New Strapped Porphyrins as Hosts for Fullerenes: Synthesis and

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is © The Royal Society of Chemistry 2011

Supporting Information New Strapped Porphyrins as Hosts for Fullerenes: Synthesis and Complexation Study

Jean-Benoît Giguère and Jean-François Morin* Department of Chemistry and Centre de recherche sur les matériaux avancés (CERMA), 1045 Ave de la Médecine, Université Laval, Québec, Canada G1V 0A6 [email protected]

Table of Contents 1.

General procedure ....................................................................................................................... 2

2.

Experiment Details for the Complexation Study of hosts H1-H7 with Fullerenes..................... 3

3.

Experimental data for compounds 2-6, 8, 9, 12, H1-H7. .......................................................... 13

4.

References ................................................................................................................................. 46

1


1. General procedure

Chemical reagents were purchased from Sigma-Aldrich Co. Canada, Alfa Aesar Co. or TCI America Co. and were used as received. Solvents used for organic synthesis were obtained from Fisher Scientific and purified with a Solvent Purifier System (SPS) (Vacuum Atmosphere Co., Hawthorne, USA) except CH2Cl2 for porphyrin synthesis was used as received. Other solvents were obtained from Fisher Scientific and were used as received. Analytical thin-layer chromatography was performed with silica gel 60 F254, 0.25 mm pre-coated TLC plates (Silicycle, Québec, Canada). Flash column chromatographies were performed on 230-400 mesh silica gel R10030B (Silicycle, Québec, Canada). Nuclear magnetic resonance (NMR) spectra were recorded on a Varian Inova AS400 spectrometer (Varian, Palo Alto, USA) at 400 MHz (1H), 376 MHz (19F) and 100 MHz (13C). Signals are reported as m (multiplet), s (singlet), d (doublet), t (triplet), dd (doublet of doublet) and br s (broad singlet) and coupling constants are reported in hertz (Hz). The chemical shifts are reported in ppm (δ) relative to residual solvent peak or TMS. High-resolution mass spectra (HRMS) were recorded with a Agilent 6210 Time-of-Flight (TOF) LC-MS apparatus equipped with a ESI or APPI ion source (Agilent Technologies, Toronto, Canada). UV-visible absorption spectra were recorded on a Varian diode-array spectrophotometer (model Cary 500).

Molecular geometry optimizations were done using HyperChemTM with Amber molecular force field in vacuo.

2


2. Experiment Details for the Complexation Study of hosts H1-H7 with Fullerenes

General Procedure UV-visible titration experiments were carried out with solutions of porphyrin hosts H1-H7 (1.2 µM to 1.7 µM) in toluene or in acetonitrile/toluene 1:1 (3 mL) in a quartz cuvette (1 cm path length). For C60 titration experiments, a C60 solution (7.5x10-4 M) containing the same host concentration as the sample cell (1.2 – 1.7 µM) was added in aliquots (10 to 50 µL) to the sample cell and the same volume of a C60 stock solution (7.5x10-4 M) was added to the reference cell. For C70 titration experiments, a stock solution (5.9x10-4 M) was added in aliquots (5 to 50 µL) to both the sample cell and the reference cell and the absorbance was corrected for dilution. The absorbance of the Soret band (415-425 nm) was recorded after each addition and a plot of ∆A versus [fullerene] was carried out and the binding constant (Ka) was evaluated by non-linear curve fitting with OriginPro 8.0 (OriginLab) using the equation1:

Δ‫= ܣ‬

Δ‫ ܣ‬ஶ ൬ሺ1 + ‫ܭ‬௔ ሾ‫ܨ‬ሿ + ሾ‫ܪ‬ሿ‫ܭ‬௔ ሻ − ඥሺ1 + ‫ܭ‬௔ ሾ‫ܨ‬ሿ + ሾ‫ܪ‬ሿ‫ܭ‬௔ ሻଶ − 4‫ܭ‬௔ଶ ሾ‫ܨ‬ሿሾ‫ܪ‬ሿ൰ 2‫ܭ‬௔ ሾ‫ܪ‬ሿ

where ∆A = A – A0, [H] is the concentration of the host solution and [F] is the concentration of the fullerene solution and ∆A∞ the absorbance difference at saturation of the binding sites.

3


Complexation of C60 by H1 [1.6 µM] in MeCN/Toluene 1:1

0 eq. C60

Absorbance (a.u.)

0.8

∆A 0.07 0.06

0.7

85 eq. C60

0.6

0.05 0.04 -1

Ka=7 000 M 2 R =0.9995

0.03

0.5

0.02

0.4 0.01

0.3

0.00 0

20

40

60

80

100

120

140

160

6

[C60] (x10 M)

0.2 0.1 0.0 420

430

440

450

460

470

Wavelength (nm)

Absorbance (a.u.)


0.8

0 eq. C60

0.05

∆A 0.04

0.7

95 eq. C60

0.03

0.6 -1

Ka=5 000 M 2 R =0.992

0.02

0.5 0.01

0.4 0.00

0.3

0

20

40

60

80

100 6

120

140

160

[C60] (x10 M)

0.2 0.1 0.0

415 420 425 430 435 440 445 450 455 460 465 470 475 480

Wavelength (nm)

4


Complexation of C60 by H4 [1.5 µM] in Toluene

Absorbance (a.u.)

0 eq. C60

0.10

∆A 0.08

0.7

105 eq. C60

0.06

0.6 0.04

Ka=1000 M 2 R =0.9997

0.5 0.02

-1

0.4 0.00

0.3

0

20

40

60

80

100 120 140 160 180 6

[C60] (x10 M) 0.2 0.1 0.0 415 420 425 430 435 440 445 450 455 460 465 470 475

Wavelength (nm)

Absorbance (a.u.)


0 eq. C60 ∆A

0.8

0.35 0.30

0.7

0.25

71 eq. C60

0.20 -1

0.6

Ka=18 000 M 2 R =0.9999

0.15 0.10

0.5

0.05

0.4

0.00 0

0.3

10 20 30 40 50 60 70 80 90 100 110 120 6

[C60] (x10 M)

0.2 0.1 0.0 400

420

440

460

480

500

520

540

560

580

Wavelength (nm)

5


Absorbance (a.u.)


0 eq. C70

∆A

0.20

0.8

15 eq. C70

0.7

0.15

0.6

0.10

0.5

-1

Ka=22 000 M 2 R =0.994

0.05

0.4 0.00

0.3

0

5

10

15

20

25

6

[C70] (x10 M)

0.2 0.1 0.0 400

420

440

460

480

500

520

540

560

580

Wavelength (nm)

Absorbance (a.u.)


∆A

0.9

0 eq. C60

0.8

0.030 0.025 0.020

0.7

92 eq. C60 0.015 -1

0.6

Ka=4000 M 2 R =0.989

0.010

0.5 0.005

0.4 0.000 0

0.3

20

40

60

80

100

120

140

160

6

[C60] (x10 M)

0.2 0.1 0.0 410

420

430

440

450

460

470

Wavelength (nm)

6


Absorbance (a.u.)


0 eq. C60 ∆A

1.0

0.25

0.9 0.8

41 eq. C60

0.7

0.20 0.15

0.6

-1

Ka=31 000 M 2 R =0.9998

0.10

0.5 0.05

0.4

0.00

0.3

0

10

20

30

40

50

60

70

6

0.2

[C60] (x10 M)

0.1 0.0 410

420

430

440

450

460

470

480

490

500

Wavelength (nm) Complexation of C70 by H5 [1.5 µM] in MeCN/Toluene 1:1

∆A 0.18

Absorbance (a.u.)

1.0

0 eq. C70

0.9

0.16 0.14 0.12

0.8

24 eq. C70

0.10 0.08

0.7

Ka=37 000 M 2 R =0.998

0.06

0.6

-1

0.04

0.5

0.02

0.4

0.00 0

5

10

15

20 B

0.3

25

30

35

40

6

[C70] (x10 M)

0.2 0.1 0.0 400

420

440

460

480

500

Wavelength (nm)

7



Absorbance (a.u.)

