# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and

# The Centre National de la Recherche Scientifique, 2005

Supplementary Data

Synthesis and Electrochemical Properties of Slipped-Cofacial Porphyrin Dimer

of Ferrocene Functionalized Zn-Imidazolyl-Porphyrins as a Terminal Electron

Donor in Photosynthetic Model

Dipak Kalita, Mitsuhiko Morisue, Yoshiaki Kobuke*

Graduate School of Materials Science, Nara Institute of Science and Technology, 8916-5

Takayama, Ikoma 630-0101, Japan

Improved synthetic route of 1-formyl-2,2′,3,3′,4,4′,5,5′-octamethyl ferrocene 11:

Me

Me Me

MeO

Me Me

MeMe

n-BuLiFeCl2.1.5THF, 76%

O

OO

H

OO

HO

KOH/MeOH KOH/MeOH

LiAlH4/HCl reflux

DMF/POCl3

11

21 22 23 24

2526

57% 54%

75%

75%

93-95%

p-TsOHToluene

H2SO4/HCOOHLit. yield 38% Ref. 1

or

LiAlH4/33%H2SO4Lit. yield 25-30 % Ref. 2

FeCl2Lit. yield 50% Ref. 3

Fe

MeCHO

Me

Me

Me

MeMe

Me

Me Fe

Me

Me

Me

Me

MeMe

Me

Me

Reference: 1. Whitesides, G.M. Inorg. Chem. 1976, 15, 466-469.

2. Fendric, C.M.; Schertz, L.D.; Day, V.W.; Marks, T.J. Organometallics 1988, 7, 1828-1838.

3. (a) Koeler, F.H.; Doll, K.H. Z. Naturforsch. 1982, 37b, 144-150. (b) Schmitt, V.G.; Ozman, S.

Chem. Ztg. 1976, 100, 143.

S1

# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and

# The Centre National de la Recherche Scientifique, 2005

xx

*

1H NMR

N

NH N

HN N

N

Me

O

O 1-H2

Cross (x) indicates solvent CDCl3 or TMS, asterisk (*) indicates impurity.

0

10

20

30

40

50

60

70

80

90

100

%Int.

400 600 800 1000 1200 1400 1600 1800 2000Mass/Charge

24 mV[sum= 2428 mV] Profiles 1-100 Smooth Gauss 1 -Baseline 10

After Maintenance 2004/11/10 Data: DDK-265 Ph-Por-Im H20001.F1 8 Jan 2005 13:42 Cal: 040612_760_1050 20 Oct 2004 11:44 Kratos PC Axima LNR V2.4.0: Mode Linear, Power: 63, P.Ext. @ 662 (bin 54)

662.33

663.39

661.31

664.38

S2

N

NH N

HN N

N

Me

O

O 1-H2

# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and

# The Centre National de la Recherche Scientifique, 2005

x

x

Compound 1-ZnD

1H NMR

0

10

20

30

40

50

60

70

80

90

100

%Int.

400 600 800 1000 1200 1400 1600 1800 2000Mass/Charge

42 mV[sum= 4172 mV] Profiles 1-100 Smooth Gauss 1 -Baseline 10

After Maintenance 2004/11/10 Data: DDK-266 Ph-Por-Im Zn0001.F2 8 Jan 2005 13:51 Cal: 040612_760_1050 20 Oct 2004 11:44 Kratos PC Axima LNR V2.4.0: Mode Linear, Power: 70, P.Ext. @ 724 (bin 54)

724.30

723.24

725.31

727.31

728.33

1448.02

1451.11729.351453.08

730.291467.11

S3

Compound 1-ZnD

# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and

# The Centre National de la Recherche Scientifique, 2005

N

NH N

HN N

N

Me

O

O 2-H2

1H NMR

x

x

*

Fe

13C NMRCompound 2-H2

x

S4

# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and

# The Centre National de la Recherche Scientifique, 2005

0

10

20

30

40

50

60

70

80

90

100

%Int.

