Synthesis, characterization, luminescent properties of

Polyhedron 134 (2017) 319–329

Contents lists available at ScienceDirect

Polyhedron journal homepage: www.elsevier.com/locate/poly

Synthesis, characterization, luminescent properties of silver (I) complexes based on organic P-donor ligands and mercaptan ligands Sen Lin a, Yang-Zhe Cui a, Qi-Ming Qiu a, Hong-Liang Han a, Zhong-Feng Li a, Min Liu b, Xiu-Lan Xin c, Qiong-Hua Jin a,⇑ a b c

Department of Chemistry, Capital Normal University, Beijing 100048, China The College of Materials Science and Engineering, Beijing University of Technology, Beijing 100022, China School of Food and Chemical Engineering, Beijing Technology and Business University, Beijing 100048, China

a r t i c l e

i n f o

Article history: Received 24 April 2017 Accepted 24 June 2017 Available online 1 July 2017 Keywords: Silver (I) complexes Crystal structures Organic P-donor ligands Mercaptan ligands Luminescence

a b s t r a c t Eight silver (I) complexes with P-donor ligands [triphenylphosphine (PPh3), bis(diphenylphosphino) methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe) and 1,4-bis(diphenylphosphino)butane (dppb)] and mercaptan ligands [3-amino-5-mercapto-1,2,4-triazole (H2AMTA), 2-amino-5-mercapto1,3,4-thiadiazole (HAMTD), 2-mercapto-6-nitrobenzothiazole (HMNBT) and 2-mercapto-5-methyl-benzimidazole (HMMBD)] named by [Ag2(PPh3)4(HAMTA)2]n (1), [Ag3(dppm)3(AMTD)2]2(BF4)2(dppm) (2), [Ag3(dppm)3(AMTD)2]2(ClO4)2(dppm) (3), [Ag4(dppm)4(MNBT)2](SO4)(H2O) (4), [Ag4(dppe)4 (HAMTA)2(AMTA)] (5), [Ag2(dppb)2(HAMTD)2](CF3SO3)22(CH3OH) (6), [Ag2(dppb)2(HMNBT)2](CF3SO3)2 (7) and {[Ag(dppb)(HMMBD)2](CF3SO3)2(CH3OH)(H2O)}n (8) are characterized by X-ray diffraction, NMR and fluorescence spectroscopy. Complexes 1 and 8 show 2D network structure. Complexes 2–5 are multi-nuclear clusters. Complexes 6–7 are of di-nuclear structure. In complex 7, the offset p p interactions between the neighboring benzene rings help to form the 1-D infinite chain. All the emission peaks of these complexes are attributed to ligands-centered [p–p⁄] transitions. Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction For several decades, the wide development of coinage metals complexes was attracted great interest, because their unusual structural diversity [1–3] and their excellent behavior in medicine [4,5], luminescence [6,7], catalysis [8,9]. The crystal structures of several silver(I) complexes with mixed ligands were reported extensively, especially which has luminescence property [10–12]. According to the Hard-Soft-Acid-Base (HSAB) concept [13], silver (I) is easily coordinated to ligands with S or P donor atoms. If the unsymmetrical multidentate ligands are coordinated with silver (I) ions, the generated complexes tends to form 1D infinite chains, 2D networks or 3D topological structures. So the organic P-donor ligands and mercaptan ligands are selected as co-ligands in our study. The mercaptan ligands have been known due to their interesting coordination patterns toward a metal atom [14–16]. For example, the py2SH in the complex [Ag(DPEphos)(py2SH)2]NO3 is bonded to silver atom in a monodentate fashion [15] and the tzdSH

⇑ Corresponding author. Fax +86 10 68902320. E-mail address: [email protected] (Q.-H. Jin). http://dx.doi.org/10.1016/j.poly.2017.06.036 0277-5387/Ó 2017 Elsevier Ltd. All rights reserved.

in the complex [Ag2(g1-S-tzdSH)2(l-S-tzdSH)2(PPh3)2](NO3)2 is bonded to silver atom in a sulfur atom-bridging fashion [16]. Particularly, heterocyclic-2-thiol ligands have been intensively investigated by Lobana and co-workers [17,18] because these ligands possess chemically active groups –N@C(–SH)– in equilibrium with its thione form (–N(H)–C(@S)–) [19]. Since the silver(I) complexes based on heterocyclic thione or thiolate were reported in the early 1990 [20], a number of silver(I) complexes with heterocyclic-2thione have been studied extensively [21,22], and we have reported a series of copper(I) complexes with heterocyclic-2thione [23]. The heterocyclic-2-thione ligands are used as a coligand in the formation of particular structure with some weak interactions (hydrogen bonds, p p interaction, C–H p interaction, anion p and metal metal interaction) [25]. In this context, we prepared eight functional silver (I) complexes with organic P-donor ligands [triphenylphosphine (PPh3), bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe) and 1,4-bis(diphenylphosphino)butane (dppb)] and mercaptan ligands [3-amino-5-mercapto-1,2,4-triazole(H2AMTA), 2-amino-5-mercapto-1,3,4-thiadiazole (HAMTD), 2-mercapto-6-nitrobenzothiazole (HMNBT) and 2-mercapto-5methyl-benzimidazole (HMMBD)] (Scheme. 1). [Ag2(PPh3)4

320

S. Lin et al. / Polyhedron 134 (2017) 319–329

Scheme 1. The materials of synthesis for complexes 1–8.

(HAMTA)2]n (1), [Ag3(dppm)3(AMTD)2]2(BF4)2(dppm) (2), [Ag3 (dppm)3(AMTD)2]2(ClO4)2(dppm) (3), [Ag4(dppm)4(MNBT)2] (SO4)(H2O) (4), [Ag4(dppe)4(HAMTA)2(AMTA)] (5) [Ag2(dppb)2 (HAMTD)2](CF3SO3)22(CH3OH) (6), [Ag2(dppb)2(HMNBT)2](CF3SO3)2 (7) and {[Ag(dppb)(HMMBD)2](CF3SO3)2(CH3OH)(H2O)}n (8). The 6–8 were obtained by using the 14-membered ring structure [Ag2(dppb)2(CF3SO3)2] as a precursor, just as the 2-D (6,3) network complex {[Ag2(dppb)3](CF3SO3)2(4,40 -bipy)(CH3CN)2}n (4,40 bipy = 4,40 -bipyridine) in [24]. These complexes are characterized by IR, X-ray diffraction, 1H NMR, 31P NMR and fluorescence spectroscopy. In these complexes, weak interactions can help to form special topological structure and stabilize the supramolecular framework. 2. Experimental 2.1. Materials and measurements All chemical reagents silver chloride (AgCl), silver trifluoromethanesulfonate (AgCF3SO3), silver tetrafluoroborate (AgBF4), silver perchlorate (AgClO4), silver nitrite(AgNO2), silver sulfate (Ag2SO4), triphenylphosphine (PPh3), bis(diphenylphosphino) methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,4bis(diphenylphosphino)butane (dppb), 3-amino-5-mercapto1,2,4-triazole (H2AMTA), 2-amino-5-mercapto-1,3,4-thiadiazole (HAMTD), 2-mercapto-6-nitrobenzothiazole (HMNBT), 2-mercapto-5-methyl-benzimidazole (HMMBD) and sodium hydroxide (NaOH) are commercially available and used without further purification. Elemental analyses (C, H, N) were determined on a Elementar Vario MICRO CUBE (Germany) elemental analyzer. Infrared spectra were recorded on a Brucker EQUINOX 55 FT-IR spectrometer using the KBr pellet in the range of 400–4000 cm1. Excitation and emission spectra of the solid samples were recorded on an F-4500 fluorescence spectrophotometer at room temperature. 1H and 31P NMR spectra were recorded at room temperature with Varian VNMRS 600 MHz and 243 MHz spectrometers, respectively.