0.9

0 eq. C60 ∆A

0.20

56 eq. C60

0.15

0.6 0.10

Ka=23 000 M 2 R =0.9998

-1

0.05

0.3

0.00 0

10

20

30

40

50

60

70

6

[C60] (x10 M)

0.0 420

450

480

510

540

570

Wavelength (nm)

Absorbance (a.u.)


0.8

0 eq. C60 ∆A

0.4

0.7

39 eq. C60

0.6

0.3 -1

0.5

0.2

0.4

0.1

0.3

Ka=315 000 M 2 R =0.9987

0.0 0

10

20

30

40

50

6

0.2

[C60] (x10 M)

0.1 0.0 390

420

450

480

510

540

570

Wavelength (nm)

8



Absorbance (a.u.)

0.9

0 eq. C70 ∆A

0.8

0.16 0.14 0.12

0.7

23 eq. C70

0.6

0.10 -1

0.08

Ka=29 000 M 2 R =0.9998

0.06

0.5

0.04

0.4

0.02

0.3

0.00 0

5

10

15

20

25

30

6

0.2

[C70] (x10 M)

0.1 0.0 400 420 440 460 480 500 520 540 560 580 600 620


Absorbance (a.u.)

0.8

0 eq. C70 ∆A

0.4

0.7 0.6

17 eq. C70

0.3 -1

0.5

Ka=389 000 M 2 R =0.9991

0.2

0.4

0.1

0.3

0.0 0.0

0.5

1.0

1.5

2.0

6

[C70] (x10 M)

0.2 0.1 0.0

380 400 420 440 460 480 500 520 540 560 580 600 620

Wavelength (nm)

9



0 eq. C60 ∆ A

Absorbance (a.u.)

0.55 0.50

0.12

0.10

65 eq. C60

0.45 0.40

0.08

0.06

Ka=9 000 M 2 R =0.9995

0.35 0.04

-1

0.30 0.02

0.25 0.00

0.20

0

20

40

60

80

100

120

6

[C 60 ] (x10 M)

0.15 0.10 0.05 0.00 400

450

500

550

600


Absorbance (a.u.)

0.5

0 eq. C60

∆A

0.20 0.18 0.16 0.14

0.4

14 eq. C60

0.12

Ka=120 000 M 2 R =0.9999

0.10 0.08

0.3

-1

0.06 0.04

0.2

0.02 0.00 0

5

10

15

20

25

6

0.1

[C60] (x10 M)

0.0 400 420 440 460 480 500 520 540 560 580

Wavelength (nm)

10



0 eq. C70

∆A 0.14 0.12

Absorbance (a.u.)

0.5

24 eq. C70

0.10 0.08

0.4

-1

Ka=21 000 M 2 R =0.9997

0.06 0.04

0.3

0.02 0.00 0

0.2

5

10

15

20

25

30

35

40

6

[C70] (x10 M) 0.1

0.0 410

420

430

440

450

460

Wavelength (nm)

Absorbance (a.u.)

Complexation of C70 by H7 [1.7 µM] in MeCN/Toluene

∆A

0.5

0 eq. C70

0.20

0.15

0.4 6 eq. C70

Ka=350 000 M 2 R =0.9998

0.10

0.3

-1

0.05

0.2

0.00 0

1

2

3

4

5

6

7

8

9

10 11

6

[C 70 ] (x10 M)

0.1

0.0 400

450

500

550

600

Wavelength (nm)

11


Job’s plot of H7 with C60 in MeCN/Toluene 1:1 at a fixed [H7]+[C60]=4x10-6 M.

0.5

0.67

0.04 ∆A

0.03

0.02

0.01

0.00 0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

[H]/([H]+[C60]

Job’s plot of H7 with C70 in MeCN/Toluene 1:1 at a fixed [H7]+[C70]=4x10-6 M.

0.5

0.67

0.10

∆A

0.08

0.06

0.04

0.02

0.00 0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

[H]/([H]+[C70]

12


3. Experimental data for compounds 2-6, 8, 9, 12, H1-H7.

Synthesis of compound 2a: To a 500 mL round bottom flask equipped with a stir bar and sealed with a septum was added 3hydroxybenzaldehyde (293 mg, 2.40 mmol), 5-(2,6-dichlorophenyl)dipyrromethane 1 (700 mg, 2.40 mmol) and CH2Cl2 (240 mL) and the mixture was degassed with a flow of nitrogen for 15 minutes. Trifluoroacetic acid (263 mg, 2.31 mmol) was added dropwise and the reaction was stirred for 60 minutes. Then, p-chloranil (480 mg, 1.95 mmol) was added and the solution was stirred for 30 minutes at room temperature and afterward heated to reflux for 2 hours. The acid was neutralized with triethylamine (494 mg, 4.90 mmol) and silica gel (3.5 g) was added and the solvent evaporated under pressure. The product adsorbed on silica gel was loaded on the top of a silica gel chromatography column and eluted with toluene followed by 7% AcOEt/93% toluene. The product obtained was dissolved in a mixture CH2Cl2 and MeOH and layered with hexanes. A purple precipitate appeared and it was recovered via filtration to afford 485 mg of compound 2a (51% yield) as a purple solid. Mp: >250 °C. 1H NMR (DMSO, 300 MHz): 9.90 (s, 2H), 8.92 (d, 2H,

J = 4.7 Hz), ), 8.71 (d, 2H, J = 4.8 Hz), 8.02 (m, 4H), 7.92 (m, 2H), 7.70-7.56 (m, 6H), 7.24 (m, 2H), -2.84 (s, 2H).13C NMR: 155.88, 141.79, 138.56, 137.46, 132.34 (2C), 131.94, 129.94 (2C), 128.37, 127.98, 125.80, 121.93, 120.29, 115.28, 113.82. HRMS (APPI+): calcd. for C44H26Cl4N4O2: 782.0804, found: 782.0802 (M)+.

13


9.0

PPM

8.0

-2.8401 1.618

2.5000

3.3551

1.915

7.6845 7.6602 7.6184 7.5904 7.2549 7.2288 6.448

8.0310 8.0059 7.9532 7.9294 4.247 2.313

8.9295 8.9137 8.7261 8.7104 3.707

3.798

1.921

9.9034

SpinWorks 2.5: JBG-4-199

7.0

6.0

5.0

4.0

3.0

file: C:\Users\Jean-Benoit\Documents\RMN\JBG 4 - 5\jbg-4-199\JBG40F.201 expt: M00 transmitter freq.: 300.136584 MHz time domain size: 16384 points width: 6024.13 Hz = 20.071304 ppm = 0.367684 Hz/pt number of scans: 16

2.0

1.0

0.0

-1.0

-2.0

freq. of 0 ppm: 300.134790 MHz processed size: 8192 complex points LB: 0.735 GB: 0.0000

PPM

150.0

140.0

130.0

120.0

file: C:\Users\Jean-Benoit\Documents\RMN\JBG 4 - 5\jbg-4-199\JBG40F.019 expt: M02 transmitter freq.: 75.476535 MHz time domain size: 32768 points width: 18520.37 Hz = 245.379192 ppm = 0.565197 Hz/pt number of scans: 10000

115.2813 113.8231

120.2943

121.9307

128.3754 127.9856 125.8021

131.9490

138.5558 137.4644

141.7900

155.8795


110.0

100.0

90.0

80.0

70.0

60.0

50.0

40.0

30.0

20.0

10.0


14


. Synthesis of compound 2b: To a round bottom flask equipped with a stir bar and sealed with a septum was added free base porphyrin 2a (250 mg, 0.32 mmol), Zn(OAc)2.2H2O (700 mg, 3.20 mmol), CH2Cl2 (10 mL) and MeOH (10 mL) and the mixture was stirred at room temperature overnight. The solvent was evaporated under reduced pressure and the residue was purified by column chromatography on silica gel (eluent: AcOEt) to afford 277 mg (quant. yield) of compound 2b as a purple solid. Mp: >250 °C. 1H NMR (DMSO, 300 MHz): 9.81 (s, 2H), 8.84 (d, 2H, J = 4.5 Hz), 8.61 (d, 2H, J = 4.6 Hz), 8.00-7.94 (m, 4H), 7.92-7.85 (m, 2H), 7.65-7.53 (m, 6H) 7.20 (m, 2H). 13C NMR: 155.52, 149.47, 148.40, 143.58, 140.08, 137.62, 132.59, 131.27, 129.84, 128.05, 127.47,

125.78,

121.93,

120.44,

114.62, 114.13.