400 600 800 1000 1200 1400 1600 1800 2000Mass/Charge

7.8 mV[sum= 779 mV] Profiles 1-100 Smooth Gauss 1 -Baseline 10

After Maintenance 2004/11/10 InsulinB 500fmol CHCAData: DDK-220 Fc-Por-Im H20001.F4 8 Jan 2005 14:03 Cal: 040612_760_1050 20 Oct 2004 11:44 Kratos PC Axima LNR V2.4.0: Mode Linear, Power: 66, P.Ext. @ 769 (bin 54)

770.30

771.35

769.28

768.31

x

x

1H NMRCompound 2-ZnD

S5

N

NH N

HN N

N

Me

O

O 2-H2

Fe

# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and

# The Centre National de la Recherche Scientifique, 2005

x

13C NMR

Compound 2-ZnD

0

10

20

30

40

50

60

70

80

90

100

%Int.

500 1000 1500 2000 2500 3000Mass/Charge

4.8 mV[sum= 481 mV] Profiles 1-100 Smooth Gauss 1 -Baseline 10

After Maintenance 2004/11/10 Data: DDK-222A Fc-Por-Im -Zn0002.F5 8 Jan 2005 14:08 Cal: 040612_760_1050 20 Oct 2004 11:44 Kratos PC Axima LNR V2.4.0: Mode Linear, Power: 64, P.Ext. @ 832 (bin 54)

833.2

832.1

835.2

834.1

1664.7

S6

Compound 2-ZnD

# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and

# The Centre National de la Recherche Scientifique, 2005

13C NMR

N

NH N

HN N

N

Me

O

O3-H2

x

Fe

Me

Me

Me

Me

MeMe

Me

Me

0

10

20

30

40

50

60

70

80

90

100

%Int.

400 600 800 1000 1200 1400 1600 1800 2000 2200Mass/Charge

6.7 mV[sum= 669 mV] Profiles 1-100 Smooth Gauss 1 -Baseline 10

After Maintenance 2004/11/10 Data: DDK-275 (CH3)8- Fc-Por-Im H20001.F7 8 Jan 2005 14:14 Cal: 040612_760_1050 20 Oct 2004 11:44 Kratos PC Axima LNR V2.4.0: Mode Linear, Power: 60, P.Ext. @ 882 (bin 54)

882.42

881.44

883.44

883.86

S7

N

NH N

HN N

N

Me

O

O3-H2

Fe

Me

Me

Me

Me

MeMe

Me

Me

# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and

# The Centre National de la Recherche Scientifique, 2005

xx

1H NMR

Compound 3-ZnD

13C NMRCompound 3-ZnD

x

S8

# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and

# The Centre National de la Recherche Scientifique, 2005

0

10

20

30

40

50

60

70

80

90

100

%Int.

400 600 800 1000 1200 1400 1600 1800 2000 2200Mass/Charge

4.0 mV[sum= 402 mV] Profiles 1-100 Smooth Gauss 1 -Baseline 10

After Maintenance 2004/11/10 Data: DDK-223 (CH3)8- Fc-Por-Im Zn0002.F9 8 Jan 2005 14:26 Cal: InsulinB 10 Nov 2004 18:30 Kratos PC Axima LNR V2.4.0: Mode Linear, Power: 63, P.Ext. @ 944 (bin 54)

944.34

946.35

945.30

948.30

949.46

1H NMRH H

CHO

16 Z-isomer

x*x

Fe

S9

Compound 3-ZnD

# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and

# The Centre National de la Recherche Scientifique, 2005

1H NMR

CHO

H

H

16 E-isomer

*

x

x

Fe

13C NMR

CHO

H

H

16x

Fe

S10

# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and

# The Centre National de la Recherche Scientifique, 2005

CHO

H

H

17 E-isomer

x

*x

Fe

Me

Me

Me

Me

MeMe

Me

Me

1H NMR

13C NMR

x

CHO

H

H

17 E-isomer

Fe

Me

Me

Me

Me

MeMe

Me

Me

S11

# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and

# The Centre National de la Recherche Scientifique, 2005

N

NH N

HN N

N

Me

O

O

H

H

4-H2

13C NMR

xFe

0

10

20

30

40

50

60

70

80

90

100

%Int.

