01548300 -0.37664800 -0.19177600 0.01430300 -1.57621200 0.49804900 1.91233100 3.12026400 1.68428500 3.21113300 2.58846600 2.26737700 1.03623800 2.78892300 3.27931700 3.04674100 2.29753700 5.21116300 7.45212800 7.61520100 5.53535200 1.93852900 4.43770200 5.38709700 3.78463300 -2.64632300 -3.06268200 -1.83298800 1.60330400 0.61976600 -1.84677000 -3.19490100 3.11181500 2.26106700

-0.20898000 1.28509600 1.04251800 0.91749100 3.00126200 2.88409400 2.98329300 3.98196500 4.01416300 3.01450100 2.00476100 1.98872300 -2.10691100 -3.24568700 -4.51883400 -4.61678700 -3.43899900 -2.19254300 -0.89718000 0.01456600 0.15958100 0.10836100 0.27333800 0.50685500 0.57158300 0.39288600 0.46538300 1.47234800 -0.01523500 -1.29523400 -2.20007700 -1.76122500 -0.44419100 0.40850200 1.79697000 2.96939700 2.20767800 1.55480100 2.18696100 3.55451700 4.23116700 3.52795600 4.17395700 4.30582700 3.65959600 1.89670000 -0.34166900 -1.13589300 -0.60921900 0.64253100 -0.54307900 0.75148300 2.35994300 1.81155400 1.73356400 2.08208100 3.01563700 3.89708800 5.18792700 3.58930500 4.99779900 4.77022900 -1.58749400 -3.22023800 -2.43075700 -0.06827700 0.49285800 1.61787600 4.08455800 5.29343200 0.76014600 0.64131400 0.22039500 -0.05641100 3.02545900 4.79893400 4.73950000 -3.11734000 -5.40673000 -5.59154800 -3.47683300 -0.00077200 -1.00650600

Cu Cu O N N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H O O

S39  

1.71097800 -0.87216100 0.14654200 2.55179900 -2.03077700 -1.90335200 -0.51784600 -0.18437100 1.05721900 1.96109400 1.65328600 0.42377300 1.52976800 1.53406700 1.25969000 0.96216800 0.95706700 1.24294400 1.25864700 2.55300300 3.48882000 3.36913700 4.46391800 5.74656100 5.87431100 4.72942200 4.85270900 3.95614100 -2.61608000 -2.55493600 -3.59243200 -4.74167400 -4.80936700 -3.73076200 -3.78248600 -3.49362700 -0.12807400 0.09524900 0.64719100 0.98852500 0.75856500 0.19861700 -0.08938600 -1.57882600 -2.55747500 -2.31470300 0.38792100 1.13613600 3.40979600 2.72426600 4.64636300 5.90210700 3.88652800 4.42906700 -4.78588200 -3.07007700 -4.01430600 -3.90548700 0.19943600 0.53457200 -2.18951500 -1.80347800 -1.63620800 -3.49492500 -5.57220300 -5.69190700 -0.17512900 0.80554000 1.42339900 1.00941100 6.85467000 6.62799500 4.30637000 2.35111000 2.91060500 1.30771500 -0.91499900 1.75991600 1.27758900 0.74108900 0.73308800 0.57331100 0.32737400

1.00896400 2.52056700 0.70668100 -0.70694600 1.60019800 0.09766000 -0.49179000 -1.40814500 -2.06929300 -1.83403500 -0.92047900 -0.20369500 -0.04344800 0.65993800 0.08192400 -1.28883600 -2.01972100 -1.37029000 -2.12559000 -1.93420000 2.23473500 3.57982700 4.45151200 3.91373700 2.52560500 1.70749000 0.20748000 -0.41783700 3.18188000 3.31575700 3.87613900 4.32582200 4.18208100 3.60250700 3.38529000 1.92334300 4.09005800 5.32647600 6.36717000 6.11308400 4.83244800 3.83590500 2.44549100 2.05068800 -0.37325100 -0.14388300 -1.83012800 -3.20078600 -1.85817900 -2.82315600 -0.26972100 -0.03448000 0.26171800 -1.35607600 3.66239700 4.06513700 1.68163000 1.25164400 2.39365500 1.70585600 2.92096700 1.24484900 2.95921500 3.95809900 4.77351800 4.51058100 5.47097700 7.34846600 6.89727100 4.59801500 2.06701900 4.55959800 5.52669100 3.95194700 -2.37650300 -2.77730400 -1.62288100 1.72433700 0.69431100 -1.78064800 -3.08906100 2.44444200 3.29301800

-0.23992600 1.46436400 1.10486400 0.86366200 3.10399400 2.97203600 3.07588700 4.08548400 4.08642300 3.03811700 2.01507500 2.04192200 -2.10819600 -3.26452100 -4.50926100 -4.55762900 -3.36145300 -2.14548500 -0.83314700 -0.01655900 -0.08958900 -0.21426800 -0.17933200 -0.00007600 0.13945400 0.08754500 0.22946100 1.32039500 0.39595700 -0.95048700 -1.70534700 -1.03766200 0.35513100 1.04886400 2.54594900 2.94950300 2.76890700 2.26702500 3.02355100 4.36106500 4.88326700 4.06167800 4.58024800 4.46918100 3.73378700 1.97579900 -0.21664100 -1.04477500 -0.70595700 0.62075000 -0.74733900 0.46681500 2.18526700 1.67225700 2.91011300 3.05126000 3.89847000 2.17867800 5.64377600 4.04861400 4.76262100 5.19629500 -1.42075700 -2.78995300 -1.59006500 0.90907200 1.21931200 2.57122400 4.98657100 5.92047700 0.28849600 0.03525900 -0.28804600 -0.33009300 3.01996300 4.88078900 4.87294900 -3.17384100 -5.41321100 -5.50870800 -3.36140500 -0.95217200 0.08985900