HRMS

(APPI+):

calcd.

for

C44H25Cl4N4O2Zn: 845.0018, found: 845.0002 (M+H)+.

15


PPM

150.0

140.0

130.0

120.0

file: C:\Users\Jean-Benoit\Documents\RMN\JBG 4 - 5\jbg-5-107\JBG51F.107 expt: X02 transmitter freq.: 75.476535 MHz time domain size: 32768 points width: 18520.37 Hz = 245.379192 ppm = 0.565197 Hz/pt number of scans: 1280

110.0

100.0

90.0

80.0

70.0

60.0

50.0

40.0

30.0

20.0

14.1268

20.7963

40.4096 40.1307 39.8519 39.7018 39.5752 39.2962 39.0194 38.8459 38.7418 38.6038

59.7883

114.6180 114.1260

121.9315 120.4450

125.7800

132.5887 131.2761 129.8350 128.0536 127.4722

137.6281

140.0824

143.5897

149.4757 148.4035

155.5241


10.0

0.0


16


Synthesis of compound 4: To a 500 mL round bottom flask equipped with a stir bar and sealed with a septum was added 3-(8bromooctyloxy)benzaldehyde (750 mg, 2.39 mmol), 5-(2,6-Dichlorophenyl)dipyrromethane 1 (700 mg, 2.40 mmol) and CH2Cl2 (240 mL) and the mixture was degassed with a continuous flow of nitrogen for 15 minutes. Trifluoroacetic acid (486 mg, 4.27 mmol) was added dropwise and the reaction was stirred for 60 minutes. Then, p-chloranil (884 mg, 3.60 mmol) was added and the reaction allowed to stir overnight. The acid was neutralized with triethylamine (ca. 1.5 mL) and the solvent was removed under reduced pressure. The crude solid was triturated with methanol and run through a silica gel column chromatography on using 50% toluene/50% hexanes as eluent. This afforded the free base porphyrin (ca. 600 mg) that was dissolved in CH2Cl2 (15 mL) and methanol (5 mL) and Zn(OAc)2.2H2O (470 mg, 2.14 mg) was added to the resulting solution. The reaction was heated at 40 °C overnight, the solvent was removed and the crude product was purified by column chromatography on silica gel (eluent: 40% CH2Cl2/60% hexanes) to afford 585 mg (40% yield) of compound 4 as a purple solid. Mp: 135-137 °C, 1H NMR (CDCl3, 400 MHz): 8.99 (d, 2H, J = 4.6 Hz), 8.73 (d, 4H, J = 4.6

Hz), 7.80 (d, 2H, J = 7.2 Hz), 7.77-7.72 (m, 6H), 7.67-7.62 (m, 2H), 7.58 (t, 2H, J = 8.1 Hz), 7.24 (dd, 2H, J = 4.43 Hz, J = 2.0 Hz), 4.05 (t, 4H, J = 6.3 Hz), 3.32 (t, 4H, J = 6.9 Hz), 1.83-1.73 (m, 8H), 1.48-1.25 (m, 16 H).

13

C NMR: 157.53, 150.69, 149.41, 143.41,

140.68, 138.87, 138.84, 138.81, 133.41, 130.32, 127.99, 127.79, 127.54, 121.33, 121.16, 115.17, 114.45, 114.42, 68.41, 34.27, 33.00, 29.55, 29.45, 28.92, 28.32, 26.24. HRMS (APPI+): calcd. for C60H55Cl4N4O2Zn: 1225.0732, found: 1225.0683 (M+H)+.

17


SpinWorks 3: jbg-5-21

PPM

8.4

8.0

7.6

7.2

6.8

6.4

6.0

5.6

5.2

4.8

4.4

4.0

3.6

3.2

2.8

file: ...g-5-21_12Jun2011\PROTON_01.fid\fid block# 1 expt: "s2pul" transmitter freq.: 399.775827 MHz

freq. of 0 ppm: 399.773444 MHz

time domain size: 47896 points width: 6396.42 Hz = 16.0000 ppm = 0.133548 Hz/pt

LB: 1.500 GF: 0.0000 Hz/cm: 151.701 ppm/cm: 0.37946

2.4

2.0

1.6

1.2

0.8

0.4

0.0

processed size: 65536 complex points

number of scans: 8

18


Synthesis of compound 3: To a 500 mL round bottom flask equipped with a stir bar and sealed with a septum was added 3-(8bromohexyloxy)benzaldehyde (370 mg, 1.30 mmol), 5-(2,6-dichlorophenyl)dipyrromethane 1 (380 mg, 1.30 mmol) and CH2Cl2 (130 mL) and the mixture was degassed with a continuous flow of nitrogen for 15 minutes. Trifluoroacetic acid (263 mg, 2.31 mmol) was added dropwise and the reaction was stirred for 60 minutes. Then, p-chloranil (480 mg, 1.95 mmol) was added and the reaction heated to reflux for 60 minutes. The acid was neutralized with triethylamine (256 mg, 2.54 mmol) and Zn(OAc)2.2H2O (1,42 g, 6.50 mmol) and methanol (20 mL) were added and the resulting solution was heated to reflux for 60 minutes. The solvent was removed under reduced pressure and the crude product triturated with methanol (30 mL) and the residue was purified by column chromatography on silica gel (eluent: gradient from 30% CH2Cl2/70% hexanes to 45% CH2Cl2/55% hexanes) to afford 316 mg (41% yield) of compound 3 as a purple solid. Mp: 171-173 °C. 1H NMR (CDCl3, 400 MHz): 8.98 (d, 2H, J = 4.7 Hz), 8.72 (d, 4H, J = 4.6 Hz), 7.82-

7.75 (m,8H), 7.77-7.72 (m, 6H), 7.67 (t, 2H, J = 8.2 Hz), 7.59 (t, 2H, J = 8.1 Hz), 7.27 (dd, 2H, J = 4.4 Hz, J = 2.0 Hz), 4.11 (t, 4H, J = 6.5 Hz), 3.38 (t, 4H, J = 6.7 Hz), 1.91-1.80 (m, 8H), 1.55-1.47 (m, 8 H).

13

C NMR: 157.48, 150.63, 149.37, 144.05, 140.72, 138.87,

138.85, 138.82, 133.32, 130.50, 130.27, 127.98, 127.52, 121.22, 121.13, 115.10, 114.33, 68.19, 34.07, 32.93, 29.45, 28.21, 25.60. HRMS (APPI+): calcd. for C56H47Cl4N4O2Zn: 1169.0106, found: 1169.0136 (M+H)+.

19



PPM

8.8

8.4

8.0

7.6

7.2

6.8

6.4

6.0

5.6

5.2

4.8

4.4

4.0

3.6

3.2

2.8

file: ...-5-117_09Jul2011\PROTON_01.fid\fid block# 1 expt: "s2pul" transmitter freq.: 399.775827 MHz



LB: 1.500 GF: 0.0000 Hz/cm: 159.571 ppm/cm: 0.39915

2.4

2.0

1.6

1.2

0.8

0.4

0.0


number of scans: 8

20


O O HO

O

3

OH 3

O

Synthesis of compound 5: To a 10 mL round bottom flask equipped with a stir bar and sealed with a septum was added anthraflavic acid ( 300 mg, 1.25 mmol), 2-[2-(2-chloroethoxy)ethoxy]ethanol (527 mg, 3.13 mmol), K2CO3 (431 mg, 3.13 mmol) and NaI (47 mg, 0.31 mmol) and DMF (3 mL). The reaction mixture was heated and stirred at 120 °C for 2 hours. Once cooled, CH2Cl2 and EtOAc were added and the organic layer was washed twice with water, dried over Na2SO4 and the solvent removed under reduced pressure. The crude product was recrystallized from EtOAc (ca. 25 mL) to afford 466 mg (76% yield) of compound 5 as an off-white solid. Mp: 119-121 °C. 1H NMR (CDCl3, 400 MHz): 8.21 (d, 2H, J = 8.6 Hz), 7.71 (d, 2H, J = 2.4

Hz), 7.26 (dd, 2H, J = 4.3 Hz, J = 2.5 Hz), 4.31 (t, 4H, J = 4.3 Hz), 3.93 (t, 4H, J = 4.6 Hz) 3.80-3.69 (m, 12H), 3.63 (t, 4H, J = 4.6 Hz) 2.47 (bs, 2H).