(0.6 mmol, 0.1574 g), H2AMTA (0.3 mmol, 0.0348 g) and NaOH (0.3 mmol, 0.0120 g) into the reaction at ambient temperature. After 6 h, the mixture solution was filtered and removed into a beaker. The beaker was sealed by a thin film. Crystal 1 was obtained by slow evaporation for a week. Yields: 62%. Anal. Calc. for C76H66Ag2N8P4S2: C, 61.00; H, 4.41; N, 7.49%. Found: C, 60.52; H, 4.53; N, 7.10%. IR (cm1, KBr pellets):3444w, 3303w, 3046w, 1538m, 1477m, 1433s, 1309m, 1275m, 1092m, 1024m, 742s, 693s, 503s. 1H NMR (600 MHz, CDCl3, 298 K) d, ppm: 3.2 (s, HAMTA-NH), 5.7 (s, HAMTA-NH2), 7.2–7.6 (m, overlap with the solvent peak signal and PPh3-aromatic ring). 31P NMR (243 MHz, CDCl3, 298 K) d, ppm: 29.1 (s, PPh3). 2.2.2. Synthesis of [Ag3(dppm)3(AMTD)2]2(BF4)2(dppm) (2) Follow a similar method as for 1, only replacing AgBF4 (0.2 mmol, 0.389 g), dppm (0.2 mmol, 0.0770 g), HAMTD (0.4 mmol, 0.0538 g) and NaOH (0.4 mmol, 0.0160 g). Yields: 56%. Anal. Calc. for C183H162Ag6B2F8N12P14S8: C, 54.35; H, 4.01; N, 4.16%. Found: C, 54.21; H, 4.10; N, 4.13%. IR (cm1, KBr pellets): 3046w, 1503w, 1470m, 1432s, 1382w, 1308w, 1088w, 1017w, 993w, 777w, 742s, 694s, 503w. 1H NMR (600 MHz, DMSO-d6, 298 K) d, ppm: 3.2 (s, dppm-CH2), 5.7 (s, AMTD-NH2), 7.0–7.4 (m, dppm-aromatic ring). 31P NMR (243 MHz, DMSO-d6, 298 K) d, ppm: 24.9 (s, dppm), 2.2 [dq, 1J(109Ag-31P) = 407.75 Hz, 1J (107Ag-31P) = 409.21 Hz]. 2.2.3. Synthesis of [Ag3(dppm)3(AMTD)2]2(ClO4)2(dppm) (3) Follow a similar method as for 1, only replacing AgClO4 (0.2 mmol, 0.414 g), dppm (0.2 mmol, 0.0770 g), HAMTD (0.4 mmol, 0.0538 g) and NaOH (0.4 mmol, 0.0160 g). Yields: 58%. Calc. for C183H162Ag6Cl2N12O8P14S8: C, 54.02; H, 3.99; N, 4.13%. Found: C, 53.75; H, 3.96; N, 4.24%. IR (cm1, KBr pellets): 3054w, 1611m, 1507m, 1434s, 1392w, 1304w, 1096s, 1025m, 998w, 775w, 737s, 693s, 513w. 1H NMR (600 MHz, DMSO-d6, 298 K) d, ppm: 3.2 (s, dppm-CH2), 5.7 (s, AMTD-NH2), 7.0–7.4 (m, dppm-aromatic ring). 31P NMR (243 MHz, DMSO-d6, 298 K) d, ppm: 24.9 (s, 1 107 dppm), 2.2[dq,1J(109Ag-31P) = 407.69 Hz, J( Ag-31P) = 409.27 Hz].

2.2. Preparation of the complexes 2.2.1. Synthesis of [Ag2(PPh3)4(HAMTA)2]n (1) AgCl (0.3 mmol, 0.0430 g) was dissolved in a stirring solution of methanol (5mL) and dichloromethane (5mL), adding PPh3

2.2.4. Synthesis of [Ag4(dppm)4(MNBT)2](SO4)(H2O) (4) Follow a similar method as for 1, replacing Ag2SO4 (0.15 mmol, 0.0468 g), dppm (0.3 mmol, 0.0798 g), HMNBT (0.2 mmol, 0.0425 g) and NaOH (0.2 mmol, 0.0080 g). It is noteworthy that


complex 4 is obtained in solution lacking of NaOH. Yields: 21%. Calc. for C114H98Ag4N4O14P8S6: C, 52.22; H, 3.74; N, 2.14%. Found: C, 52.51; H, 3.77; N, 2.20%. IR (cm1, KBr pellets):2360m, 1509m, 1474w, 1434m, 1366w, 1321s, 1100w, 1007w, 823w, 739m, 694m, 582w. 1H NMR (600 MHz, CDCl3, 298 K) d, ppm: 3.7 (s, dppm-CH2), 7.0–7.5 (m, overlap with the solvent peak signal, dppm-aromatic ring and MNBT-aromatic ring). 31P NMR (243 MHz, CDCl3, 298 K) d, ppm: 5.2[d, 1J(109,107Ag-31P) = 243.86 Hz], 2.7[1J(109,107Ag-31P) = 437.41 Hz].

2.2.5. Synthesis of [Ag4(dppe)4(HAMTA)2(AMTA)] (5) Follow a similar method as for 1, replacing AgNO2 (0.2 mmol, 0.0231 g), dppe (0.2 mmol, 0.0797 g), H2AMTA (0.15 mmol, 0.0174 g) and NaOH (0.2 mmol, 0.0080 g). Yields: 38%. Calc. for C110H104Ag4N12P8S3: C, 55.71; H, 4.39; N, 7.09%. Found: C, 55.62; H, 4.23; N, 7.13%. IR (cm1, KBr pellets): 3423m, 3054w, 1644w, 1536w, 1507w, 1433m, 1270s, 1100w, 933w, 740m, 694s, 640w, 511m. 1H NMR (600 MHz, DMSO-d6, 298 K) d, ppm: 3.1 (t, dppeCH2), 3.2 (s, HAMTA-NH), 5.2 (s, HAMTA or AMTA-NH2), 7.2–7.4 (m, dppe-aromatic ring). 31P NMR (243 MHz, DMSO-d6, 298 K) d, ppm: 5.5 [d,1J(109,107Ag-31P) = 274.59 Hz].