400 600 800 1000 1200 1400 1600 1800 2000 2200Mass/Charge

73 mV[sum= 7316 mV] Profiles 1-100 Smooth Gauss 1 -Baseline 10

After Maintenance 2004/11/10 Data: DDK-226 Fc-CH=Ch-Ph--Por-Im H20001.F10 8 Jan 2005 14:28 Cal: InsulinB 10 Nov 2004 18:30 Kratos PC Axima LNR V2.4.0: Mode Linear, Power: 63, P.Ext. @ 872 (bin 54)

873.35

874.33

872.28

875.44

S12

N

NH N

HN N

N

Me

O

O

H

H

4-H2

Fe

# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and

# The Centre National de la Recherche Scientifique, 2005

x

*

x

Compound 4-ZnD

1H NMR

13C NMR

Compound 4-ZnD

x

S13

# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and

# The Centre National de la Recherche Scientifique, 2005

0

10

20

30

40

50

60

70

80

90

100

%Int.

400 600 800 1000 1200 1400 1600 1800 2000 2200Mass/Charge

21 mV[sum= 2102 mV] Profiles 1-100 Smooth Gauss 1 -Baseline 10

After Maintenance 2004/11/10 Data: DDK-227 Fc-CH=Ch-Ph--Por-Im Zn0001.F11 8 Jan 2005 14:32 Cal: InsulinB 10 Nov 2004 18:30 Kratos PC Axima LNR V2.4.0: Mode Linear, Power: 63, P.Ext. @ 934 (bin 54)

934.38

937.44

938.46

939.48

940.50

1870.88933.36

1H NMR

N

NH N

HN N

N

Me

O

O

H

H

5-H2x

x

Fe

Me

Me

Me

Me

MeMe

Me

Me

S14

Compound 4-ZnD

# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and

# The Centre National de la Recherche Scientifique, 2005

13C NMR

5-H2

x

N

NH N

HN N

N

Me

O

O

H

HFe

Me

Me

Me

Me

MeMe

Me

Me

0

10

20

30

40

50

60

70

80

90

100

%Int.

400 600 800 1000 1200 1400 1600 1800 2000 2200Mass/Charge

13 mV[sum= 1296 mV] Profiles 1-100 Smooth Gauss 1 -Baseline 10

After Maintenance 2004/11/10 Data: DDK-228 (CH3)8-Fc-CH=Ch-Ph--Por-Im H20001.F12 8 Jan 2005 14:35 Cal: InsulinB 10 Nov 2004 18:30 Kratos PC Axima LNR V2.4.0: Mode Linear, Power: 59, P.Ext. @ 984 (bin 56)

985.48

984.48

986.48

987.52

S15

N

NH N

HN N

N

Me

O

O

H

H

5-H2

Fe

Me

Me

Me

Me

MeMe

Me

Me

# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and

# The Centre National de la Recherche Scientifique, 2005

xx

1H NMRCompound 5-ZnD

13C NMR

Compound 5-ZnD

x

S16

# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and

# The Centre National de la Recherche Scientifique, 2005

0

10

20

30

40

50

60

70

80

90

100

%Int.

500 1000 1500 2000 2500 3000 3500 4000Mass/Charge

19 mV[sum= 1916 mV] Profiles 1-100 Smooth Gauss 1 -Baseline 10

After Maintenance 2004/11/10 Data: DDK-229 (CH3)8-Fc-CH=Ch-Ph--Por-Im Zn0003.E1 8 Jan 2005 14:48 Cal: InsulinB 10 Nov 2004 18:30 Kratos PC Axima LNR V2.4.0: Mode Linear, Power: 63, P.Ext. @ 1046 (bin 57)

1045.48

1047.50

1048.51

1050.58

1051.601050.00

1H NMR

6-H2x

*

*

x

N

NH N

HN N

N

Me

O

O

Fe

S17

Compound 5-ZnD

# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and

# The Centre National de la Recherche Scientifique, 2005

0

10

20

30

40

50

60

70

80

90

100

%Int.

500 1000 1500 2000 2500 3000 3500 4000Mass/Charge

1.8 mV[sum= 176 mV] Profiles 1-100 Smooth Gauss 1 -Baseline 10

After Maintenance 2004/11/10 Data: DDK-325 Fc-CH2CH2-Ph--Por-Im H20001.E2 8 Jan 2005 14:51 Cal: InsulinB 10 Nov 2004 18:30 Kratos PC Axima LNR V2.4.0: Mode Linear, Power: 63, P.Ext. @ 874 (bin 54)

874.70

873.69

x

x

1H NMRCompound 6-ZnD

S18

6-H2

N

NH N

HN N

N

Me

O

O

Fe

# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and

# The Centre National de la Recherche Scientifique, 2005

0

10

20

30

40

50

60

70

80

90

100

%Int.