13

C NMR: 182.34, 163.79,

135.95, 129.92, 127.49, 121.40, 110.76, 72.74, 71.15, 70.60, 69.66, 68.27, 62.00. HRMS (APPI+): calcd. for C26H33O10: 505.2068, found: 505.2041 (M+H)+.

21



PPM

7.6

7.2

6.8

6.4

6.0

5.6

5.2

4.8

4.4

4.0

3.6

3.2

2.8

2.4

file: ...-5-005_11May2011\PROTON_01.fid\fid block# 1 expt: "s2pul" transmitter freq.: 399.775827 MHz



LB: 1.500 GF: 0.0000 Hz/cm: 139.210 ppm/cm: 0.34822

2.0

1.6

1.2

0.8

0.4

0.0


number of scans: 8

22


Synthesis of compound 6: To a flame dried 10 mL round bottom flask equipped with a stir bar and sealed with a septum was added anthraquinone 5 (250 mg, 0.495 mmol), triethylamine (200 mg, 1.98 mmol) and anhydrous CH2Cl2 (2 mL). The reaction vessel was then cooled to 0 °C using an ice bath and tosyl chloride (236 mg, 1.24 mmol) was added. The reaction was left to warm to room temperature overnight. The solvent was removed under reduce pressure and the crude product was purified by column chromatography on silica gel using (eluent: 3% MeOH/97% CH2Cl2) to afford 380 mg (94% yield) of compound 6 as a yellow solid. Mp: 98-101 °C. 1H NMR (CDCl3, 400 MHz): 8.21 (d, 2H, J = 8.6 Hz), 7.79 (d, 4H, J = 8.3

Hz), 7.70 (d, 2H, J = 2.3 Hz), 7.33 (d, 4H, J = 7.7 Hz), 7.25 (dd, 2H, J=4.4 Hz, J=2.5 Hz), 4.29 (t, 4H, J = 4.3 Hz), 4.17 (t, 4H, J = 4.7), 3.89 (t, 4H, J = 4.7 Hz), 3.73-3.66 (m, 8H), 3.66-3.61 (m, 4H), 2.43 (s, 6H). 13C NMR: 182.31, 163.83, 145.08, 135.95, 133.15, 130.07, 129.91, 128.20, 127.45, 121.29, 110.85, 71.06, 71.03, 69.70, 69.48, 68.99, 68.32, 21.89. HRMS (APPI+): calcd. for C40H45O14S2: 813.2245, found: 813.2210 (M+H)+.

23



PPM

7.6

7.2

6.8

6.4

6.0

5.6

5.2

4.8

4.4

4.0

3.6

3.2

2.8

2.4

file: ...-5-007_12Jun2011\PROTON_01.fid\fid block# 1 expt: "s2pul" transmitter freq.: 399.775827 MHz



LB: 1.500 GF: 0.0000 Hz/cm: 138.203 ppm/cm: 0.34570

2.0

1.6

1.2

0.8

0.4

0.0


number of scans: 8

24


Synthesis of compound 8: To a 25 mL round bottom flask equipped with a stir bar and sealed with a septum was added 2,6dimethoxyanthracene (180 mg, 0.75 mmol), 2-carboxybenzenediazonium chloride (696 mg, 3.77 mmol), 1,2-epoxypropane (1,5 mL) and dichloroethane (15 mL). The reaction vessel was put under a low vacuum and backfilled with nitrogen 4 times and refluxed for 2 hours. The solvent was removed under reduced pressure, and the residue was purified by column chromatography on silica gel (eluent: gradient from 25% CH2Cl2/75% hexanes to 35% CH2Cl2/65% hexanes) to afford 212 mg (89% yield) of compound 8 as a white solid. Mp: 168-172 °C. 1H NMR (CDCl3, 400 MHz): 7.33 (m, 2H), 7.23 (d, 2H, J = 7.5 Hz), 6.96

(m, 4H), 6.45 (dd, 2H, J = 3.2 Hz, J = 1.9 Hz), 5.29 (s, 2H), 3.69 (s, 6H).

13

C NMR:

157.56, 147.49, 145.78, 137.73, 125.39, 124.33, 123.64, 110.96, 109.31, 55.70, 53.69. HRMS (APPI+): calcd. for C22H18O2: 314.1301, found: 314.1260 (M)+.

25


5.997

1.969

1.944

4.403

2.231 2.069

26


Synthesis of compound 9: To a flame dried 25 mL round bottom flask equipped with a stir bar and sealed with a septum under nitrogen was added 2,6-dimethoxytriptycene 6 (212 mg,0.67 mmol), and anhydrous CH2Cl2 (7 mL) and the reaction vessel was cooled to 0 °C with an ice bath. Boron tribromide (1.00 g, 4.02 mmol) was added dropwise and the solution was allowed to warm to room temperature over 2 hours. The reaction was quenched with water and extracted three times with a mixture of CH2Cl2/EtOAc (1:1, 3x15 mL). The organic layers were dried over Na2SO4 and the solvent was removed under reduced pressure. The crude product was purified by column chromatography on silica gel (eluent: 10% AcOEt/90% CH2Cl2) to afford 133 mg (70% yield) of compound 9 as an off-white solid. Mp: >250 °C. 1H NMR ((CD3)2CO, 400 MHz): 8.14 (s, 2H), 7.35 (dd, 2H, J = 2.7 Hz, J = 3.3 Hz), 7.19 (d, J = 7.8 Hz), 6.95 (d, 2H, J = 1.7 Hz), 6.93 (dd, 2H, J = 2.7 Hz, J = 3.3 Hz), 6.41 (dd, 2H, J = 4.1 Hz, J = 2.0 Hz), 5.37 (s, 2H). 13C NMR: 154.98, 148.07, 146.54, 136.90, 124.90, 124.23,

123.34, 111.68, 110.53. HRMS (APPI+): calcd. for C20H14O2: 286.0988, found: 286.0975 (M)+.

27


28


Bu

Bu Br(H2C)8O

N

O(CH2)8Br

N Zn

N Bu

N Bu

Synthesis of compound 12 To a 250 mL round bottom flask equipped with a stir bar and sealed with a septum was added 3-(8bromooctyloxy)benzaldehyde

(274

mg,

0.874

mmol),

4,4´-dimethyl-3,3´-dibutyl-2,2´-

dipyrrylmethane 12 (250 mg, 0.874 mmol) and CH2Cl2 (140 mL) and the mixture was degassed with a flow of nitrogen for 15 minutes. Trifluoroacetic acid (29 mg, 0.25 mmol) was added and the reaction was stirred for 2 hours at room temperature. Then, p-chloranil (318 mg, 1.30 mmol) was added and the reaction was stirred overnight. The acid was neutralized with triethylamine (ca. 0.5 mL) and Zn(OAc)2.2H2O (952 mg, 4.35 mmol) and methanol (20 mL) were added. The resulting solution was heated to reflux for 30 minutes. Once cooled, the reaction mixture was washed successively with NaOH aq. (0.1 M), water, brine and then dried over Na2SO4. The solvent was evaporated under reduced pressure and purified by a first column chromatography on silica gel (eluent 30% CH2Cl2/70% hexanes) and a second column chromatography on silica gel (eluent 50% toluene/50% texanes) to afford a purple gummy solid that was triturated with cold methanol to afford a 304 mg (60% yield) of compound 12 as a purple solid. Mp: 155-157 °C. 1H NMR

(CDCl3, 400 MHz): 10.15 (d, 2H, J= 2.6 Hz), 7.67 (t, 2H, J = 6.7 Hz), 7.61 (m, 4H), 7.33(m, 2H), 4.09 (m, 4H), 3.95 (t, 8H, J = 8 Hz), 3.34 (t, 4H, J = 6.7 Hz), 2.54 (s, 12H), 2.16 (m, 8H), 1.87-1.72 (m, 16 H), 1.50-1.28 (m, 18H), 1.11 (t, 12H, J = 7.4 Hz).