  µ-1,1-SC1 Cu Cu O N N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H O O

µ-1,1-SC4 1.42801700 -1.84861600 -0.07481200 2.51861200 -2.94785800 -2.18216600 -0.83621600 -0.54679600 0.73934800 1.75528000 1.48271400 0.18882100 2.45750000 2.65273300 3.26062200 3.67910300 3.48327400 2.86683700 2.67805200 3.34408900 2.26577900 1.58669600 2.06370200 3.30522400 4.01043000 3.46872300 4.20985400 3.40541000 -2.24982600 -2.42922800 -2.69112700 -2.76982700 -2.59148400 -2.33289400 -2.17207800 -3.20977800 -3.17567200 -2.73257500 -3.58752300 -4.97083200 -5.43386300 -4.51620700 -4.98456300 -4.27245100 -2.05931400 -2.82520800 1.60122800 3.11826200 4.31829700 3.54391400 4.56969000 5.11607900 2.75039800 4.09895100 -1.14770500 -2.29896300 -4.19767000 -3.28157500 -4.85813400 -6.06722700 -4.92162800 -4.08568100 -2.34914800 -2.82849800 -2.97140300 -2.65349000 -1.65374000 -3.17266300 -5.67469100 -6.50261900 4.97732900 3.71582700 1.47459000 0.62560100 2.75645800 0.95373100 -1.33347100 2.30794600 3.39955800 4.15667300 3.80704200 -0.32361600 -0.42396300

0.07888100 -0.11199400 0.04589200 -0.83107200 -0.75096800 -0.34756100 -1.00068400 -1.82735500 -2.36724600 -2.07765400 -1.26226100 -0.72313600 -0.71846200 -0.01894400 -0.58201300 -1.91982700 -2.63759900 -2.01492400 -2.72684900 -1.98276300 2.11251100 3.18746000 4.49859400 4.70969100 3.60143900 2.31052000 1.09476500 0.21243300 -1.85155700 -1.75871200 -2.87117100 -4.13444400 -4.23018300 -3.06948300 -3.11025800 -2.24340700 1.42016500 2.50695300 3.47237200 3.30826600 2.19381500 1.26452400 0.08138000 -0.02632500 0.74759600 -0.56954100 -2.87537500 -3.73416000 -1.58371100 -2.68761000 0.48993700 1.43748100 0.84074000 -0.31947700 -2.81248900 -4.14982600 -2.41463300 -2.57505700 -0.85451700 0.18306800 -0.54861000 0.98463900 -0.75839600 -2.74443800 -5.02856700 -5.19594000 2.60007600 4.32830400 4.03699800 2.03861600 3.72912100 5.71738900 5.32785300 2.97947700 -2.48470200 -3.00247600 -2.04420400 1.01531400 0.01900200 -2.39553200 -3.67688800 0.42608200 0.69379100

-0.25241000 -0.09262700 1.01149300 1.30675000 1.59172800 2.84540800 3.03269900 4.13067000 4.30956800 3.38470000 2.27337700 2.09522200 -1.78695800 -2.93080900 -4.05665300 -3.99464200 -2.80580700 -1.70778500 -0.38560600 0.78993100 -0.13100900 -0.59565000 -0.49514500 0.12321500 0.61234200 0.47081700 0.98897300 1.96900300 -1.25632200 -2.59542800 -3.40245600 -2.79652900 -1.40901900 -0.65843400 0.84373000 1.58892900 -0.71567800 -1.39433000 -1.93410500 -1.77043300 -1.05870600 -0.53749200 0.27953800 1.64214100 2.78243500 3.71734900 -0.17139200 -0.45767400 0.46768700 1.61381900 0.13470000 1.51478100 2.59290000 2.64737200 1.12880700 1.18847900 1.13192300 2.64147000 -0.29765300 0.45836300 2.37031800 2.03844200 -3.02519600 -4.47799000 -3.39193400 -0.90268800 -1.50783100 -2.46951700 -2.18008200 -0.89732900 1.10412000 0.22561900 -0.89142500 -1.06941200 3.54650500 5.17222500 4.85991700 -2.93369400 -4.95693200 -4.85473700 -2.72068500 -1.38799900 -2.64752900

Cu Cu O N N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H O O

S40  

1.54456800 -1.70392500 0.05303900 2.59222800 -2.80233400 -1.90003600 -0.66442100 -0.39714800 0.82858300 1.81299000 1.56026800 0.30965000 2.39934500 2.60623600 3.12245800 3.43445700 3.22620600 2.70559800 2.50417600 3.28220200 2.55165400 1.95052900 2.55821700 3.84861800 4.47128900 3.80017200 4.44473300 3.60627000 -2.07378400 -1.25965100 -1.45394600 -2.54515800 -3.39226100 -3.13740300 -4.05694400 -3.35756700 -3.10425600 -3.28401400 -4.13639500 -4.82410700 -4.64747700 -3.78121300 -3.60526700 -3.92881000 -1.60620300 -2.51141400 1.42723200 2.84613400 4.27579300 3.44887900 4.69617800 5.40720200 3.04715500 4.27620300 -4.79394100 -4.64485800 -4.07020300 -2.52069300 -4.28316300 -2.57987900 -4.81422500 -4.18914700 -0.42580300 -0.76577100 -2.73377100 -4.25172700 -2.72630000 -4.25219200 -5.49496300 -5.17946800 5.47265600 4.35984200 2.02979300 0.94723300 2.77836600 1.02751200 -1.14708600 2.34005500 3.27301800 3.83855800 3.46611700 -0.15784700 -0.23871000

0.39689800 0.42974700 0.19023300 -0.89848200 -0.17687400 -0.17700000 -1.04005600 -2.05325900 -2.74202500 -2.40476900 -1.40728200 -0.74729900 -0.23693800 0.62605500 0.21650900 -1.13966300 -2.02940100 -1.55510100 -2.46721500 -2.00455000 2.27373600 3.47091400 4.69202900 4.67408100 3.43687800 2.24884000 0.89592100 -0.08653600 -1.40164200 -1.73298500 -2.86216800 -3.69863600 -3.36254000 -2.20484100 -1.81229200 -1.56688200 1.69028200 1.81562700 2.77617500 3.64126400 3.49846100 2.50925600 2.25637600 0.79564600 0.87458400 -0.49374200 -2.55833900 -3.48029100 -1.63882800 -2.86172300 0.44061700 1.04902400 0.46550800 -0.79634000 -2.61902200 -0.92320100 -1.75815100 -2.27364800 2.92008800 2.52315900 0.46667900 0.73315600 -1.05604600 -3.07449400 -4.59353800 -3.98957700 1.12647600 2.83989900 4.40795100 4.14408300 3.38482700 5.60467300 5.62919100 3.44100300 -2.91612100 -3.52294600 -2.29278800 1.66801000 0.94751600 -1.49914200 -3.08962600 1.15858300 1.82333800