2.2.6. Synthesis of [Ag2(dppb)2(HAMTD)2](CF3SO3)22(CH3OH) (6) [Ag2(dppb)2(CF3SO3)2] was obtained similarly to 1, replacing AgCF3SO3 (0.2 mmol, 0.0514 g) and dppb (0.2 mmol, 0.0853 g). [Ag2(dppb)2(CF3SO3)2] (0.1367 g) was dissolved in a solution of 3 mL CH3OH and 7 mL CH2Cl2, then HAMTD (0.2 mmol, 0.0269 g) and NaOH (0.2 mmol, 0.0080 g) were added. The solution was stirred for 6 h, and then it was filtrated. After slow evaporation, the filtrate resulted in the formation of crystals of 6. Yields: 71%. Calc. for C66H78Ag2F6N6O10P4S6: C, 44.96; H, 4.43; N, 4.77%. Found: C, 44.95; H, 4.44; N, 4.80%. IR (cm1, KBr pellets):3282w, 2929w, 1619w, 1555m, 1434w, 1292s, 1241s, 1156m, 1055w, 1027s, 743m, 695m, 635m, 510w. 1H NMR (600 MHz, DMSO-d6, 298 K) d, ppm: 1.6 (s, CH3OH-CH3), 1.7–2.2 (m, dppb-CH2), 3.6 (s, HAMTD-NH), 5.7 (s, AMTD-NH2), 7.3–7.6 (m, dppb-aromatic ring). 31P NMR (243 MHz, DMSO-d6, 298 K) d, ppm: 2.7 (s, dppb).

2.2.7. Synthesis of [Ag2(dppb)2(HMNBT)2](CF3SO3)2 (7) Follow a similar method as for 6, replacing HMNBT (0.2 mmol, 0.0425 g). Yields: 69%. Calc. for C70H62Ag2N4O4P4S4: C, 56.33; H, 4.16; N, 3.76%. Found: C, 55.92; H, 4.15; N, 3.77%. IR (cm1, KBr pellets):3431w, 3046w, 2934w, 1561w, 1506w, 1377w, 1312s, 1268m, 1120w, 1098w, 973w, 885w, 739m, 693m, 507w. 1H NMR (600 MHz, CDCl3, 298 K) d, ppm: 1.7–2.2 (m, dppb-CH2), 3.4 (s, HMNBT-NH), 7.1–7.4 (m, overlap with the solvent peak signal, dppb-aromatic ring and HMNBT-aromatic ring). 31P NMR (243 MHz, CDCl3, 298 K) d, ppm: 0.3[d, 1J(109,107Ag-31P) = 396.82 Hz].

2.2.8. Synthesis of {[Ag(dppb)(HMMBD)2](CF3SO3)2(CH3OH)(H2O)}n (8) Follow a similar method as for 6, replacing HMMBD (0.2 mmol, 0.0328 g). Yields: 37%. Calc. for C47H54AgF3N4O6P2S3: C, 51.60; H, 4.94; N, 5.12%. Found: C, 52.17; H, 4.53; N, 5.28%. IR (cm1, KBr pellets):3386w, 3183w, 2855w, 1618w, 1518w, 1518m, 1485m, 1458w, 1384w, 1285m, 1165m, 1096w, 1028m, 806w, 745w, 795m, 636m, 507w. 1H NMR (600 MHz, DMSO-d6, 298 K) d, ppm: 1.5 (CH3OH-CH3), 1.7–2.2 (m, dppb-CH2), 2.3 (s, HMMBD-CH3), 3.3 (s, HMMBD-NH), 7.2–7.4 (m, dppb-aromatic ring and HMNBT-aromatic ring). 31P NMR (243 MHz, CDCl3, 298 K) d, ppm: 3.3 (br, dppb).

321

2.3. Crystal structure determination and refinement Single crystals of the complexes were mounted on a Bruker Smart 1000 CCD diffractometer equipped with a graphitemonochromated Mo Ka (k = 0.71073Å) for 1–8 at 298 K by scaning to collect independent diffraction point. The data is restored by using BRUKER SAINT. All the structures were solved by direct methods using SHELXS program of the SHELXL-97 or SHELXS-97 package and refined with SHELXL-97 [26,27]. Metal atom centers were located from the E-maps and other non-hydrogen atoms were located in successive difference Fourier syntheses. The final refinements were performed by full matrix least-squares methods with anisotropic thermal parameters for non-hydrogen atoms on F2. The hydrogen atoms were generated geometrically and refined with displacement parameters riding on the concerned atoms. The crystallization solvent was lost from the crystal and could not be resolved unambiguously. The contribution of the missing solvent to the calculated structure factors was taken into account by using a SQUEEZE routine of PLATON [28]. The missing solvent was not taken into account in the unit cell content. Crystallographic data and experimental details for structural analysis are summarized in Table 1. 3. Results and discussion 3.1. Synthesis of complexes 1–8 Five new silver(I) complexes 1–5 are synthesized by the onepot reaction of different Ag salts, organic P-donor ligands and mercaptan ligands in mixed solution(CH3OH/CH2Cl2 = 1:1). (Scheme. 2) In the synthesis of complexes 1–5, the mercaptan ligands show various coordination patterns owing to deprotonation by precise ratio of sodium hydroxide (NaOH). Complexes 6–8 were obtained by the reaction of different mercaptan ligands with the complex [Ag2(dppb)2(CF3SO3)2] without any inorganic alkali. The complexes 6–7 are di-nuclear complexes, in which two silver atoms are linked by bridging thione group. Complex 7 is of 1D infinite chain and complex 8 is of 2D network structure. From the structures of 6 and 7, the HAMTD and HMNBT ligands don’t make the ring [Ag2(PP)2]2+ open, but the HMMBD ligand in the complex 8 open the ring [Ag2(dppb)2]2+, just as in the 2-D (6,3) network complex {[Ag2(dppb)3](CF3SO3)2(4,40 bipy)(CH3CN)2}n where the ring is opened by 4,40 -bipy [24], and in the chain complex {[Ag(l-dppb)(phen)](BF4)(CH3CN)}n where the ring is opened by phen [29]. 3.2. Single Crystal X-ray studies The structures of complexes 1–8 were elucidated by X-ray crystallography. The selected bond lengths and angles of 1–8 are given in Table 2. 3.2.1. Crystal structure of complex [Ag2(PPh3)4(HAMTA)2]n (1) In complex 1, each asymmetric unit (Fig. 1) is comprised of double [Ag(PPh3)2(HAMTA)] moieties in which each Ag is connected by two P atoms from two PPh3 ligands, one S and one N from one HAMTA ligand. The geometry around each Ag center is distorted tetrahedral as is evident from the angles ranging from 98.4(4)° to 123.4(15)°. The tetrahedral distortion may be attributed to the steric interactions between the bulky phosphine ligands. The HAMTA ligand deprotonated from H2AMTA acts as a bidentatebridging ligand to link adjacent [Ag(PPh3)2] moieties through the sulfur atom and the nitrogen atom to construct the 1-D infinite chain. Two hydrogen bonds N–H. . .S (N. . .S distance = 3.579 (15) Å, N–H. . .S angle = 159.1°; N. . .S distance = 3.600(2) Å, N–

322


Table 1 Crystal data for complexes 1–8.

a b

Compound

1

2

3

4

Formula Formula weight Crystal system Space group a (Å) b (Å) c (Å) a (°) b (°) c (°) V (Å3) Z Dcalc (Mg/m3) l (mm1) F(0 0 0) Rint Reflections collected Data/restraint/parameters Goodness-of-fit on F2 R1a [I > 2r(I)] wR2b [I > 2r(I)] R1a (all data) wR2b (all data)

C76H66Ag2N8P4S2 1495.11 Monoclinic Cc 33.129(3) 13.3187(12) 19.0403(17) 90.00 107.9320(10) 90.00 7993.2(12) 4 1.242 0.665 3056 0.0717 19335 10322/2/830 1.037 0.0848 0.2248 0.1217 0.2665