13

C

NMR: 158.81, 147.83, 146.61, 145.09, 143.64, 138.44, 128.64, 126.55, 119.84, 119.46, 115.25, 97.83, 68.52, 35.78, 34.22, 33.00, 29.58, 29.48, 28.94, 28.33, 29.72, 26.21, 23.66, 15.33, 14.54. HRMS (APPI+): calcd. for C68H91Br2N4O2Zn: 1217.4800, found: 1217.4748 (M+H)+.

29


9.0

PPM

7.0

6.0

5.0

file: C:\Users\Jean-Benoit\Documents\RMN\JBG 4 - 5\jbg-5-169_15Sep2011\PROTON_01.fid\fid block# 1 expt: "s2pul" transmitter freq.: 399.775827 MHz time domain size: 47896 points width: 6396.42 Hz = 16.000012 ppm = 0.133548 Hz/pt number of scans: 8

4.0

2.0

-0.0000

13.45

19.62

17.34

2.1754 2.1576 2.1396 1.8420 1.8236 1.8053 1.7828 1.7631 1.7445 1.7262 1.4757 1.4597 1.4149 1.3970 1.3703 1.3357 1.3104 1.2515 1.1275 1.1092 1.0908

3.0

8.178

2.5375 11.57

3.3609 3.3439 3.3270 4.050

8.247

4.056

4.1041 4.0961 4.0889 4.0805 4.0730 3.9643 3.9465 3.9287

7.3431 2.040

8.0

7.2239

7.6728 7.6567 7.6127 7.5937 2.220 4.076

1.999

10.1507 10.1439

SpinWorks 2.5: jbg-5-169

1.0

0.0


120.0

110.0

file: C:\Users\Jean-Benoit\Documents\RMN\JBG 4 - 5\jbg-5-169_15Sep2011\CARBON_01.fid\fid block# 1 expt: "s2pul" transmitter freq.: 100.534142 MHz time domain size: 60288 points width: 25133.52 Hz = 249.999864 ppm = 0.416891 Hz/pt number of scans: 256

100.0

90.0

80.0

70.0

60.0

50.0

40.0

30.0

15.3309 14.5408

29.5877 29.4805 28.9441 28.3394 26.7272 26.2149 23.6606

35.7836 34.2256 33.0096

68.5195

77.5985 77.2809 76.9627

97.8356 97.8186

115.2532

130.0

119.8499 119.4678

140.0

126.5562

128.6411

150.0

138.4479

PPM

147.8301 146.6196 145.0917 143.6491

158.8150


20.0

10.0


30


Synthesis of compound H1: To a 250 mL round bottom flask equipped with a stir bar and sealed with a septum was added porphyrin 4 (150 mg, 0.122 mmol), anthraflavic acid (21 mg, 0.86 mmol), K2CO3 (67 mg, 0.49 mmol), NaI (18 mg, 0.12 mmol) and DMF (100 mL). The reaction vessel was put under a low vacuum and backfilled with nitrogen 4 times. The solution was then heated at 80 °C overnight. Once cooled, the solvent was evaporated under reduced pressure and the residue was dissolved in toluene, filtered and the solvent evaporated. The residue was purified by column chromatography on silica gel (eluent: toluene) to afford 81 mg (50% yield) of compound H1 as a purple solid. 1

H NMR ((CDCl3, 400 MHz): 8.95 (d, 4H, J= 4.6 Hz), 8.68 (d, 4H, J= 4.5 Hz), 7.78-7.70 (m, 8H),

7.64 (t, 2H, J = 7.9 Hz), 7.57 (t, 2H, J = 7.7 Hz), 7.26 (dd, 2H, J = 4.2 Hz, J = 1.9 Hz), 6.63 (dd, 2H, J = 4.4 Hz, J = 2.1 Hz), 6.46 (d, 2H, J = 6.5 Hz), 6.30 (d, 2H, J = 2.3 Hz), 4.17 (t, 4H, J = 6.0 Hz), 3.73 (t, 4H, J = 5.6 Hz), 1.90-1.81 (m, 4H), 1.71-1.63 (m, 4H), 1.58-1.49 (m, 4H), 1.44-1.29 (m, 12H).

13

C NMR: 181.64, 163.63, 157.49, 150.58, 149.31, 144.29, 140.93, 138.89, 138.85,

134.79, 133.1, 130.34, ,30.17, 129.13, 127.88, 127.85, 127.38, 125.81, 122.31, 121.05, 121.03, 115.01, 112.79, 109.56, 68.37, 67.92, 28.76, 28.32, 28.08, 27.92, 25.13, 24.99. HRMS (APPI+):

calcd. for C74H61Cl4N4O6Zn: 1305.2631, found: 1305.2646 (M+H)+.

31


0.0000

1.3303 1.3466 1.3586 1.3923 1.4074 1.4250 1.5192 1.5368 1.5530 1.6644 1.6801 1.6949 1.8366 1.8532 1.8691

3.7152 3.7298 3.7442

4.1589 4.1736 4.1881

6.3004 6.3062

6.4514 6.4728 6.6228 6.6291 6.6442 6.6505

7.2448 7.2722 7.2759

7.5570 7.5770 7.5973 7.6262 7.6465 7.6666 7.7156 7.7363 7.7438 7.7461 7.7567 7.7631 7.7662 8.6795 8.6910 8.9467 8.9583

15.44

4.776 4.560

4.916

3.960

3.925

2.155

2.023

2.049

3.289

2.385 2.544 8.916

3.898

3.994

PPM

170.0

160.0

150.0

140.0

130.0

file: C:\Users\Jean-Benoit\Documents\RMN\JBG 4 - 5\jbg-5-27_12Jun2011\CARBON_01.fid\fid block# 1 expt: "s2pul" transmitter freq.: 100.534142 MHz time domain size: 60288 points width: 25133.52 Hz = 249.999864 ppm = 0.416891 Hz/pt number of scans: 256

120.0

110.0

100.0

90.0

80.0

70.0

28.7650 28.3288 28.0767 27.9253 25.1344 24.9958

68.3724 67.9271

77.5935 77.2759 76.9578

109.5690

112.8024

115.0138

122.3212 121.0561 121.0363

144.3031 140.9360 138.8964 138.8625 134.7935 133.1576 130.3466 130.1796 129.1298 127.8909 127.8571 127.3884 125.8168

150.5899 149.3188

157.4954

163.6437

181.3724


60.0

50.0

40.0

30.0

20.0

10.0

0.0


32


Synthesis of compound H2: To a 100 mL round bottom flask equipped with a stir bar and sealed with a septum was added porphyrin 2a (96 mg, 0.123 mmol), bis-tosyl anthraquinone 6 (100 mg, 0.123 mmol), K2CO3 (340 mg, 2.46 mmol) and DMF (30 mL). The reaction vessel was put under a low vacuum and backfilled with nitrogen 4 times. The reaction was then heated at 75 °C overnight. Once cooled, the solvent was evaporated under reduced pressure. This residue was purified by column chromatography on silica gel (eluent: 40% AcOEt/60% toluene). The porphyrin was dissolved in CH2Cl2 (20 mL), MeOH (4 mL) and Zn(OAc)2.2H2O (88 mg, 0.40 mmol) and the solution was stirred overnight at room temperature. The solvent was removed under reduced pressure and the residue purified by chromatography column on silica gel (eluent: 50% AcOEt/50% CH2Cl2) to afford 49 mg (29% yield) of compound H2 as a purple solid. 1

H NMR (CDCl3, 400 MHz): 8.90 (d, 4H, J = 4.6 Hz), 8.65 (d, 4H, J = 4.6 Hz), 7.75 (t, 4H, J = 8.8

Hz), 7.69-7.59 (m, 6H), 7.56 (t, 2H, J = 7.9 Hz), 7.26 (m, 2H), 6.42 (dd, 2H J = 4.6 Hz, J = 2.0 Hz), 5.29 (d, 2H, J = 8.4), 4.26 (t, 4H, J = 4.3 Hz), 3.86 (m, 4H), 3.75 (m, 4H), 3.68-3.58 (m, 12H). 13C NMR: 180.64, 163.00, 157.16, 150.50, 149.29, 144.46, 141.06, 138.86, 138.83, 133.94, 132.94, 130.27, 128.84, 128.02, 127.88, 127.76, 127.39, 125.13, 121.72, 120.92, 120.87, 114.99, 113.45, 109.07, 71.46, 71.22, 70.12, 69.39, 68.09, 68.03. HRMS (APPI+): calcd. for C70H53Cl4N4O10Zn:

1313.1802, found: 1313.1804 (M+H)+.