500 1000 1500 2000 2500 3000 3500 4000Mass/Charge

22 mV[sum= 2153 mV] Profiles 1-100 Smooth Gauss 1 -Baseline 10

After Maintenance 2004/11/10 Data: DDK-325 Fc-CH2CH2-Ph--Por-Im Zn0001.E3 8 Jan 2005 14:56 Cal: InsulinB 10 Nov 2004 18:30 Kratos PC Axima LNR V2.4.0: Mode Linear, Power: 67, P.Ext. @ 936 (bin 54)

936.87

939.93

940.96

941.99

1877.16943.16

3-H23-H2

1-H2

3-Zn-Py

3-ZnD

Q-BandSoret Band

Q-Band

a) b)

350 400 450 500 550 600 650 700 7500

0.02

0.04

0.06

0.08

0.1

0.12

0.14

Abs

orba

nce

Wavelength (nm)

450 500 550 600 650 700 750 800

Wavelength (nm)

Abs

orba

nce

Figure S1. UV-visible absorption spectra of a) free base porphyrin 3-H2 (bold broken line), Zn-dimer

3-ZnD (bold solid line) and compound 3-ZnD in pyridine, 3-Zn-Py (thin line) b) inset Q-band region of the

reference free base sample 1-H2 (thin line) and 3-H2 (bold broken line) in CH2Cl2 at rt.

S19

Compound 6-ZnD

# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and

# The Centre National de la Recherche Scientifique, 2005

723

654 3-H2λex = 422 nm

3-ZnDλex = 440 nm

550 600 650 700 750 8000

1

2

3

4

5

Wavelength (nm)

Fluo

resc

ence

inte

nsity

Figure S2. Steady state fluorescence spectra of compound 3-H2 and 3-ZnD in CH2Cl2 at 25 oC,

with excitation of the Soret band in each case.

350 400 450 500 550 600 650 700 7500

0.02

0.04

0.06

0.08

0.1

0.12

Wavelength (nm)

Abs

orba

nce

Q-Band

Soret Band4-Zn-Py

4-ZnD

4-H2

Figure S3. UV-visible absorption spectra of free base porphyrin 4-H2 (bold broken line), Zn-dimer

4-ZnD (bold solid line) and compound 4-ZnD in pyridine, 4-Zn-Py (thin line) in CH2Cl2 at rt.

S20

# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and

# The Centre National de la Recherche Scientifique, 2005

550 600 650 700 750 8000

2

4

6

8

10

12

14

Wavelength (nm)

Fluo

resc

ence

Inte

nsity

4−Η2λex = 420 nm

4−ZnDλex = 440 nm

720

656

Figure S4. Steady state fluorescence spectra of compound 4-H2 and 4-ZnD in CH2Cl2 at 25 oC,

with excitation of the Soret band in each case.

Q-Band

Soret Band

5-H2

5-Zn-Py

5-ZnD

350 400 450 500 550 600 650 700 7500

0.02

0.04

0.06

0.08

0.1

0.12

Wavelength (nm)

Abs

orba

nce

Figure S5. UV-visible absorption spectra of free base porphyrin 5-H2 (bold broken line), Zn-dimer

5-ZnD (bold solid line) and compound 5-ZnD in pyridine, 5-Zn-Py (thin line) in CH2Cl2 at rt.

S21

# Supplementary Material (ESI) for New Journal of Chemistry # This journal is © The Royal Society of Chemistry and

# The Centre National de la Recherche Scientifique, 2005

550 600 650 700 750 800

4

8

12

16

20

Wavelength (nm)

Fluo

resc

ence

Inte

nsity 5-H2

λex = 418 nm

5-ZnDλex = 440 nm

Figure S6. Steady state fluorescence spectra of compound 5-H2 and 5-ZnD in CH2Cl2 at 25 oC, with excitation of the Soret band in each case.

S22