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# 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