33


8.4

8.0

7.6

7.2

6.8

6.4

5.6

5.2

4.8


4.4

0.0001

1.1126

1.2559

1.6109

3.7538 3.6679 3.6611 3.6268 3.6151

4.0

12.85

3.488

3.654

4.2572 3.451

5.4136 5.4102 5.3064 5.2850

6.0

1.642

1.657

6.4387 6.4338 6.4176 6.4126 1.732

2.947

2.584

6.128

4.091

8.6616 8.6502 3.999

PPM

7.7739 7.7520 7.7292 7.6791 7.6612 7.6376 7.6177 7.5975 7.5758 7.5559 7.5364 7.2774 7.2738 7.2466

8.9219 8.9019 8.8905 3.953


3.6

3.2

2.8

2.4

2.0

1.6

1.2

0.8

0.4


PPM

170.0

160.0

150.0

140.0

130.0


120.0

110.0

100.0

90.0

80.0

71.4585 71.2199 70.1216 69.3947 68.0970 68.0306

77.5966 77.2786 76.9608

109.0697

114.9898 113.4523

121.7206 120.9296 120.8734

144.4603 141.0579 138.8664 138.8343 133.9409 132.9445 130.2758 130.1531 128.8481 128.0217 127.8872 127.7675 127.3980 125.1265

150.5089 149.2926

157.1636

163.0028

180.6481


70.0

60.0

50.0

40.0

30.0

20.0

10.0


34


O

O

O

Cl Cl

N N Zn N N Cl

Cl

O

Synthesis of compound H3: To a 250 mL round bottom flask equipped with a stir bar and sealed with a septum was added porphyrin 4 (76 mg, 0.061 mmol), 2,6-dihydroxynaphthalene (10 mg, 0.061 mmol), K2CO3 (90 mg, 0.65 mmol), NaI (24mg, 0.16 mmol) and DMF (80 mL). The reaction vessel was degassed using a low vacuum and backfilled with nitrogen 4 times and heated to 80 °C overnight. Once cooled, the solvent was evaporated under reduced pressure and the residue was dissolved in toluene, filtered and the solvent was evaporated. The residue was purified by column chromatography on silica gel (eluent: toluene) to afford 16 mg (22 % yield, 95% purity) of host H3 as a purple solid. 1

H NMR (CDCl3, 400 MHz): 8.95 (d, 4H, J = 4.5 Hz), 8.70 (d, 4H, J = 4.5 Hz), 7.81 (t, 4H, J = 8.9

Hz), 7.75 (m, 4H), 7.67 (d, 2H, J = 8.1 Hz), 7.60 (d, 2H, J = 8.0 Hz), 7.28 (dd, 2H, J = 4.2 Hz, J = 1.9 Hz), 6.61 (d, 2H, J = 8.7 Hz), 6.28 (dd, 2H, J = 4.4 Hz, J = 2.0 Hz), 6.10 (d, 2H, J = 1.9 Hz), 4.14 (t, 4H, J = 6.5 Hz), 3.40 (t, 4H, 6.1 Hz), 1.86 (m, 4H), 1.50-1.20 (m, 20H).

13

C NMR: 157.41,

154.68, 150.61, 149.30, 144.09, 140.80, 139.07, 138.65, 133.29, 130.46, 130.46, 130.13, 128.69, 128.00, 127.97, 127.45, 127.40, 127.09, 121.97, 121.15, 118.59, 114.99, 113.79, 106.30, 106.27, 68.20, 67.73, 29.96, 29.02, 28.83, 28.79, 28.54, 25.39. HRMS (APPI+): calcd. for

C70H60Cl4N4O6Zn: 1223.2631, found: 1226.2638 (M)+.

35


PPM

8.8

8.4

8.0

7.6

7.2

6.8

6.4

6.0

5.6

5.2


4.8

4.4

4.0

3.6

3.2

2.8

2.4

2.0

-0.0000

1.4746 1.4562 1.4371 1.4168 1.4050 1.3789 1.3494 1.3294 1.3174 1.2986 1.2534 0.8786 36.79

1.8846 1.8679 1.8510 4.199

3.4183 3.4031 3.3877 3.990

4.1592 4.1431 4.1270 3.988

6.0976 6.0932

6.2950 6.2901 6.2732 6.2682

1.989

6.6183 6.5962 2.058

2.224

4.247 4.345 2.320 2.209

7.8403 7.8179 7.7945 7.7631 7.7420 7.6935 7.6732 7.6529 7.6217 7.6017 7.5823 7.2905 7.2861 7.2699 7.2654 7.2419

8.7105 8.6990 4.018

3.997

8.9538 8.9422


1.6

1.2

0.8

0.4


PPM

150.0

140.0

130.0

120.0

110.0


100.0

90.0

80.0

70.0

29.9658 29.0280 28.8310 28.7906 28.5457 25.3975

77.5874 77.5068 77.4837 77.4605 77.2697 77.1852 77.1590 77.1410 76.9519 76.8731 76.8552 68.2091 67.7357

106.3051 106.2754

114.9903 113.7996

118.5982

121.9769 121.1525

140.8003 139.0759 138.6555 133.2900 130.4613 130.1323 128.6992 127.9723 127.4556 127.4023 127.0917

144.0938

150.6167 149.3036

154.6822

157.4265


60.0

50.0

40.0

30.0

20.0

10.0


36


Synthesis of compound H4: To a 250 mL round bottom flask equipped with a stir bar was added porphyrin 4 (100 mg, 0.081 mmol), K2CO3 (90 mg, 0.65 mmol) and DMF (40 mL). The reaction vessel was put under low vacuum and backfilled with nitrogen 4 times and heated to 80 °C. The 2,6-dihydroxytriptycene 9 (23 mg, 0.081 mmol) was dissolved in DMF (10 mL) under nitrogen and added to reaction vessel over 14 hours at a rate of 0.7 mL/h using a syringe pump. After the addition the reaction vessel was heated for 2 hours. Once cooled, the solvent was removed under reduced pressure and the residue was dissolved in toluene, filtered and the solvent was evaporated. This residue was purified by a first column chromatography on silica gel (eluent: toluene) and a second column chromatography on silica gel (eluent: 50% CH2Cl2/50% hexanes) to afford 45 mg (41% yield, 95% purity) of host H4 as a purple solid. 1

H NMR (CDCl3, 400 MHz): 9.00 (m, 4H), 8.76 (m, 4H), 7.94 (d, 4H, J = 7.3 Hz), 7.71-7.62 (m,

6H), 7.31 (dd, 2H, J = 4.2 Hz, J = 1.9 Hz), 7.03 (dd, 2H, J = 2.6 Hz, J = 3.1 Hz), 6.81 (d, 2H, J = 7.9 Hz), 6.60 (m, 4H), 6.04 (dd, 2H, J = 4 Hz, J = 2.1 Hz), 4.92 (s, 2H), 4.06 (t, 4H, J = 6.7 Hz), 3.52 (m, 4H), 1.80 (m, 4H), 1.47-1.10 (m, 24H). 13C NMR: 157.45, 146.59, 150.69, 149.41, 146.68, 145.55, 144.05, 140.78, 138.94, 137.15, 133.35, 130.50, 130.28, 128.01, 127.97, 127.59, 127.30, 124.96, 123.88, 123.27, 121.28, 121.23, 115.13, 114.69, 111.08, 109.80, 68.97, 68.08, 53.34, 29.34, 29.17, 29.05, 25.99, 25.60. HRMS (APPI+): calcd. for C80H66Cl4N4O4Zn: 1350.3130, found:

1350.3124 (M)+.