-0.14019000 0.24574900 1.16105700 1.17564100 1.94295200 3.16722400 3.08721900 4.02321700 4.00860700 3.06514200 2.10868500 2.10392900 -1.86601900 -2.88996100 -4.12320300 -4.30234600 -3.23838300 -2.02228300 -0.83131000 0.41733900 0.35862500 0.15938300 0.47146600 1.02198000 1.23867900 0.89556400 1.11862300 1.96647000 -1.00586000 -2.03716700 -2.84003100 -2.56169500 -1.49751300 -0.73829000 0.39884200 1.75083700 -0.49946100 -1.83633200 -2.38950500 -1.52545200 -0.14129100 0.35130600 1.83142000 2.21091200 3.33016500 4.03227900 -0.58807900 -1.09819900 0.11428600 1.09158600 0.14152100 1.63334900 2.73845000 2.48706800 0.54403500 0.10063800 2.57682100 1.87121100 2.39177800 2.15344900 1.64598500 3.28357900 -2.22881600 -3.66059600 -3.16014200 -1.25031800 -2.46972500 -3.47281100 -1.92080100 0.56037700 1.67234000 1.28141200 0.28592000 -0.27027400 3.09540900 4.74641000 4.78325700 -2.70803500 -4.91952200 -5.25193000 -3.34186800 -1.04952200 -2.15385300

  µ-1,1-SC5 Cu Cu O N N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H O O

µ-1,2-SC1 1.62563500 -1.33222700 0.03765400 2.67114600 -2.51689600 -2.12623900 -0.68444100 -0.32445600 1.01857800 2.02215600 1.68327200 0.33826300 1.52194500 1.08518300 1.00806300 1.40851700 1.86044100 1.90271800 2.34547800 3.33200600 3.18771600 2.94589600 3.89483400 5.15804600 5.40844700 4.41302500 4.77620100 3.67023900 -2.82291300 -2.60514600 -3.57167000 -4.80591400 -5.03134400 -4.02134300 -4.22494300 -3.97639500 -0.41997100 0.75876700 1.36898800 0.73071800 -0.48721000 -1.04350700 -2.36290400 -2.32021000 -2.78344400 -2.36337000 1.45328100 2.82755900 4.05843400 3.89937200 5.39261300 5.46169900 3.08673500 4.16254700 -3.57449000 -5.26116800 -4.40388700 -4.50044000 -3.13954400 -2.68667000 -3.10398700 -1.34933700 -1.63054500 -3.35518600 -5.58432700 -5.98494300 1.22316000 2.31775400 1.17209900 -1.01090100 6.37948600 5.92969200 3.64120500 1.94640800 3.05991300 1.28152900 -1.10539600 0.77930700 0.64464600 1.37090400 2.18076600 0.04444500 -0.15475600

1.02556500 1.95824700 0.53527000 -0.14136300 1.01858700 -0.44746000 -0.72342300 -1.51914800 -1.86594700 -1.42421700 -0.61802200 -0.25227700 -0.46935200 -0.07886400 -0.93980300 -2.27374900 -2.68364900 -1.76244800 -2.21667000 -1.29662300 2.23404800 3.05546000 3.93967400 3.99433100 3.15459900 2.27116400 1.33285600 0.76181000 2.97941700 4.21886600 4.90498800 4.28052400 3.00190400 2.36845600 1.02208700 1.07775100 3.52573200 4.11526100 5.08484800 5.46118200 4.85189800 3.88838800 3.22136800 1.67880600 -0.91723200 -0.90082200 -2.38852400 -3.20266100 -0.88165800 -1.89041700 0.51138700 1.87623800 1.57389200 0.19825700 0.25972500 0.68983800 2.01066200 0.24269100 3.57551800 3.56319100 1.29346500 1.33896900 4.66210500 5.90368100 4.78325300 2.49265700 3.79911500 5.53088100 6.21277000 5.11651100 3.16843000 4.67652000 4.57040900 3.00603900 -1.71870100 -2.49117800 -1.88732300 0.96584900 -0.56929700 -2.98088200 -3.71450600 2.29961900 2.96492800

-0.13142800 0.94378300 0.96554000 1.24589500 2.42019700 2.52629100 2.87964900 3.98082200 4.21471200 3.33648100 2.23830700 2.02383500 -1.76519000 -2.98736800 -4.08695600 -3.91724600 -2.65618600 -1.59134700 -0.21314800 0.52936300 -0.69066800 -1.74931500 -2.26296300 -1.65417700 -0.56538300 -0.09837800 1.03622000 1.92840600 0.05687500 -0.44528100 -1.18634100 -1.42124600 -0.89075400 -0.14904400 0.50740100 2.02961100 2.26102100 1.94920200 2.75270300 3.94421000 4.27498600 3.41285300 3.74266900 3.76351000 3.28101000 1.54741600 0.42026200 -0.31710200 -0.18641400 1.27116500 0.62248600 1.71087400 2.39533600 2.74312500 0.03659100 0.33471000 2.42825900 2.53008700 3.03801500 4.73928100 4.44432400 4.15842300 -0.24187500 -1.56944800 -2.00042900 -1.04386700 1.01281900 2.44780800 4.60367700 5.19629500 -0.06557600 -2.01920000 -3.11679900 -2.18472100 3.51312900 5.07121800 4.65327100 -3.08008600 -5.04752600 -4.74992400 -2.48817100 -0.67071700 -1.76378700

Cu Cu O N N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H O O

S41  

1.51507200 -1.96654700 -0.13470900 2.50478000 -3.01346900 -2.28076900 -0.91206300 -0.62386500 0.67224800 1.69786800 1.42908400 0.12104200 2.54159900 2.81527100 3.37739200 3.66113200 3.38418600 2.82330700 2.56291900 3.27040600 2.48157100 1.88222300 2.46835200 3.73867100 4.35957300 3.70801600 4.34846900 3.45003300 -2.24731500 -2.43217100 -2.58578100 -2.54674000 -2.36176100 -2.21344800 -2.03442700 -3.12436300 -3.45009300 -3.09629700 -4.02864000 -5.39158200 -5.76204100 -4.77169500 -5.13163000 -4.40928500 -2.21456600 -2.92080200 1.47540600 2.92621600 4.25819800 3.44457500 4.68387900 5.26399200 2.82904300 4.08199400 -1.03100800 -2.07985200 -4.10196800 -3.13954800 -4.91073100 -6.21907800 -4.99023200 -4.33246600 -2.45161400 -2.73192300 -2.66271900 -2.33437000 -2.02863700 -3.68725900 -6.15157900 -6.81375100 5.34428100 4.23380200 1.93830500 0.89685000 2.71049500 0.88440400 -1.42514600 2.57072300 3.58354900 4.09690400 3.60294000 -0.92878500 0.35030900