C183H162Ag6B2F8N12P14S8 4040.15 Triclinic P-1 12.1840(8) 15.6124(16) 24.996(2) 75.1820(10) 86.204(2) 88.532(2) 4586.4(7) 1 1.463 0.903 2046 0.0433 23217 15951/0/1268 1.040 0.0784 0.2067 0.1572 0.2322

C183H162Ag6Cl2N12O8P14S8 4065.43 Triclinic P-1 12.1566(11) 15.8349(14) 25.036(2) 75.9850(10) 86.156(2) 88.603(2) 4665.2(7) 1 1.447 0.913 2062 0.0479 23735 16238/0/1268 1.027 0.0774 0.1968 0.1496 0.2221

C114H98Ag4N4O14P8S6 2619.56 Triclinic P-1 13.6664(12) 15.1940(15) 16.8779(17) 101.3570(10) 106.532(2) 106.056(2) 3080.8(5) 1 1.412 0.890 1326 0.0469 15489 10635/1/676 1.101 0.0826 0.2269 0.1462 0.2993

Compound

5

6

7

8

Formula Formula weight Crystal system Space group a (Å) b (Å) c (Å) a (°) b (°) c (°) V (Å3) Z Dcalc(Mg/m3) l (mm1) F(0 0 0) Rint Reflections collected Data/restraint/parameters Goodness-of-fit on F2 R1a [I > 2r(I)] wR2b [I > 2r(I)] R1a (all data) wR2b (all data)

C110H104Ag4N12P8S3 2369.47 monoclinic P2(1)/c 13.9220(12) 25.814(2) 17.9081(14) 90.00 98.2120(10) 90.00 6369.9(9) 2 1.235 0.800 2408 0.0738 31989 11231/0/704 1.079 0.0645 0.1521 0.1371 0.1697

C66H78Ag2F6N6O10P4S6 1761.32 triclinic P-1 9.9790(8) 13.9260(11) 14.2110(12) 93.8020(10) 99.796(2) 100.092(2) 1906.5(3) 1 1.534 0.835 900 0.0329 9442 6582/0/453 1.060 0.0678 0.1605 0.1124 0.1944

C70H62Ag2N4O4P4S4 1491.10 triclinic P-1 12.0650(11) 12.1779(12) 12.8501(13) 88.970(2) 71.8220(10) 66.9880(10) 1639.3(3) 1 1.510 0.875 760 0.0403 8560 5692/8/397 0.984 0.0592 0.1252 0.1080 0.1585

C47H54AgF3N4O6P2S3 1093.93 triclinic P-1 11.6780(11) 13.7269(12) 17.3001(15) 88.630(2) 75.4020(10) 84.9920(10) 2673.5(4) 2 1.359 0.612 1128 0.1110 13618 9299/0/627 1.036 0.0892 0.1870 0.1991 0.2194

P P R1 = (||Fo| |Fc||)/ |Fo|. P P 2 wR2 = [ w(|Fo| |Fc|2)2/ w(Fo2)]1/2.

Scheme 2. The routine of synthesis for complexes 1–8.


323

Table 2 Selected bond lengths (Ǻ) and angles (°) for complexes 1–8. Complex 1 Bond length (Å) Ag(1)-N(2) Ag(1)-P(1) Ag(1)-P(2) Ag(1)-S(2)#1 Bond angle (°) P(1)-Ag(1)-P(2) N(2)-Ag(1)-P(1) N(2)-Ag(1)-P(2) N(2)-Ag(1)-S(2)#1 P(1)-Ag(1)-S(2) #1 P(2)-Ag(1)-S(2) #1 Complex 2 Bond length (Å) Ag(1)-P(1) Ag(1)-P(3) Ag(1)-S(2) Ag(1)-S(4) Ag(1)-Ag(2) Ag(1)-Ag(3) Ag(2)-P(5) Bond angle (°) P(1)-Ag(1)-P(3) P(1)-Ag(1)-S(2) P(3)-Ag(1)-S(2) P(1)-Ag(1)-S(4) P(3)-Ag(1)-S(4) S(2)-Ag(1)-S(4) P(1)-Ag(1)-Ag(2) P(3)-Ag(1)-Ag(2) S(2)-Ag(1)-Ag(2) S(4)-Ag(1)-Ag(2) P(1)-Ag(1)-Ag(3) P(3)-Ag(1)-Ag(3) S(2)-Ag(1)-Ag(3) S(4)-Ag(1)-Ag(3) Ag(2)-Ag(1)-Ag(3) P(2)-Ag(3)-Ag(1) P(6)-Ag(3)-Ag(1) S(4)-Ag(3)-Ag(1) Complex 3 Bond length (Å) Ag(1)-P(1) Ag(1)-P(3) Ag(1)-S(2) Ag(1)-S(4) Ag(1)-Ag(2) Ag(1)-Ag(3) Ag(3)-S(4) Bond angle (°) P(1)-Ag(1)-P(3) P(1)-Ag(1)-S(2) P(3)-Ag(1)-S(2) P(1)-Ag(1)-S(4) P(3)-Ag(1)-S(4) S(2)-Ag(1)-S(4) P(1)-Ag(1)-Ag(2) P(3)-Ag(1)-Ag(2) P(6)-Ag(3)-N(1) P(2)-Ag(3)-S(4) P(6)-Ag(3)-S(4) N(1)-Ag(3)-S(4) P(2)-Ag(3)-Ag(1) P(6)-Ag(3)-Ag(1) N(1)-Ag(3)-Ag(1) S(4)-Ag(3)-Ag(1) Complex 4 Bond length (Å) Ag(1)-P(3) Ag(1)-P(1) Ag(1)-S(2) Ag(1)-S(2)#1

2.357(4) 2.471(4) 2.496(4) 2.566(4)

Ag(2)-N(6) Ag(2)-P(4) Ag(2)-P(3) Ag(2)-S(1)

2.324(3) 2.470(4) 2.497(5) 2.642(5)

123.4(5) 109.9(4) 98.4(4) 113.2(4) 107.7(6) 104.0(7)

N(6)-Ag(2)-P(4) N(6)-Ag(2)-P(3) P(4)-Ag(2)-P(3) N(6)-Ag(2)-S(1) P(4)-Ag(2)-S(1) P(3)-Ag(2)-S(1)

109.4(4) 107.2(4) 123.6(5) 110.1(4) 101.2(6) 104.6(8)

2.447(3) 2.513(3) 2.617(2) 2.621(3) 3.292(4) 3.302(9) 2.449(3)

Ag(2)-P(4) Ag(2)-S(2) Ag(2)-S(4) Ag(3)-P(2) Ag(3)-P(6) Ag(3)-N(1) Ag(3)-S(4)

2.459(3) 2.568(3) 2.968(2) 2.449(3) 2.488(3) 2.578(8) 2.601(3)

122.1(9) 121.4(9) 97.4(8) 110.1(9) 95.7(9) 106.0(8) 151.2(7) 86.3(6) 49.9(6) 58.9(6) 85.4(6) 144.2(7) 83.79(6) 50.4(7) 67.0(2) 89.4(7) 139.1(7) 51.0(6)

