Spin Selective Electron Transfer and Charge
Recombination in Self-Assembled Porphyrin
Naphthalenediimide Dyads:
Supporting Information
Andrey G. Moiseev, Prashanth K. Poddutoori and Art van der Est*
Department of Chemistry, Brock University,
500 Glenridge Avenue, St. Catharines, L2S 3A1, ON, Canada.
1

Synthesis and Characterization of Compounds
General: 1 H and 13 C NMR spectra of solutions of the compounds in deutereated chloroform were recorded on Bruker DPX-300 or DPX-600 spectrometers. The signal from the residual protons of the deuterated solvent was used as a frequency reference for 1 H spectra (  7.26). The multiplet from the solvent at (  77.16) was used as a reference for the 13 C spectra. IR spectra as KBr pellets were measured on an ATI Mattson FTIR spectrometer. Mass spectra were obtained on an MSI/Kratos Concept 1S Mass
Spectrometer. Dimethylforamide (DMF) was distilled before use. Naphthalene dianhydride, 2ethylhexylamine and 2M n-BuLi in pentane were purchased from Aldrich and used without further purification.
Synthesis of Al(OCOPh)TPP
Al(OCOPh)TPP was synthesized as described in [1]
Synthesis of ZnTPP
ZnTPP was synthesized by procedure similar to that reported by Lee et al.[2] 1 H NMR (600 MHz,
CDCl
3
) δ 8.98(s, 4H), 8.26(d, J = 7.8, 4H), 7.79 (m, 6H). 13 C NMR (151 MHz, CDCl
3
) δ 150.2, 142.8,
134.5, 132.0, 127.5, 126.6, 121.2.
Synthesis of N-(2-ethylhexyl)-1,8-dicarboxyanhidride-4,5-dicarboxyimide (5).
O O O O N O
NH
2
DMF reflux
O O O O O O
5
The procedure for the preparation of (5) is similar to that of reported by Greenfield et al. [3]. An ovendried 25 mL one-necked round-bottom flask was fitted with a reflux condenser, nitrogen inlet, and magnetic stir bar. A heterogeneous solution of 1,4,5,8-naphthalenetetracarboxydianhydride (1.01 g, 3.77 mmol, 1 equiv.) in dimethylformamide (10 mL) was added, and the flask was purged with nitrogen. A
2

solution of 2-ethylhexylamine (0.40 g, 3.06 mmol, 0.81 equiv.) in dimethylformamide (4 mL) was then added dropwise at 140°C via syringe to the stirred mixture over 2 hours. The reaction mixture was refluxed at 140-150°C under nitrogen atmosphere for 15 hours. After cooling to room temperature, the reaction mixture was cooled for a further 2 hours at -20°C. The solution was then filtered and the solvent was evaporated under reduced pressure to yield an orange solid. The crude product was then dissolved in acetone (15 mL), cooled to -20°C for 8 hours and filtered. The solvent was removed under reduced pressure to afford an orange brownish solid. Column chromatography on silica gel with dichloromethane as eluent afforded N-(2-ethylhexyl)-1,8-dicarboxyanhidride-4,5-dicarboxyimide (5;
0.24 g, 17 %) as a yellowish solid. 1 H and 13 C NMR spectra of product 5 are in agreement with reported spectroscopic data. [3]
1 H NMR (300 MHz, CDCl
3
) δ 8.82 (4H, s), 4.15 (2H, m), 1.93 (1H, m), 1.36 (8H, m), 0.91 (6H, m);
13 C NMR (75 MHz, CDCl
3
) δ 162.7, 159.0, 133.3, 131.4, 128.1, 123.0, 45.0, 38.1, 30.8, 28.8, 24.2,
23.2, 14.2, 10.7; MS (EI) 379 (M + , 25), 281 (8), 268 (18), 237 (5), 117 (100), 82 (22), 70 (6), 57 (17), 41
(31).
Synthesis of Pyr(CH
2
)
2
NDI
NH
2
(CH
2
)
2
O N O O N O
4a
N
DMF reflux
O O O O N O
(CH
2
)
2
5
N
Pyr(CH
2
)
2
NDI
An oven-dried 5 mL one-necked round-bottom flask was fitted with a reflux condenser, nitrogen inlet, and magnetic stir bar. A solution of 5 (0.10 g, 0.26 mmol, 1.0 equv.) in dimethylformamide (1.0 mL) was added, and the flask was purged with nitrogen. A solution of 4-(2-aminoethyl)pyridine 4a synthesized by the procedure reported by Steinmetzer et al .. [4] (0.036 g, 0.3 mmol, 1.1 equiv.) in dimethylformamide (1.0 mL) was then added dropwise at 150°C via syringe to the stirred mixture over 1
3