0.14292400 0.08273700 -0.01696800 -0.78210600 -0.75443400 -0.31846000 -0.91038300 -1.63144000 -2.10342300 -1.84550000 -1.14028600 -0.67161200 -0.86745500 -0.26683000 -0.95385600 -2.32015500 -2.93887900 -2.18807100 -2.78614300 -2.00335300 2.12893100 3.24386700 4.51307200 4.63954000 3.49174300 2.24778500 0.99449000 0.19892200 -1.63088600 -1.47530500 -2.55598400 -3.85573400 -4.01854300 -2.88539600 -3.00149200 -2.26654200 1.53964700 2.73008300 3.64965700 3.32447700 2.10362900 1.23092200 -0.05413800 -0.18129800 0.78292400 -0.57050900 -2.83615300 -3.82620500 -1.66963700 -2.66304100 0.34776100 1.28031200 0.88950500 -0.36962400 -2.64731500 -4.06597300 -2.50695600 -2.65125600 -0.92738700 -0.07317100 -0.82212500 0.81327300 -0.44797700 -2.37784600 -4.72693600 -5.01496000 2.94357100 4.59517300 4.01222000 1.82352700 3.55101400 5.61207800 5.37610800 3.10673300 -2.19226400 -2.65571200 -1.81263200 0.79376600 -0.42629500 -2.89277900 -3.99749900 0.96044400 0.84449900

-0.26354500 -0.09397000 0.86078900 1.34305300 1.49589200 2.75404500 2.96759000 4.13848000 4.40121300 3.48145300 2.29586000 2.02321800 -1.76120600 -2.94425500 -4.02456100 -3.87560600 -2.64818300 -1.60089500 -0.23637800 0.88686700 -0.08080500 -0.56390400 -0.51265000 0.06905600 0.57976700 0.49180400 1.04738700 2.01677500 -1.40430200 -2.73701800 -3.61231600 -3.08444200 -1.70405600 -0.88429800 0.61238400 1.41991400 -0.56464500 -1.11020300 -1.59951300 -1.53188600 -0.95280100 -0.46922600 0.23913000 1.59280800 2.69495400 3.61964300 -0.03021400 -0.22494800 0.53298400 1.75340500 0.21418700 1.59097700 2.60888800 2.72405000 0.90342400 0.89642100 0.97279000 2.45593400 -0.40402500 0.41565300 2.28205700 2.05997100 -3.10529000 -4.67940500 -3.73415800 -1.25748800 -1.15777200 -2.02481900 -1.91099300 -0.86274400 1.04875000 0.12922300 -0.92037700 -1.01154200 3.70166300 5.31954700 4.86150000 -3.01852200 -4.95761100 -4.69809600 -2.49325500 -1.61501200 -1.75647800

  µ-1,2-SC3 Cu Cu O N N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H O O

µ-1,2-SC4 1.71074600 -1.74677900 0.02910900 2.65682900 -2.80004400 -2.20907000 -0.81830400 -0.55043500 0.74924100 1.80020800 1.55435200 0.24411500 2.86214600 3.17793500 3.81932000 4.14003400 3.82073100 3.18095100 2.86984800 3.48438700 2.63018700 2.03636900 2.58762700 3.81598400 4.43295300 3.81788400 4.45872700 3.53295100 -2.68352500 -3.24875500 -3.88018400 -3.92254300 -3.33279900 -2.71416200 -2.05456200 -2.73273000 -2.90642900 -2.43911300 -3.07504000 -4.26839300 -4.75783100 -4.05667900 -4.59361900 -4.24811800 -2.19585700 -2.88409800 1.77549000 3.27455200 4.48221100 3.62450900 4.85284300 5.33760200 2.85874400 4.14168800 -0.99090200 -2.06280800 -3.75804800 -2.17399300 -5.69703600 -4.33666200 -4.57243200 -4.83389500 -3.18707500 -4.32496700 -4.40620100 -3.34364700 -1.51832200 -2.64482200 -4.80442600 -5.68317800 5.38701900 4.28284600 2.06405500 1.08526300 2.81440600 0.94316600 -1.37439000 2.90204700 4.05649400 4.63661900 4.06584600 -0.70534900 0.58682200

0.14464200 0.02056100 0.01822600 -0.65948300 -0.85586600 -0.32746700 -0.82858300 -1.47952000 -1.88738600 -1.64096000 -1.00617500 -0.59465400 -0.87946000 -0.31703000 -1.02636200 -2.37470900 -2.95270300 -2.18095000 -2.73181800 -1.87518900 2.16553400 3.22747000 4.51323300 4.71420600 3.62086200 2.35602500 1.15793500 0.39445200 -1.21879200 -0.77273900 -1.63250100 -3.00426900 -3.46340400 -2.54492300 -2.94899000 -2.37571400 1.93737300 2.97326200 4.21295400 4.40478100 3.34597200 2.12252100 1.03008200 -0.43296100 0.77189100 -0.59446900 -2.82004000 -3.75389700 -1.52805400 -2.48982200 0.47283800 1.50139700 1.09852000 -0.10587800 -2.64122100 -4.04776700 -2.77327900 -2.73307700 1.08367000 1.27959400 -0.70883700 -1.04701200 0.30076900 -1.23185900 -3.70622800 -4.52466300 2.78733700 5.00301700 5.35615700 3.45379800 3.73906300 5.70218900 5.33159000 3.03067000 -1.94141300 -2.38430400 -1.65978000 0.73040200 -0.52990600 -2.96452300 -3.99590000 0.74984400 0.70794200

-0.19080800 -0.12438100 0.88839900 1.50457000 1.40690200 2.69720400 2.99851700 4.21532800 4.55329800 3.65985700 2.43085200 2.08450800 -1.57860700 -2.76984500 -3.78986300 -3.56926400 -2.33234100 -1.34746400 0.02639300 1.15081600 -0.10559800 -0.70090800 -0.70312900 -0.05599200 0.56682600 0.52629400 1.19238700 2.16197300 -1.51187700 -2.65697100 -3.56220600 -3.26731800 -2.07995600 -1.21579900 0.08082500 1.34386800 -0.02977200 -0.77675100 -0.86602400 -0.15236800 0.61780400 0.66800600 1.57032400 1.27606100 2.61051700 3.53137100 0.17675200 0.10280000 0.84062300 2.05548000 0.41761700 1.76248600 2.67475900 2.93779800 0.06167800 0.17488000 1.42282000 2.22188700 1.53975600 2.61786100 0.25944000 1.98612400 -2.84409900 -4.47492200 -3.95112200 -1.82257700 -1.32922300 -1.48448700 -0.19708400 1.18861200 1.08525000 -0.03318700 -1.20123300 -1.19768500 3.93393900 5.50658800 4.91244800 -2.90019700 -4.73255500 -4.34376500 -2.12236000 -1.71308100 -1.77906200