P(5)-Ag(2)-P(4) P(5)-Ag(2)-S(2) P(4)-Ag(2)-S(2) P(5)-Ag(2)-S(4) P(4)-Ag(2)-S(4) S(2)-Ag(2)-S(4) P(5)-Ag(2)-Ag(1) P(4)-Ag(2)-Ag(1) S(2)-Ag(2)-Ag(1) S(4)-Ag(2)-Ag(1) P(2)-Ag(3)-P(6) P(2)-Ag(3)-N(1) P(6)-Ag(3)-N(1) P(2)-Ag(3)-S(4) P(6)-Ag(3)-S(4) N(1)-Ag(3)-S(4) N(1)-Ag(3)-Ag(1)

130.9(1) 115.8(1) 103.7(9) 107.9(9) 93.2(9) 97.9(8) 137.1(8) 90.1(6) 51.2(5) 49.1(5) 131.3(1) 107.5(2) 87.7(9) 111.6(9) 101.7(1) 115.2(2) 80.7(2)

2.457(2) 2.523(3) 2.617(2) 2.624(3) 3.278(7) 3.312(5) 2.617(3)

Ag(2)-P(5) Ag(2)-P(4) Ag(2)-S(2) Ag(3)-P(2) Ag(3)-P(6) Ag(3)-N(1)

2.452(3) 2.463(3) 2.571(3) 2.446(3) 2.489(3) 2.549(8)

122.4(8) 121.1(8) 97.6(8) 109.7(8) 95.3(9) 106.6(8) 151.3(7) 86.0(6) 87.9(9) 110.7(9) 101.7(9) 115.0(2) 88.9(7) 139.0(7) 80.6(9) 50.9(6)

S(2)-Ag(1)-Ag(2) S(4)-Ag(1)-Ag(2) P(1)-Ag(1)-Ag(3) P(3)-Ag(1)-Ag(3) S(2)-Ag(1)-Ag(3) S(4)-Ag(1)-Ag(3) Ag(2)-Ag(1)-Ag(3) P(5)-Ag(2)-P(4) P(5)-Ag(2)-S(2) P(4)-Ag(2)-S(2) P(5)-Ag(2)-Ag(1) P(4)-Ag(2)-Ag(1) S(2)-Ag(2)-Ag(1) P(2)-Ag(3)-P(6) P(2)-Ag(3)-N(1)

50.1(6) 59.3(5) 85.4(6) 143.9(7) 83.6(6) 50.7(6) 67.1(2) 130.5(1) 114.8(1) 105.3(9) 136.8(7) 90.7(6) 51.4(5) 131.8(9) 108.1(2)

2.480(3) 2.496(3) 2.662(3) 2.872(3)

Ag(1)-Ag(2) Ag(2)-N(1) Ag(2)-P(4) Ag(2)-P(2)

3.142(2) 2.390(9) 2.409(3) 2.462(3) (continued on next page)

324


Table 2 (continued) Bond angle (°) P(3)-Ag(1)-P(1) P(3)-Ag(1)-S(2)#1 P(1)-Ag(1)-S(2)#1 P(3)-Ag(1)-S(2) P(1)-Ag(1)-S(2) N(1)-Ag(2)-Ag(1) P(4)-Ag(2)-Ag(1) P(2)-Ag(2)-Ag(1) Complex 5 Bond length (Å) Ag(1)-P(3) Ag(1)-P(1) Ag(1)-N(2) Ag(1)-S(1)#1 Ag(1)-S(2)#1 Bond angle (°) P(3)-Ag(1)-P(1) P(3)-Ag(1)-N(2) P(1)-Ag(1)-N(2) P(3)-Ag(1)-S(1)#1 P(1)-Ag(1)-S(1)#1 P(3)-Ag(1)-S(2)#1 P(2)-Ag(2)-S(1) S(2)-Ag(2)-S(1) Complex 6 Bond length (Å) Ag(1)-P(1) Ag(1)-P(2) Bond angle (°) P(1)-Ag(1)-P(2) P(1)-Ag(1)-S(2)#1 P(2)-Ag(1)-S(2)#1 Complex 7 Bond length (Å) Ag(1)-P(2) Ag(1)-P(1) Bond angle (°) P(2)-Ag(1)-P(1) P(2)-Ag(1)-S(2) P(1)-Ag(1)-S(2) Complex 8 Bond length (Å) Ag(1)-P(1) Ag(1)-P(2) Bond angle (°) P(1)-Ag(1)-P(2) P(1)-Ag(1)-S(1) P(2)-Ag(1)-S(1)

128.4(1) 108.2(0) 115.5(9) 126.0(1) 92.7(9) 104.9(2) 93.4(9) 90.1(8)

S(2)-Ag(1)-S(2)#1 P(3)-Ag(1)-Ag(2) P(1)-Ag(1)-Ag(2) S(2)#1-Ag(1)-Ag(2) S(2)-Ag(1)-Ag(2) N(1)-Ag(2)-P(4) N(1)-Ag(2)-P(2) P(4)-Ag(2)-P(2)

73.0(1) 84.0(8) 85.2(7) 133.1(7) 64.0(6) 119.4(2) 98.3(2) 139.5(2)

2.463(2) 2.468(2) 2.500(8) 2.640(3) 2.656(3)

Ag(2)-P(5) Ag(2)-P(2) Ag(2)-S(2) Ag(2)-S(1)

2.464(2) 2.465(2) 2.586(2) 2.710(3)

128.7(8) 109.1(8) 102.3(9) 102.4(7) 106.4(6) 100.5(8) 104.6(7) 97.0(6)

P(1)-Ag(1)-S(2)#1 N(2)-Ag(1)-S(2)#1 S(1)#1-Ag(1)-S(2)#1 P(5)-Ag(2)-P(2) P(5)-Ag(2)-S(2) P(2)-Ag(2)-S(2) P(5)-Ag(2)-S(1)

116.5(8) 94.3(9) 97.0(7) 124.7(7) 106.3(8) 119.7(8) 97.9(7)

2.464(2) 2.494(2)

Ag(1)-S(2)#1 Ag(1)-S(2)

2.564(2) 2.982(3)

129.4(7) 117.5(7) 102.8(7)

P(1)-Ag(1)-S(2) P(2)-Ag(1)-S(2) S(2)-Ag(1)-S(2)#1

100.0(7) 105.3 (7) 95.4(7)

2.480(9) 2.494(9)

Ag(1)-S(2) Ag(1)-S(2)#1

2.643(9) 2.749(9)

131.0(6) 113.3(6) 104.9(6)

P(2)-Ag(1)-S(2) #1 P(1)-Ag(1)-S(2) #1 S(2)-Ag(1)-S(2)#1

98.4(6) 110.3(6) 91.3(5)

2.489(3) 2.545(3)

Ag(1)-S(1) Ag(1)-S(2)

2.625(3) 2.716(3)

107.4(9) 126.4(1) 102.3(9)

P(1)-Ag(1)-S(2) P(2)-Ag(1)-S(2) S(1)-Ag(1)-S(2)

100.4(9) 118.8(1) 102.6(9)

H. . .S angle = 168.2°, symmetry code: x, y + 1, z + 1/2) are formed between the –NH group of the HAMTA ligand and the S atom of another HAMTA ligand. The hydrogen bonds stabilize the 1D structure of the complex (Fig. 1b).