37


9.0

PPM

8.0

6.0

5.0


4.0

3.0

0.0000

9.574

4.019 5.754

1.8265 1.8093 1.7919 1.7753 1.4538 1.4389 1.4237 1.3932 1.3745 1.3495 1.3221 1.2550 1.2414 1.2221 1.1630 4.251

2.3877

2.6132

3.5079 3.4921 3.4815 3.4655 3.913

4.0446 4.0279 4.0112 4.004

4.8802 1.918

6.5659 6.5612 6.5533

6.0147 6.0092 5.9949 5.9895

6.7842 6.7643

3.968

7.0

2.104

7.0085 7.0003 6.9958 6.9876

2.107

7.2850 7.2808 7.2643 7.2601 7.2285

1.948

2.042

6.574

4.125

2.128

7.9090 7.8906 7.7871 7.7663 7.7409 7.6736 7.6536 7.6384 7.6338 7.6189 7.5994

3.908

3.998

8.9806 8.9743 8.9693 8.9631 8.7362 8.7286 8.7252 8.7175


2.0

1.0

0.0


PPM

160.0

150.0

140.0

130.0

120.0


110.0

100.0

90.0

80.0

70.0

60.0

29.3403 29.1735 29.0566 25.9876 25.6046

53.3399

68.4690 68.0799

77.6031 77.2849 76.9675

111.0808 109.8040

115.1320 114.6968

124.9600 123.8781 123.2703 121.2802 121.2384

140.7836 138.9423 138.8031 137.1519 133.3512 130.5053 130.2814 128.0128 127.9718 127.5876 127.2966

146.9786 145.5556 144.0554

150.6916 149.4182

157.4485 156.5931


50.0

40.0

30.0

20.0

10.0

0.0


38


Synthesis of compound H5: To a 100 mL round bottom flask equipped with a stir bar was added porphyrin 4 (100 mg, 0.081 mmol), K2CO3 (90 mg, 0.65 mmol) and DMF (40 mL). The reaction vessel was put under a low vacuum and backfilled with nitrogen 4 times and heated to 80 °C. The 2,6-dihydroxy-exTTF 10 (34 mg, 0.081 mmol) was dissolved in DMF (12 mL) under nitrogen and added to reaction vessel over 15 hours at a rate of 0.8 mL/h using a syringe pump. After the addition, the reaction vessel was heated for an additional 2 hours. Once cooled, the solvent was evaporated under reduced pressure and the residue dissolved in toluene, filtered and the solvent evaporated. This residue was purified by column chromatography on silica gel (eluent: toluene) and afforded 28 mg (23% yield, 95% purity) of host H5 as a purple solid. Note: This product is sensitive to acids and decomposes when kept in chloroform. 1

H NMR (CDCl3, 400 MHz): 8.97 (t, 4H, J = 4.2 Hz), 8.70 (t, 4H, J = 5.2 Hz), 7.84 (d, 2H, J = 7.3

Hz), 7.77 (s, 2H), 7.70 (m, 4H), 7.60 (m, 4H), 7.27 (m, 2H), 6.52 (d, 2H, J = 2.2 Hz), 6.49 (d, 2H, J = 8.5 Hz), 6.31 (dd, 2H, J = 4.2 Hz, J = 2.2 Hz), 5.61 (d, 2H, J = 6.5 Hz), 5.10 (d, 2H, J = 6.6 Hz), 4.12 (t, 4H, J = 6.2 Hz), 3.73 (m, 4H), 1.84 (m 4H), 1.61 (m, 4H), 1.47 (m, 4H), 1.38-1.28 (m, 12H). 13C NMR: 157.55, 156.78, 150.75, 150.64, 149.40, 149.37, 144.16, 140.69, 138.99, 138.78, 136.35, 133.36, 132.64, 130.42, 130.30, 127.95, 127.91, 127.67, 127.62, 127.50, 125.80, 122.41, 121.68, 121.24, 116.53, 116.28, 115.16, 113.56, 112.35, 110.49, 68.18, 68.02, 29.17, 28.75, 28.64, 28.52, 25.56, 25.36. HRMS (APPI+): calcd. for C88H101N4O4S4Zn: 1469.5992, found:

1469.5860 (M+H)+.

39


8.4

8.0

7.6

7.2

6.4

6.0

5.6

5.2

4.8

4.4

file: C:\Users\Jean-Benoit\Documents\RMN\JBG 4 - 5\jbg-5-133_19Jul2011\PROTON_01.fid\fid block# 1 expt: "s2pul" transmitter freq.: 399.775827 MHz time domain size: 47896 points width: 6396.42 Hz = 16.000012 ppm = 0.133548 Hz/pt number of scans: 8

4.0

3.6

2.8

2.4

2.0

-0.0000

18.34

5.283

1.8585 1.8421 1.8253 1.6152 1.6005 1.4764 1.4596 1.3524 1.3386 1.3206 1.3031

3.2

4.319

4.311

3.7516 3.7131 3.958

4.1325 4.1173 4.1018 3.999

5.1074 5.0908 1.831

5.6130 5.5963 1.851

1.922

6.6204 6.6150 6.5036 6.4825 6.3192 6.3137 6.2982 6.2926

6.8

1.907

1.904

2.333

1.999 2.550 4.544 4.795

8.7126 8.6994 8.6858 4.415

PPM

7.8506 7.8322 7.7681 7.7197 7.7150 7.7003 7.6950 7.6299 7.6209 7.6097 7.6012 7.5897 7.5816 7.2799 7.2628 7.2593 7.2321

8.9935 8.9827 8.9717 4.543


1.6

1.2

0.8

0.4

-0.0


PPM

150.0

140.0

130.0

120.0

110.0

file: C:\Users\Jean-Benoit\Documents\RMN\JBG 4 - 5\jbg-5-133_19Jul2011\CARBON_01.fid\fid block# 1 expt: "s2pul" transmitter freq.: 100.534142 MHz time domain size: 60288 points width: 25133.52 Hz = 249.999864 ppm = 0.416891 Hz/pt number of scans: 256

100.0

90.0

80.0

70.0

28.7547 28.6451 28.5297 25.5680 25.3695

68.1841 68.0204

77.6119 77.3643 77.2941 76.9762

110.4991

116.5305 116.2820 115.1690 112.3525

140.6939 138.9920 138.7804 136.3544 133.3623 132.6410 130.4256 130.3067 127.9524 127.9155 127.6767 127.6208 127.5092 125.8051 122.4156 121.6847 121.2459

144.1627

150.7523 150.6489 149.4091 149.3722

157.5552 156.7815


60.0

50.0

40.0

30.0

20.0

10.0


40


Synthesis of compound H6: To a 100 mL round bottom flask equipped with a stir bar and sealed with a septum was added porphyrin 3 (90 mg, 0.077 mmol), free base porphyrin 2a (60 mg, 0.077 mmol), K2CO3 (85 mg, 0.61 mmol), NaI (23 mg, 0.153 mmol) and DMF (40 mL). The reaction vessel put under a low vacuum and backfilled with nitrogen 4 times and heated to 80 °C overnight. Once cooled, the solvent was removed under reduced pressure and the residue was dissolved in toluene, filtered and the solvent evaporated. This residue was purified by two successive column chromatography on silica gel (eluent: toluene) to afford 17 mg (12% yield) of host H6 as a red solid. Note: Host H6 shows a complicated NMR spectrum due to the presence of conformational isomers2 and the two different porphyrin moieties. The product was analytically pure on TLC and the HRMS spectrum was unambiguous. 1

H NMR (CDCl3, 400 MHz): 8.98 (m, 1H), 8.84 (t, 2H, J = 4.2 Hz), 8.77 (d, 1H, J = 4.8 Hz), 8.73

(d, 2H, J = 4.8 Hz), 8.63 (d, 1H, J = 4.8 Hz), 8.57 (d, 1H, J = 4.4 Hz), 8.46 (t, 2H, J = 4.5 Hz), 8.30 (d, 1H, J = 4.8 Hz), 8.19 (d, 1H, J = 4.0 Hz), 7.68 (d, 1H, J = 4.6 Hz), 7.82-7.76 (m, 3H), 7.68-7.40 (m, 15H), 6.84 (m, 1H), 6.64 (m, 0.5H), 6.55 (m, 0.5H), 6.44-6.35 (m, 2H), 4.15-3.94 (m, 8H), 1.96-1.78 (m, 8H), 1.58-1.46 (m, 8H), -2.81 (s, 0.5H), -2.88 (s, 0.5H), -3.11 (s, 0.5H). 13C NMR: Due to the presence of conformational isomers, a clear spectrum with significant resolution and S/N ratio could not be obtained. HRMS (APPI+): calcd. for C100H71Cl8N8O4Zn: 1791.2392,

found: 1791.2388 (M+H)+.