Cu Cu O N N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H O O

S42  

1.67398500 -1.79083100 -0.00461700 2.53606300 -2.92298400 -2.04789100 -0.80536900 -0.58932200 0.61802900 1.63449800 1.43525800 0.19946100 2.51079800 2.84715100 3.29635400 3.39474900 3.05345300 2.61468000 2.29475600 3.11819300 2.86136900 2.38686700 3.12323800 4.41385900 4.90549400 4.10641100 4.59351900 3.62090300 -2.07093000 -1.23602800 -1.35329500 -2.38558900 -3.25378700 -3.07821800 -4.02808900 -3.36055700 -3.31930900 -3.46698700 -4.36397500 -5.13224500 -4.98678600 -4.07240700 -3.92627400 -4.13440800 -1.77704000 -2.66557500 1.21424600 2.51178300 4.13994600 3.20548200 4.81169500 5.55467100 3.11350100 4.18626000 -4.68403000 -4.69956000 -4.06251200 -2.47128600 -4.67843100 -2.93980800 -4.97062800 -4.42088300 -0.44883400 -0.65218400 -2.51310700 -4.06879000 -2.84382500 -4.45153900 -5.83899800 -5.57884400 5.90187600 5.02385700 2.69128500 1.38192300 2.58976600 0.77589800 -1.37242700 2.74736900 3.55946000 3.73845100 3.12950300 -0.69553000 0.59586200

0.55187600 0.62005400 0.28644500 -0.88099600 -0.09382500 -0.03545500 -0.88642500 -1.87762800 -2.59194100 -2.29330500 -1.31513900 -0.62843300 -0.20023600 0.63201600 0.16523400 -1.22060700 -2.08105200 -1.54490100 -2.42239400 -2.04165900 2.27274500 3.53556900 4.66829500 4.48880800 3.18395400 2.09211300 0.66876800 -0.23766800 -1.16041500 -1.36682000 -2.45173300 -3.37629900 -3.16847400 -2.04707100 -1.78431900 -1.51920500 1.79626900 1.94278400 2.85691300 3.65673500 3.49413300 2.55033700 2.26686500 0.77099200 1.02595400 -0.33837800 -2.38037100 -3.47115400 -1.76572900 -2.91163500 0.23179400 0.68366800 0.34458900 -1.04598200 -2.66274900 -0.94683300 -1.79062300 -2.15977600 2.84770900 2.60930000 0.39529300 0.63719100 -0.62398200 -2.56363200 -4.24113200 -3.86724800 1.30833800 2.93755900 4.38784000 4.08790200 3.00452900 5.34659700 5.66319100 3.63384400 -2.81900300 -3.35699000 -2.07945600 1.70096200 0.87486000 -1.62492000 -3.16431100 1.72865300 1.77744000

-0.04456200 0.17968600 1.04667800 1.22587600 1.79882700 3.03647700 2.99956900 3.97210100 4.02354600 3.10552400 2.11664000 2.03271900 -1.80659300 -2.82176500 -4.06099400 -4.25959900 -3.20624900 -1.98304300 -0.79351900 0.45149800 0.61545500 0.48850500 0.85182600 1.37160200 1.51388800 1.12912900 1.29233000 2.07544400 -1.16286500 -2.20889100 -3.08436900 -2.86436800 -1.78426000 -0.95086900 0.19970500 1.56400400 -0.56167300 -1.90047500 -2.46062300 -1.60056100 -0.21573800 0.28115800 1.75735700 2.06550000 3.17483000 3.90199000 -0.55305100 -1.05224500 0.14615900 1.12415500 0.29912800 1.83197700 2.86050000 2.57476200 0.31566100 -0.07119400 2.37660000 1.67415400 2.31510100 2.12551300 1.45682700 3.12480300 -2.35119500 -3.91388100 -3.52048700 -1.58275800 -2.53121500 -3.54550100 -2.00079000 0.48361200 1.92375900 1.66606200 0.72718300 0.07512600 3.17780200 4.78726300 4.70920900 -2.62671500 -4.84746900 -5.21500100 -3.32199300 -1.19831900 -1.22208300

  µ-1,2-SC5 Cu Cu O N N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H O O

µ-1,2-SC6 1.66007400 -1.23580200 0.11967400 2.42287500 -1.92710000 -2.08011200 -0.79240700 -0.62522500 0.51347400 1.50713600 1.36462700 0.21901300 2.19679700 2.55012100 2.76286500 2.59556700 2.23641300 2.04258600 1.71161700 2.71703700 3.22810800 2.99027800 3.96014600 5.24283800 5.49326300 4.46754200 4.70926900 3.68056900 -3.23700500 -3.28121500 -4.46635200 -5.68371100 -5.64860600 -4.41424600 -4.43983100 -3.25110600 -0.80364300 -0.67241700 -0.32034200 -0.07879200 -0.22180800 -0.59637800 -0.83246100 -0.89610800 -2.66100600 -2.68546600 0.68460100 1.72213600 3.73073300 2.73102500 4.75002000 5.70810400 3.36142400 4.15021300 -4.64154500 -5.32482200 -3.12138500 -3.49425400 -1.74574700 -0.01830000 -1.10775700 0.08131100 -2.32040500 -4.42953300 -6.63638800 -6.57336100 -0.85893000 -0.23725100 0.20810700 -0.05458700 6.47737600 6.03100700 3.71075400 1.98352300 2.39734800 0.62698500 -1.40564500 2.66084200 3.04977100 2.74799100 2.10755100 -0.44720000 0.63283800