3.2.2. Crystal structures of clusters [Ag3(dppm)3(AMTD)2]2(BF4)2 (dppm) (2) and [Ag3(dppm)3(AMTD)2]2(ClO4)2(dppm) (3) Each asymmetric unit of clusters 2–3 composes of a molecule containing three Ag atoms, two AMTD ligands and three dppm ligands along with a free dppm molecule with 50% occupancy and a free anion (Fig. 2). Three dppm ligands are bonded to three silver atoms in a bidentate-bridging fashion. The coordination structure of the Ag3N1P9S2 core is similar to the Cu3I1P3S2 core of the complex [Cu3I2(dppm)3(dtc)] [25](Fig. 3). Three Ag Ag distances are 3.292(13), 3.643(13), 3.303 (11) Å for cluster 2, and 3.278(12), 3.644(12), 3.312 (11) Å for cluster 3, respectively. According to the sum of van der Waals radius for the silver atoms (3.44 Å) [30], there exist metal–metal interactions between the two pairs of Ag atoms whose distances are less than 3.3 Å, and

there exist weak metal–metal interaction between the two pairs of Ag atoms whose distances are longer than 3.3 Å and less than 3.44 Å. In asymmetric unit, the sulfur atom from an AMTD ligand is coordinated to three silver atoms and caps the triangle from one side forming an Ag3S1 tetrahedron. The core is comprised of three fused distorted hexagonal rings with the S atom located at the center of three rings and is above the Ag3 plane by 1.894(23) and 1.909 (21) Å in clusters 2–3, respectively. Other sulfur atom and nitrogen atom from another AMTD ligand cap from the other side and are bonded in a l3-(g2-S, g1-N) bridging fashion.

3.2.3. Crystal structure of cluster [Ag4(dppm)4(MNBT)2](SO4)(H2O) (4) Cluster 4 is a tetra-nuclear heteroleptic formed with distinctly four soft Ag(I) atoms, four dppm ligands and two MNBT ligands along with a free sulfate and water molecule (Fig. 4). In the asymmetric unit, two dppm ligands are bonded to two silver atoms in a l2-bridging fashion. The bond Ag Ag distance is 3.142(13) Å, which is shorter than the sum of van der Waals radii of two silver

325


Fig. 1. The asymmetry unit of complex 1. Thermal ellipsoids drawn at the 30% probability level, all hydrogen atoms are omitted for clarity. b. The 1-D network structure of 1 under hydrogen bonds. All hydrogen atoms are omitted for clarity.

Fig. 3. The silver center core of 2. Fig. 2. The molecular structure of complex 2. Thermal ellipsoids drawn at the 30% probability level, all hydrogen atoms, a free dppm ligand and BF 4 anions are omitted for clarity.

atoms (3.44 Å), indicating the presence of metal–metal interaction [30]. Two [Ag2(dppm)2]2+ moieties in the asymmetric unit of complex 4 are connected by two S atoms from different MNBT ligands to generate a tetra-nuclear cluster. It is noteworthy that each MNBT ligand is bonded in a l3-(g2-S, g1-N) bridging fashion like the AMTD in clusters 2–3. It is observed that the neighboring benzene rings form offset p p interactions to generate a 1-D infinite chain. The center-to-center distance of 4.015 Å is larger than those

of other complexes [31,32] (Fig. 4a). The p p weaker interactions stabilize the structures of this complex. 3.2.4. Crystal structure of complex [Ag4(dppe)4(HAMTA)2(AMTA)] (5) The silver(I) complex with dppe ligand is reported extensively in previous literatures [33,34]. It is noteworthy that the X-ray analysis of complex 5 reveals that there is a quadrilateral [Ag4(ldppe)4]4+ macrocycle in its structure (Fig. 5), which is rarely found in silver(I) complexes. The HAMTA and AMTA ligands are generated from the H2AMTA ligand in the basic chemical environment by deprotonating. The AMTA ligand is in the middle of four silver

326


Fig. 4. The molecular structure of complex 4. Thermal ellipsoids drawn at the 30% probability level, a part of benzene rings, all hydrogen atoms, SO2 4 anions and free solvent molecules are omitted for clarity.

Fig. 6. The molecular structure of complex 6. All hydrogen atoms, CF3SO 3 anions and free solvent molecules are omitted for clarity.

Fig. 5. The molecular structure of complex 5. Thermal ellipsoids drawn at the 30% probability level, a part of benzene rings and all hydrogen atoms are omitted for clarity.

atoms with 50% occupancy, and it is bonded in l4-(g2-S, g2-N) bridging fashion. In the asymmetric unit of complex 5, the HAMTA ligand acts as bridging ligand by a l2-S atom from thione group. The HAMTA ligands are found to be disordered with occupancy ratios of 0.5:0.5. The geometry around each silver(I) center is distorted tetrahedral as is evident from the angles in the range of 94.3(19)–128.7(8)°. The mean distance Ag-P in complex 5 (2.465 Å) is longer than that in the similar silver complex [Ag (tsac)(dppe)(CH3CN)]n (2.434 Å) [35], which is ascribed to the difference of the mercaptan ligands. 3.2.5. Crystal structures of complex [Ag2(dppb)2(HAMTD)2](CF3SO3) 22(CH3OH) (6) and [Ag2(dppb)2(HMNBT)2](CF3SO3)2 (7) X-ray structure analysis reveals that 6–7 crystallize in the Triclinic space group P-1. In complex 6, each Ag atom adopts a fourcoordinated mode, being bridged by two P atoms from different dppb ligands and two S atoms from two HAMTD ligands along with two solvent free methanol molecules (Fig. 6). The angles around Ag atom in the coordination sphere are in the range of 95.4(7)–129.4 (7)°, which indicates that the geometry around Ag atom is distortedly tetrahedral. The distortedly tetrahedral structure can be attributed to the need to accommodate the bulky ligand groups. The bond angles around the Ag(I) cation decrease in the order: PAg-P > P-Ag-S > S-Ag-S, which is just similar to that in the complex [Ag3(dppm)3{S2 P(OEt)2}2](PF6) [36].

Fig. 7. The molecular structure of complex 7. Thermal ellipsoids drawn at the 30% probability level, all hydrogen atoms and CF3SO 3 anions are omitted for clarity. a. The 1-D infinite chain of complex 7 under p p interactions. All hydrogen atoms and CF3SO 3 anions are omitted for clarity.

The coordination mode of complex 7 is similar with 6 (Fig. 7). In complex 7, a free CF3SO 3 anion is used to balance the charge. It is observed that the neighboring benzene rings form offset p p interactions with the center-to-center distance of 4.019 Å to generate a 1-D infinite chain (Fig. 7a). The structure of complex 7 is stabilized by weak p p interaction. In complexes 6–7, the C–S

327


Fig. 8. The asymmetry unit of complex 8. Thermal ellipsoids drawn at the 30% probability level, all hydrogen atoms, free solvent molecules and CF3SO 3 anions are omitted for clarity. a. The 1-D infinite chain of complex 8. All hydrogen atoms, CF3SO 3 anions and free solvent molecules are omitted for clarity. b. The 2-D network structure bridging by p p interactions of complex 8.

distances in the range of 1.699(7)–1.713(8) Å are somewhat shorter than the C–S single bond (ca. 1.81 Å) due to the delocalization over the NCS moiety [25].