41


8.0

PPM

7.0

6.0

5.0

4.0

3.0


2.0

1.0

0.0

-1.0

-2.0

-2.8859

-3.1153

0.421 0.603

0.583

0.0001

1.9120 1.8969 1.8808 1.8654 1.8549 1.8359 1.8236 1.5348 1.4908 1.2547 13.28

8.389

2.3510

4.1459 4.1301 4.1119 4.1031 4.0936 4.0871 4.0696 4.0526 3.9772 3.9692 7.998

6.3792 6.3588 2.055

0.550 0.508

1.181

7.2692 7.2500 7.2326 7.1789 7.1600

7.9660 7.9545

8.3059 8.2944 8.1982 8.1878

7.8143 7.7963 7.7780 7.6615 7.6431 7.6258 7.5998 7.5780 7.5565 7.5373 7.5171 7.4963 7.4700 7.4524 7.4266 7.4061 15.52

3.389

1.298

1.102 0.942

1.141 1.323 2.249

2.690 1.041 2.377

0.686

8.8529 8.8417 8.8304 8.7804 8.7689 8.7434 8.7320 8.6359 8.6244 8.5713 8.5601 8.4698 8.4582 8.4467


-3.0


PPM

150.0

140.0

130.0

120.0

110.0

file: C:\Users\Jean-Benoit\Documents\RMN\JBG 4 - 5\jbg-5-121_15Sep2011-205122\CARBON_01.fid\fid block# 1 expt: "s2pul" transmitter freq.: 100.534142 MHz time domain size: 60288 points width: 25133.52 Hz = 249.999864 ppm = 0.416891 Hz/pt number of scans: 10000

100.0

90.0

80.0

70.0

60.0

50.0

40.0

30.0

0.0130

25.8548 25.7063

29.3302

77.3393 77.1940 77.2250 77.1762 77.0216 76.9069 76.8793 76.8641 76.8550 76.8061 76.7038 76.5961 76.5756 76.5540 76.5312 67.8597

114.7380

120.8371 120.3922 119.9323

125.3073

142.7458 137.3774 132.9140 132.8501 130.0581 129.9275 129.9037 129.5994 129.0464 128.2369 127.6240 127.5998 127.5431 127.4648 127.4290 127.3443 127.3801 127.2667 127.2092 126.7747 126.7450

150.2319 150.1951 150.0596 148.9448 148.6460

156.9562


20.0

10.0


42


(M+H)+

43


Synthesis of compound H7: To a 100 mL round bottom flask equipped with a stir bar and sealed with a septum was added porphyrin 12 (94 mg, 0.081 mmol), K2CO3 (90 mg, 0.65 mmol) and DMF (40 mL). The reaction vessel was put under a low vacuum and backfilled with nitrogen 4 times and heated to 80 °C. The 2,6-dihydroxy-exTTF 10 (34 mg, 0.081 mmol) was dissolved in DMF (10 mL) under nitrogen and added to reaction vessel over 14 hours at a rate of 0.7 mL/h using a syringe pump. After the addition, the solution was heated for an additional 2 hours. Once cooled, the solvent was removed under reduced pressure and the residue dissolved in toluene, filtered and the solvent evaporated. This residue was purified by a column chromatography on silica gel (eluent gradient from 50% toluene/50% hexanes to 75% toluene/25% hexanes) to afforded 16 mg (13% yield) of host H7 as a purple solid. Note: This product is sensitive to acids and decomposes when kept in chloroform. 1

H NMR (CDCl3, 400 MHz): 10.17 (s, 2H), 7.76 (d, 2H, J = 7.2 Hz), 7.68-7.60 (m, 4H), 7.36 (m,

2H), 6.71 (d, 2H, J = 2.0 Hz), 6.63 (d, 2H, J = 8.2 Hz), 6.33 (dd, 2H, J = 4.3 Hz, J = 2 Hz), 5.60 (d, 2H, J = 6.6 Hz), 5.10 (d, 2H, J = 6.6 Hz), 4.14 (t, 4H, J = 6.6 Hz), 3.96 (m, 8H), 3.79 (m, 4H), 2.58 (s, 12H), 2.14 (m, 8H), 1.89 (m, 4H), 1.78-1.65 (m, 12H), 1.45-1.30 (m, 16H), 1.10 (m, 12H). 13C NMR: 158.83, 156.88, 147.91, 147.81, 146.59, 145.20, 143.651 138.41, 136.51, 132.85, 128.59, 127.83, 126.48, 125.76, 122.05, 121.62, 121.20, 120.16(2C), 119.48, 116.43, 116.33, 114.68, 112.04, 110.70, 97.80, 68.35, 67.99, 35.75, 29.97 (2C), 29.26, 28.86, 28.77, 28.70, 26.73, 25.67, 25.51, 23.64, 15.34, 14.49. HRMS (APPI+): calcd. for C88H101Cl8N8O4Zn: 1469.5992, found:

1469.5860 (M+H)+.

44


9.0

PPM

8.0

7.0

5.0


4.0

0.0001

14.63

21.39

14.27

9.424

3.0

4.894

2.5645 2.3539 2.1621 2.1407 2.1011 1.8913 1.8745 1.8572 1.7611 1.7434 1.7276 1.7112 1.6931 1.6737 1.6580 1.6423 1.5174 1.4820 1.3528 1.2539 1.0974 1.0799 1.0640 1.0464 13.09

4.711

9.255

4.1408 4.1247 4.1085 3.9652 3.9474 3.7883 3.7625

5.0991 5.0825 2.282

6.0

4.720

5.5974 5.5808 2.147

2.403

6.7028 6.6971 6.6300 6.6089 6.3320 6.3261 6.3110 6.3051 2.190 2.282

7.3518 7.3314 7.2537 2.909

5.654

2.550

2.244

7.7436 7.7254 7.6548 7.6349 7.6157 7.6007

10.1599


2.0

1.0

0.0


PPM

150.0

140.0

130.0

120.0

110.0


100.0

90.0

80.0

70.0

60.0

50.0

40.0

29.9913 29.9665 29.2646 28.8652 28.8052 28.7767 28.7043 26.7315 25.6687 25.5183 23.6448 15.3448 14.5343 14.4904 14.4388

35.7503 35.7022

68.3523 67.9939

77.5832 77.4785 77.4688 77.4362 77.4121 77.3582 77.3756 77.2656 77.1516 77.1646 77.0986 77.1259 77.1325 77.0306 77.0548 77.0726 77.0820 76.9477 76.8457 76.8135 76.7598

97.8072

112.0482 110.7027

138.4323 138.4151 136.5186 132.8548 128.5931 127.8316 126.4793 125.7646 122.0527 121.6285 121.2011 120.1867 120.1642 119.4755 116.4362 116.3353 114.6947 114.6896

147.8816 147.7894 146.6158 146.5984 145.2039 143.6530

156.8876

158.8359


30.0

20.0

10.0

0.0


45


4. References 1. Conors, K. A., Binding Constants: The Measurement of Molecular Complex Stability. Wiley & Sons: New York, NY, 1987. 2. Tashiro, K.; Aida, T.; Zheng, J.-Y.; Kinbara, K.; Saigo, K.; Sakamoto, S.; Yamaguchi, K., J. Am. Chem. Soc. 1999, 121 (40), 9477-9478.

46