0.69933100 2.17470000 0.63714500 -0.90199000 1.66457100 0.16102300 -0.63060800 -1.68313300 -2.50371300 -2.26676600 -1.21656700 -0.38543800 -0.06016000 0.76198800 0.29998400 -1.06883700 -1.91997400 -1.39025900 -2.26840100 -2.09585000 2.17899400 3.51041900 4.48206700 4.05914300 2.68405100 1.76439000 0.27445800 -0.47833800 2.06912200 2.14630500 2.12743100 2.03053900 1.95047200 1.96595700 1.81216600 2.33392100 4.20539500 5.14368300 6.47062200 6.85984600 5.90404200 4.58177200 3.61634900 2.11207700 -0.10408800 -0.11576800 -2.06693500 -3.32286000 -1.97153700 -3.00475600 -0.16461100 0.11023000 0.15583700 -1.38502000 0.75144200 2.35496700 3.40920700 2.21267200 3.94184000 3.75429700 1.60096300 1.74930200 2.23104900 2.19127700 2.01905500 1.87310800 4.80522500 7.17723600 7.88633700 6.16960200 2.31654800 4.78419400 5.54127400 3.80427600 -2.90026600 -3.31786600 -1.86725700 1.81900300 1.00020200 -1.46856300 -2.99157800 2.63874400 2.10277800

-0.27684800 0.98041800 0.97937900 0.84918000 2.79637100 2.83308600 2.83275700 3.74898500 3.71891100 2.75942000 1.83774600 1.86685500 -2.13785600 -3.15469200 -4.45709400 -4.71775000 -3.66293400 -2.37555000 -1.18861000 -0.03312900 0.23824800 0.15236800 0.42100600 0.80006300 0.89891000 0.61166300 0.71675000 1.58603200 0.05650700 -1.30167100 -2.03893600 -1.34783200 0.04700300 0.72964200 2.23846800 3.04943300 1.64547200 0.66791900 0.91864900 2.24628400 3.25550800 2.93436100 4.08175800 3.80230400 3.73618500 1.95237700 -0.82529900 -1.50835700 -0.44470600 0.59153700 -0.29830500 1.15332200 2.42838700 2.01095900 2.48176500 2.61648400 2.85355900 4.12327500 4.61589900 4.81700900 4.76138400 3.44756900 -1.80791700 -3.12808700 -1.88313000 0.62353300 -0.35139300 0.09073500 2.48783700 4.30209400 1.19816800 1.01834900 0.33310900 -0.14700900 2.74287700 4.43841300 4.49350800 -2.90777100 -5.24372800 -5.72342200 -3.82863700 -0.83659200 -1.31141900

Cu Cu O N N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H O O

S43  

1.54008600 -1.31761700 0.04382000 2.30605400 -2.05446700 -2.19023200 -0.90441800 -0.74900500 0.38505700 1.38412800 1.25371800 0.11933300 1.87227300 2.11176500 2.18080500 1.98696600 1.74958300 1.69958800 1.50538800 2.59303100 3.22327000 3.05487900 4.06556700 5.31943400 5.50169800 4.43921300 4.63707300 3.56374700 -3.20346300 -3.48485300 -4.70128400 -5.66910000 -5.38339700 -4.14121900 -3.80539500 -3.42482500 -0.51051300 -0.11845300 0.45203400 0.64059300 0.22838300 -0.35735000 -0.89284300 -1.03192200 -2.77090200 -2.80732100 0.50434600 1.53001200 3.55976500 2.71203200 4.72960800 5.60892700 3.24875500 3.99806200 -4.68821200 -3.00548300 -3.49039100 -4.16931000 -1.85682000 -0.21919900 -1.30195400 -0.06217300 -2.70386900 -4.87890900 -6.63048200 -6.11548500 -0.28119700 0.73971100 1.09224300 0.34645900 6.46289500 6.13748900 3.86756000 2.06947900 2.26738100 0.48932000 -1.53679700 2.24804600 2.37940700 2.02771500 1.60697000 0.49306400 -0.58955400

0.96754200 2.41778300 0.91194500 -0.66561600 1.81043200 0.29968200 -0.49041100 -1.60686000 -2.42946900 -2.13487600 -1.02245600 -0.18001300 0.17582800 0.99743700 0.53736100 -0.83116900 -1.68301000 -1.15427600 -2.03935700 -1.82676800 2.36112300 3.69094300 4.63593900 4.18880300 2.81663200 1.92247400 0.43585900 -0.26928900 2.89339800 2.65774700 3.01680300 3.65139200 3.88612500 3.49435100 3.68546900 2.36396700 4.33937900 5.28130400 6.50351400 6.77416200 5.81601700 4.60975900 3.64824200 2.16584200 -0.04244300 0.10893900 -1.87853600 -3.09323300 -1.63696800 -2.74236700 -0.05265700 0.27820900 0.38259000 -1.18548500 4.09272200 4.43758200 2.48129400 1.60255500 4.04347200 3.68686200 1.61987200 1.77196400 2.17006700 2.80273600 3.95211300 4.36836000 5.03726300 7.22138700 7.71311900 5.99450300 2.42929900 4.89218700 5.69366000 4.00411700 -2.77531900 -3.29208600 -1.83880900 2.05462800 1.23884200 -1.23002100 -2.75520800 2.41632200 2.91609000

-0.16185700 1.24259900 1.16770600 0.90219000 3.05430000 2.96126700 2.90538800 3.74619100 3.66794900 2.73040400 1.88323900 1.97211200 -2.08238800 -3.13264800 -4.45122600 -4.69383100 -3.60609800 -2.30436100 -1.09279500 -0.02260400 0.18287000 -0.02160200 0.18079200 0.62221400 0.83613300 0.60440600 0.80209300 1.65273400 0.45085400 -0.85470800 -1.44267300 -0.64941800 0.70234300 1.23136500 2.69158200 3.38869700 2.09797200 1.20000700 1.56265500 2.92723700 3.85861400 3.42024700 4.46432200 4.10663700 3.83749700 2.06274800 -0.64632100 -1.41352600 -0.51328100 0.58117100 -0.18676400 1.29838600 2.48342900 2.09455900 3.21113100 2.79910700 4.48557300 3.10702300 4.84168300 5.33946300 5.03166500 3.76538600 -1.43872600 -2.49816600 -1.07325500 1.35353800 0.14940600 0.79201300 3.25721900 4.92999400 1.18123600 0.79698000 -0.00326300 -0.36592200 2.67261900 4.33004300 4.46928100 -2.90045200 -5.26361000 -5.71052500 -3.75662600 -1.10846700 -0.60449200