3.2.6. Crystal structures of complex {[Ag(dppb)(HMMBD)2](CF3SO3)2 (CH3OH)(H2O)}n (8) The asymmetry unit of 8 contains a silver atom coordinated by two half of dppb and two HMMBD ligands along with a water molecule, two free methanol molecules and a free CF3SO 3 anion to balance the charge (Fig. 8). The geometry around each silver atom is best described as distorted tetrahedral since the angles are in the range 100.4(9)–126.4(10)°. Each neighboring asymmetry unit is bridged by dppb ligand to form a 1D infinite chain (Fig. 8a). Unexpectedly, the p p weak interactions with the center-to-cen-

ter distance of 3.642(6) and 3.641(7) Å are found between two HMMBD ligands. Finally, complex 8 shows a 2D network structure formed through weak intermolecular offset p p interactions (Fig. 8b). The structure of complex 8 is stabilized by weak p p interactions.

4. Spectroscopy properties analysis 4.1. 1H NMR and

31

P NMR spectra

The 1H NMR and 31P NMR spectra of complexes 1–8 have been measured in the CDCl3 or DMSO-d6 solution at room temperature. There are resonance signals in the range of 7.0–7.6 ppm, which are attributed to protons in the aromatic rings in organic P-donor

328


Table 3 The fluorescent data of complexes 1–8 and various ligands.

Complex Complex Complex Complex Complex Complex Complex Complex dppm dppe dppb HAMTD H2AMTA HMNBT HMMBD

Fig. 9. The luminescent emission spectra of 1–8 in the solid state at room temperature.

ligands and S-donor ligands. The signals of protons of methylene groups in diphosphine ligands are exhibited in the range of 1.7– 2.2 or 3.1–3.7 ppm (3.2 ppm for 2–3, 3.7 ppm for 4, 3.1 ppm for 5, 1.7–2.2 ppm for 6–8). Signals in the range of 3.2–3.6 ppm for 1 and 5–8, are assigned to N–H groups of the different thione ligands in chemical environments. Signals of amino group are shown at 5.7 ppm in the spectra of 1–3 and 6. Resonance signal of methyl group in HMMBD ligand is found at 2.3 ppm in complex 8. The 31P NMR spectra of 2–3 consists of a singlet from free dppm ligand at 24.9 ppm and a pair of well resolved quartets centered around 2.2 ppm with values of 1J(109Ag-31P) = 407 Hz, 1J (107Ag-31P) = 409 Hz, consistent with the gyromagnetic ratio c (107Ag)/c(109Ag) = 1.00. From the 31P NMR spectra of 2–3 we can see that the anions do not affect the chemical shift of 31P signals. Besides, in 31P NMR spectra of 5 and 7, the doublets signals are at 5.5 and 0.3 ppm with values of 1J(109,107Ag-31P) = 274.59 Hz and 1J(109,107Ag-31P) = 396.82 Hz, respectively. In addition, the doublets signals at 5.2 and 2.7 ppm in that of the complex 4 are found with the values of 1J(109,107Ag-31P) = 243.86 Hz and 1J (109,107Ag-31P) = 437.41 Hz.

4.2. Luminescent properties At room temperature, the solid-state excitation and emission spectra of complexes 1–8 were measured (Fig. 9). In previous literature [23,37,38], my co-workers have investigated the luminescent spectra of some complexes with P-donor and S-donor ligands. According to these reports, some data of ligands are measured and summarized in Table 3. The emission peak of HMMBD ligand is found at 433 nm (kex = 362 nm). When excitation peaks are shown at 345 nm, 354 nm, 359 nm, 344 nm, 366 nm, 355 nm, 348 nm and 355 nm respectively, the corresponding emission wavelength of complexes 1–8 displays at 415 nm, 435 nm, 436 nm, 418 nm, 430 nm, 426 nm, 420 nm and 417 nm. All emissions are attributed to ligands-centered [p–p⁄] transition. The emission peaks of complexes 1–4 and 7 are located between those of P-donor and S-donor ligands. In comparison to the P-donor ligand, the emission peaks of complexes 1, 2–3 show red-shift by about 12 nm for 1 and 5 nm (for 2–3), respectively. In comparison to the S-donor ligand, the emission peaks of complexes shows blue-shift by about 21 nm for 1, 2 nm for 2–3, respectively. In comparison to P-donor ligand, the emission peak of

1 2 3 4 5 6 7 8

kex (nm)

kem (nm)

345 354 359 344 366 355 348 355 322 310 317 362 364 352 362

415 435 436 418 430 426 420 417 431 434 450 437 436 412 433

complexes 4 and 7 show blue-shift by about 13 nm and 30 nm, respectively. In comparison to S-donor ligand, the emission peaks of complexes 4 and 7 show red-shift by about 6 nm and 8 nm, respectively. The emissions are attributed to ligands-centered [p– p⁄] transition based on both of the P-donor and S-donor ligands . The emission peaks of complexes 5, 6 and 8 are not located between those of P-donor and S-donor ligands. The emission peak of complex 5 shows blue-shift about 4 nm from that of P-donor and 6 nm from that of S-donor ligand. The emissions are attributed to ligands-centered [p–p⁄] transition based on the P-donor ligands. The emission peaks of complexes 6 and 8 are located near Sdonor ligands. The emission peak of complex 6 is about 24 nm from that of P-donor and 11 nm from that of S-donor ligand, and the emission peak of complex 8 is about 33 nm from that of Pdonor and 16 nm from that of S-donor ligand. The emissions are attributed to ligands-centered [p–p⁄] transition based on the Sdonor ligands. Complexes 6–8 are obtained by the reactions of mercaptan ligands and the complex [Ag2(l-dppb)2(CF3SO3)2] which has emission peak at 411 nm with the corresponding excitation peak at 338 nm [24]. Compared to the complex [Ag2(l-dppb)2(CF3SO3)2], the emission peaks of complexes 6–8 show red-shifts, which is ascribed to their S-donor ligands. It is noteworthy that the photo-luminescent properties of complexes 2 and 3 are similar, which is proved that the free anion doesn’t affect luminescent behavior when they have analogous structures again [39].

5. Conclusions In conclusion, complexes 1–8 have been synthesized and fully characterized by IR, 1H NMR, 31P NMR spectroscopy and solid-state luminescence spectroscopy. Their structures are determined by Xray crystallography. Complex 1 displays that the 1-D chain by hydrogen bonds. Complexes 2–4 are multi-nuclear clusters with Ag-Ag interactions. The complexes 6–8 are prepared by ring-opening reaction of [Ag2(dppb)2(CF3SO3)2], forming l-S di-nuclear structure, infinite 1D chain and 2D networks, respectively. These emissive behavior of these complexes is attributed to ligand-centered [p–p⁄] transition. It is proved that the free anion doesn’t affect luminescent behavior when they have analogous structures. In the future, we hope our results could offer new strategy for design of distinctive structures and luminescent properties of group 11 complexes in self-assembly chemistry.