  µ-1,2-SC7 Cu Cu O N N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H O O

µ-1,2-SC8 1.81281100 -1.06260000 0.19315900 2.50243600 -1.80618100 -1.96788100 -0.67449800 -0.47796200 0.67271700 1.64819600 1.47831000 0.32134500 2.10940000 2.43326900 2.46551400 2.14033900 1.81276900 1.80688400 1.52022800 2.63594300 3.43548700 3.25658800 4.28631600 5.56597500 5.75442200 4.67165900 4.83990300 3.83983800 -3.00409300 -2.97956900 -4.12770900 -5.37818400 -5.41236800 -4.21106800 -4.30270400 -3.15000100 -0.67787200 -1.02277800 -0.75564400 -0.10568700 0.25277200 -0.04257500 0.31295200 -0.90384400 -2.57152200 -2.54749600 0.54836800 1.42203900 3.61412600 2.64934700 4.76930700 5.85967600 3.64064800 4.28105000 -4.54320700 -5.19056700 -2.98371300 -3.46959600 0.88434600 0.97884000 -1.51499700 -0.52814800 -1.99352100 -4.03900100 -6.30383500 -6.36508900 -1.52361500 -1.05163400 0.11866100 0.76139800 6.73391200 6.39926700 4.08408700 2.25150500 2.54482000 0.80783700 -1.24537900 2.66881900 2.73639600 2.14860400 1.56598900 -0.22532800 0.89830600

0.82007800 2.21586300 0.62305400 -0.90409300 1.63213400 0.12829600 -0.65362100 -1.70605700 -2.50926000 -2.25684900 -1.20575700 -0.39071300 0.08570700 0.91663000 0.49787800 -0.83601200 -1.69807600 -1.21194300 -2.11115200 -2.05991700 2.14012900 3.48190700 4.37256300 3.85533500 2.46880000 1.63226200 0.13072300 -0.64599400 2.00199400 2.02102700 1.98212100 1.92881000 1.90322900 1.93298100 1.81518700 2.31040700 4.13852600 5.26966300 6.54430900 6.64755800 5.47345300 4.22470600 2.91523100 2.05009100 -0.19531300 -0.09075700 -1.85085300 -3.14966900 -1.96889100 -2.99947500 -0.20946900 -0.12432800 -0.08647800 -1.61859500 0.76371000 2.38534900 3.38982400 2.17148900 3.11287500 2.33408300 2.59203500 1.13825400 2.07481200 1.99827200 1.90612100 1.85541600 5.13973100 7.43062700 7.62600400 5.51773200 2.02717200 4.51648000 5.44429600 3.85086100 -2.88055900 -3.32342400 -1.90360900 1.94709500 1.20401700 -1.20124000 -2.74497400 2.85641300 2.38924400

-0.13654300 1.16625900 1.03469200 0.85374500 2.98666500 2.92864200 2.90679400 3.81805300 3.77120900 2.79703100 1.88102900 1.92668300 -2.09209700 -3.11181600 -4.44573500 -4.73679700 -3.68073300 -2.36170800 -1.17893700 -0.11704600 0.44944800 0.52864800 0.84896900 1.09957500 1.02707100 0.70020100 0.63659600 1.51832100 0.14091400 -1.21933100 -2.01226100 -1.37656900 0.02050300 0.75992500 2.26851000 3.14741700 1.88343000 1.22477700 1.73571600 2.97568500 3.65447300 3.08214300 3.74533300 4.13924600 3.79718800 2.01589800 -0.71542900 -1.53400300 -0.61551600 0.46244100 -0.41429500 0.96804200 2.44576400 1.80390900 2.51910400 2.59759000 2.99606300 4.19789200 4.66801800 3.07906500 4.87980100 4.62844500 -1.68015900 -3.10018500 -1.95710300 0.55323200 0.26381500 1.17157600 3.40771900 4.61967500 1.22283300 1.35055400 0.89675300 0.32189600 2.76092200 4.48695700 4.57267300 -2.84065500 -5.23281200 -5.76684500 -3.86976700 -0.58599100 -1.02743800

Cu Cu O N N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H O O

S44  

1.88031900 -1.07761500 0.23144900 2.63968400 -2.15414100 -2.10491500 -0.75806900 -0.58567700 0.63033700 1.69719300 1.54620300 0.32847300 1.38683800 0.91152900 0.63528100 0.86743500 1.35456900 1.60069100 2.06350900 3.15297800 3.76042200 3.77560000 4.93195000 6.14186500 6.13251000 4.93103400 5.00854300 3.73110100 -2.78797200 -2.79634400 -3.82686500 -4.89558100 -4.89956700 -3.83637000 -3.84523100 -3.61258900 -0.20752100 0.00933300 0.60143600 0.98776300 0.75984300 0.15931200 -0.12721000 -1.61762400 -2.81706500 -2.49010000 1.18409400 2.45480500 3.91893200 3.65160800 5.53997200 5.67875200 3.27460300 4.01782600 -4.82259100 -3.08989200 -4.07315700 -4.10306000 0.16895700 0.49835000 -2.21533000 -1.80883500 -1.94519400 -3.78558900 -5.71622100 -5.72432100 -0.30173000 0.75367000 1.45384600 1.04153400 7.05420900 7.07063100 4.87895100 2.81944600 2.64087600 0.74284600 -1.42465400 0.74154900 0.25184600 0.67327100 1.54482100 1.07880500 -0.05623300

1.23925100 2.52182600 0.95627600 -0.36116600 1.54187000 0.06175600 -0.60849300 -1.74563000 -2.44906000 -2.01168300 -0.87397600 -0.15818100 0.11272800 0.80891200 0.22802200 -1.14694400 -1.87371500 -1.22112000 -2.02682000 -1.40243400 1.99629600 2.89160700 3.53645800 3.25977200 2.33848600 1.70725900 0.65154200 0.19631900 3.29911300 3.47973800 4.14575700 4.65748900 4.45555500 3.76519000 3.44258600 1.94069800 3.99073600 5.26645300 6.23062500 5.85772100 4.53933800 3.62249700 2.19563700 1.80891400 -0.46052100 -0.02280400 -2.28244900 -2.99064700 -0.92499700 -2.20373900 -0.22635200 1.02922600 1.02682500 -0.57964300 3.72667000 4.04778500 1.63423400 1.35834400 2.06388300 1.49870900 2.62511600 0.90754400 3.07635700 4.25906100 5.19185400 4.81959600 5.51250200 7.24604000 6.58063200 4.21557600 2.09060300 3.74933400 4.24065100 3.09579700 -2.56286800 -3.33414000 -2.09414000 1.87605200 0.84037000 -1.64332600 -2.94601800 3.00587000 3.43126700