Acknowledgements This work has been supported by the National Natural Science Foundation of China (Grant Nos. 21171119, 81573822, 11574408, 21376008 and 11204191), Beijing Natural Science Foundation of (Grant No. 2172017), the National High Technology Research and Development Program 863 of China (Grant No. 2012AA063201), the Scientific Research Base Development Program of the Beijing Municipal Commission of Education, the National Special Fund for the development of Major Research Equipment and Instruments (Grant No. 2012YQ14000508), the Technology Foundation for Selected Overseas Chinese, the Beijing Municipal Education Commission (KM201510028006) and the Scientific Research Base Development Program of the Beijing Municipal Commission of Education. Appendix A. Supplementary data CCDC 1450998, 1448902, 1448903, 1448904, 1448905, 1448906, 1448908, 1448907 contains the supplementary crystallographic data for 1–8. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: [email protected]. References [1] Y.-P. Xie, J.-L. Jin, G.-X. Duan, X. Lu, T.C.W. Mak, Coord. Chem. Rev. 331 (2017) 54. [2] O. Fuhr, S. Dehnenb, D. Fenske, Chem. Soc. Rev. 42 (2013) 1871. [3] E.R.T. Tiekink, Coord. Chem. Rev. 275 (2014) 130. [4] C. Santini, M. Pellei, V. Gandin, M. Porchia, F. Tisato, C. Marzano, Chem. Rev. 114 (2014) 815. [5] S. Medici, M. Peana, G. Crisponi, V.M. Nurchi, J.I. Lachowicz, M. Remelli, M.A. Zoroddu, Coord. Chem. Rev. 327–328 (2016) 349. [6] (a) X.L. Yang, G.J. Zhou, W.-Y. Wong, Chem. Soc. Rev. 44 (2015) 8484; (b) S. Singh, S. Bhattacharya, RSC Adv. 4 (2014) 49491. [7] K. Tsugea, Y. Chishina, H. Hashiguchi, Y. Sasaki, M. Kato, S. Ishizaka, N. Kitamura, Coord. Chem. Rev. 306 (2016) 636. [8] (a) W.W. Zi, F.D. Toste, Chem. Soc. Rev. 45 (2016) 4567; (b) Z. Qin, Z. Liu, R. Cong, H. Xie, Z. Tang, H. Fan, J. Chem. Phys. 140 (2014) 114307; (c) M. Tiwari, A. Kumar, U. Shankar, R. Prakash, Biosens. Bioelectron. 85 (2016) 529.

329

[9] F. Lazreg, F. Nahra, C.S.J. Cazin, Coord. Chem. Rev. 293–294 (2015) 48. [10] J. Chen, T. Teng, L.J. Kang, X.-L. Chen, X.-Y. Wu, R.M. Yu, C.-Z. Lu, Inorg. Chem. 55 (2016) 9528. [11] D. Kakizoe, M. Nishikawa, T. Degawa, T. Tsubomura, Inorg. Chem. Front. 3 (2016) 1381. [12] D.D. Yang, W.L. Xu, X.W. Cao, S.J. Zheng, J.G. He, Q. Ju, Z.L. Fang, W. Huang, Inorg. Chem. 55 (2016) 7954. [13] R.G. Pearson, Inorg. Chim. Acta 240 (1995) 93. [14] D. Li, W.-J. Shi, L. Hou, Inorg. Chem. 44 (2005) 3907. [15] G. Christofidis, P.J. Cox, P. Aslanidis, Polyhedron 31 (2012) 502. [16] R. Sultana, T.S. Lobana, R. Sharma, A. Castineiras, T. Akitsu, K. Yahagi, Y. Aritake, Inorg. Chim. Acta 363 (2010) 3432. [17] T.S. Lobana, R. Sultana, R.J. Butcher, J.P. Jasinski, J.A. Golen, A. Castineiras, K. Pröpper, F.J. Fernandez, M.C. Vega, J. Organomet. Chem. 745–746 (2013) 460. [18] T.S. Lobana, R. Sultana, R.J. Butcher, J.P. Jasinski, T. Akitsu, Z. Anorg. Allg. Chem. 640 (2014) 1688. [19] A. Ilie, C.I. Rat, S. Scheutzow, C. Kiske, K. Lux, T.M. Klapotke, C. Silvestru, K. Karaghiosoff, Inorg. Chem. 50 (2011) 2675. [20] P. Karagiannidis, P. Aslanidis, S. Kokkou, C.J. Cheer, Inorg. Chim. Acta 172 (1990) 247. [21] S.-C. Chen, R.-M. Yu, Z.-G. Zhao, S.-M. Chen, Q.-S. Zhang, X.-Y. Wu, F. Wang, C.Z. Lu, Cryst. Growth Des. 10 (2010) 1155. [22] S. Nawaz, A.A. Isab, K. Merz, V. Vasylyeva, N. Metzler-Nolte, M. Saleem, S. Ahmad, Polyhedron 30 (2011) 1502. [23] Q.-M. Qiu, M. Liu, Z.-F. Li, Q.-H. Jin, X. Huang, Z.-W. Zhang, C.-L. Zhang, Q.-X. Meng, J. Mol. Struct. 1062 (2014) 125. [24] L.-N. Cui, Z.-F. Li, Q.-H. Jin, X.-L. Xin, C.-L. Zhang, Inorg. Chem. Commun. 20 (2012) 126. [25] G. Rajput, M.K. Yadav, M.G.B. Drew, N. Singh, Inorg. Chem. 54 (2015) 2572. [26] G.M. Sheldrick, SHELXS-97 and SHELXL-97, Software for Crystal Structure Analysis, Siemens Analytical X-ray Instruments Inc., Wisconsin, Madison, USA, 1997. [27] G.M. Sheldrick, SHELXTL NT Version 5.1, Program for Solution and Refinement of Crystal Structures, University of Göttingen, Germany, 1997. [28] A.L. Spek, J. Appl. Crystallogr. 36 (2003) 7. [29] Y.-Z. Cui, Y. Yuan, Z.-F. Li, M. Liu, Q.-H. Jin, N. Jiang, L.-N. Cui, S. Gao, Polyhedron 112 (2016) 118. [30] S. Sculfort, P. Braunstein, Chem. Soc. Rev. 40 (2011) 2741. [31] S.H. Lim, S.M. Cohen, Inorg. Chem. 52 (2013) 7862. [32] T.S. Lobana, R. Sharma, R.J. Butcher, Polyhedron 27 (2008) 1375. [33] Effendy, C.D. Nicola, C. Pettinari, A. Pizzabiocca, B.W. Skelton, N. Somers, A.H. White, Inorg. Chim. Acta 359 (2006) 64. [34] P. Teo, L.L. Koh, T.S.A. Hor, Chem. Commun. (2007) 4221. [35] M. Dennehy, O.V. Quinzani, S.D. Mandolesi, R.A. Burrow, J. Mol. Struct. 998 (2011) 119. [36] C.W. Liu, B. Sarkar, B.-J. Liaw, Y.-W. Lin, T.S. Lobana, J.-C. Wang, J. Organomet. Chem. 694 (2009) 2134. [37] Q.-H. Jin, Y. Yuan, Y.-P. Yang, Q.-M. Qiu, M. Liu, Z.-F. Li, Z.-W. Zhang, C.-L. Zhang, Polyhedron 101 (2015) 56. [38] X. Huang, Z.-F. Li, Q.-H. Jin, Q.-M. Qiu, Y.-Z. Cui, Q.-R. Yang, Polyhedron 65 (2013) 129. [39] Y.-Z. Cui, Y. Yuan, H.-L. Han, Z.-F. Li, M. Liu, Q.-H. Jin, Y.-P. Yang, Z.-W. Zhang, Z. Anorg. Allg. Chem. 642 (2016) 953.