0.11086700 1.47325100 1.18230200 1.12446200 2.98078700 2.64501000 2.74621000 3.55486900 3.57990200 2.78201100 1.97398200 1.95272800 -1.78771200 -2.84955900 -4.09125900 -4.24848800 -3.15501900 -1.93024700 -0.73066700 0.15746900 -0.40688500 -1.43327900 -1.87037000 -1.21411200 -0.16413400 0.22117100 1.30704600 2.01403800 0.48598700 -0.85833400 -1.52846100 -0.77718800 0.60945500 1.21712700 2.69379000 2.94804900 2.81374400 2.41266600 3.23544100 4.53205200 4.95092800 4.06910300 4.48027200 4.37454300 3.31088500 1.61241100 -0.10747900 -1.09715600 -0.47352200 0.73510400 0.89132500 2.10101400 2.57995100 2.74746700 3.11612200 3.23034400 3.90590900 2.15198800 5.53436100 3.89653300 4.81137000 4.98585300 -1.40743900 -2.61332500 -1.26234200 1.22590200 1.39565500 2.86447700 5.20638200 5.95534000 0.36715800 -1.51712000 -2.70254400 -1.91249200 2.79221300 4.21022100 4.16470200 -2.68777100 -4.90986700 -5.20277400 -3.24089400 -0.48470500 -0.03522800

  TS-SC4 Cu Cu O N N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C N C C C C C C C

1.67536200 -1.83677600 0.13748400 2.56550100 -2.87869400 -1.91396300 -0.75341300 -0.62276100 0.51609100 1.56289900 1.45274500 0.27713000 2.65397000 2.95728300 3.55306400 3.84716900 3.53551400 2.93292900 2.60137200 3.26163000 2.54554700 1.94465800 2.52288000 3.77319700 4.38944800 3.75650800 4.39734200 3.54912600 -2.22896500 -1.39525000 -1.63302900 -2.79253500 -3.65911700 -3.35683900 -4.27406900 -3.56792600 -3.07901100 -3.28565900 -4.05845500 -4.64026300 -4.43772400 -3.65466700 -3.45879100 -3.91206900

0.40946700 0.34365200 0.25699700 -1.05142800 -0.04577900 -0.02995400 -0.98889800 -2.08010200 -2.90404900 -2.61834000 -1.53356400 -0.74037900 -0.02210200 0.95406900 0.67920900 -0.65495500 -1.66037200 -1.32442800 -2.37905500 -2.12408100 2.23271400 3.44223700 4.62077500 4.54348700 3.29058900 2.14303600 0.77403600 -0.27493200 -1.56889400 -2.06708100 -3.26832300 -3.99302000 -3.48170600 -2.26460700 -1.69435800 -1.38411900 1.91229300 2.10937100 3.16246200 4.05697500 3.84795000 2.76252000 2.45484600 1.02570500

-0.13076800 -0.04697000 1.01329300 1.10326100 1.78655300 2.95764000 2.86559500 3.74170100 3.71397900 2.82327900 1.93908600 1.92414300 -1.80194900 -2.69329400 -3.92668000 -4.24658000 -3.31986700 -2.09597800 -1.05926900 0.31090200 0.45428600 0.34350900 0.82573300 1.45691500 1.58384600 1.07360300 1.21102500 1.97146900 -0.95339700 -1.89825500 -2.57364700 -2.26026700 -1.28540100 -0.64667500 0.41204400 1.74699500 -0.68507700 -2.01020400 -2.50879800 -1.59738500 -0.22637000 0.20478800 1.67073100 2.03838500

H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H O O

-1.53030900 -2.49283800 1.50472600 2.94315700 4.30871800 3.28124500 4.67539400 5.34624000 2.96317300 4.21563300 -5.07920900 -4.77339600 -4.30042700 -2.80866400 -4.04525100 -2.40090400 -4.81436600 -4.19486500 -0.51407800 -0.92534500 -3.01751800 -4.57105400 -2.81041300 -4.19539600 -5.24672300 -4.88513400 5.35823000 4.25907600 2.00139500 0.97223500 2.46713400 0.60298400 -1.41776800 2.70646300 3.77912800 4.31570500 3.75605100 -0.55587500 -0.13296800

1.00062000 -0.24356900 -2.46624000 -3.35748400 -1.81522500 -3.06167400 0.38775100 0.89413400 0.21644300 -1.00904400 -2.42117900 -0.78737100 -1.42123300 -2.15699000 3.17072800 2.61144900 0.77638800 0.98352200 -1.46612600 -3.61992800 -4.93670300 -4.01759100 1.39677900 3.27495100 4.89642400 4.51516400 3.19448700 5.44087500 5.57222300 3.45138400 -3.23138400 -3.74545300 -2.27806900 1.97400500 1.49560600 -0.90965700 -2.70723100 0.75328700 1.96782100

3.03462500 3.87620800 -0.92864000 -1.43351500 0.16467400 0.89125700 0.21201100 1.75868900 2.76396200 2.46186500 0.60803200 0.02027700 2.57746400 1.94589000 2.26907600 1.95495400 1.45740800 3.10802300 -2.12431700 -3.32690400 -2.76362200 -1.01377400 -2.68582700 -3.58595600 -1.94663100 0.51350700 2.07867500 1.84805000 0.70605700 -0.15180500 2.84497300 4.40553500 4.46747600 -2.39996200 -4.61450200 -5.20031100 -3.53763300 -1.57267300 -1.64455400

19. References (1) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M. J.; Heyd, J.; Brothers, E. N.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A. P.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, N. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J.; Gaussian, Inc.: Wallingford, CT, USA, 2009. (2) Mahroof-Tahir, M.; Murthy, N. N.; Karlin, K. D.; Blackburn, N. J.; Shaikh, S. N.; Zubieta, J. Inorg. Chem. 1992, 31, 3001. (3) Connelly, N. G.; Geiger, W. E. Chem. Rev. 1996, 96, 877. (4) Thorp, H. H. Inorg. Chem. 1992, 31, 1585. (5) Murthy, N. N.; Karlin, K. D.; Bertini, I.; Luchinat, C. J. Am. Chem. Soc. 1997, 119, 2156. (6) Marcus, R. A.; Sutin, N. Biochim. Biophys. Acta, 1985, 811, 265. (7) Nielson, R. M.; McManis, G. E.; Safford, L. K.; Weaver, M. J. J. Phys. Chem. 1989, 93, 2152.

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