hour. The reaction mixture was refluxed at 140-150°C under nitrogen atmosphere for 12 hours. After cooling to room temperature, the solvent was removed under reduced pressure to yield a yellowish solid.
The product was purified by column chromatography (silica, CH
2
Cl
2
 EtOAc) to afford N-(2ethylhexyl)-N-(4-(2-ethyl)pyridyl) 1,4,5,8-naphthalene diimide as a slightly yellowish solid (0.051 g, 40
%).
Pyr(CH
2
)
2
NDI: 1 H NMR (300 MHz, CDCl
3
) δ 8.79 (s, 4H), 8.56 (d, J = 6 Hz, 2H), 7.29 (d, J = 6 Hz,
2H), 4.48 (m, 2H), 4.17 (m, 2H), 3.09 (t, J = 7.5 Hz , 2H), 1.96 (m, 1H), 1.39 (m, 8H), 0.93 (m, 6H); 13 C
NMR (75MHz, CDCl
3
) δ 163.2, 162.9, 150.1, 147.2, 131.3, 131.2, 127.0, 126.9, 126.8, 126.4, 124.4,
44.8, 41.1, 38.1, 33.6, 30.8, 24.2, 23.2, 14.2, 10.7, 1.2; MS (EI) 483 (M + , 43), 378 (27), 372(11),
296(6), 280(8), 267(8), 249(6), 153(11), 106(100), 105(17), 70(7), 57(10), 55(8), 43(8), 41(8); IR (KBr)
ν (cm -1 ) 3078 (m), 2962 (s), 2931 (s), 2858 (m), 1703 (s), 1657 (s), 1604 (s), 1581 (s) 1454 (s), 1421
(m), 1375 (s), 1338 (s), 1259 (s), 1244 (s), 1178(s), 1161 (m), 1086 (s), 1014(s), 893(m), 800(s), 769 (s),
714 (m), 575 (m); HRMS(EI) exact mass calculated for C
29
H
29
N
3
O
4
483.2158, found 483.2152
Synthesis of Pyr(CH
2
)
4
NDI
NH
2
C
N
CH
3
Na
CN LiAlH
4
Et
2
O
N N N
4b
Preparation of 4-(4-cyanobutyl)pyridine was carried out using a method similar to that of reported by
Magnus et al. [5] Then reduction of 4-(4-cyanobutyl)pyridine with LiAlH
4
in diethyl ether formed 4-(4aminobutyl)pyridine ( 4b ) in 82 % yield similar to that of reported by Kassiou et al. [6]
4

NH
2
(CH
2
)
4
O N O
O N O
4b
N
DMF reflux
O O O
O N O
(CH
2
)
4
5
N
Pyr(CH
2
)
4
NDI
An oven-dried 10 mL one-necked round-bottom flask was fitted with a reflux condenser, nitrogen inlet, and magnetic stir bar. A solution of 5 (0.10 g, 0.26 mmol, 1.0 equv.) in dimethylformamide (2.0 mL) was added, and the flask was purged with nitrogen. A solution of 4-(4-aminobutyl)pyridine 4b
(0.047 g, 0.31 mmol, 1.2 equiv.) in dimethylformamide (2.0 mL) was then added dropwise at 150°C using a syringe to the stirred mixture over 1 hour. The reaction mixture was refluxed at 140-150°C under nitrogen atmosphere for 12 hours. After cooling to room temperature, the solvent was removed under reduced pressure to a yield orange solid. The product was purified by column chromatography
(silica, CH
2
Cl
2
 EtOAc) to afford N-(2-ethylhexyl)-N-(4-(4-butyl)pyridyl) 1,4,5,8-naphthalene diimide as an orange solid ( Pyr(CH
2
)
4
NDI ; 0.11 g, 76 %).
Pyr(CH
2
)
4
NDI: 1 H NMR (300 MHz, CDCl
3
) δ 8.75 (s, 4H), 8.48 (d, J = 4.2 Hz, 2H), 7.13 (d, J = 6
Hz, 2H), 4.24 (m, 2H), 4.14 (m, 2H), 2.71 (m, 2H), 1.94 (m, 1H), 1.80 (m, 4H), 1.36 (m, 8H), 0.91 (m,
6H); 13 C NMR (75MHz, CDCl
3
) δ 163.3, 163.0, 151.0, 149.9, 131.1, 131.1, 126.8, 126.6, 124.02, 44.8,
40.6, 38.1, 30.8, 28.7, 27.8, 27.7, 24.2, 23.1, 14.2, 10.7; MS (EI) 511 (M + , 100), 483(9), 482 (9), 468(8),
454(8), 414(13), 413(32), 412(8), 401(12), 400(37), 378(6), 330(5), 281(5), 280(5), 269(5), 267(7),
249(7), 132(7), 129(8), 120(9), 107(9), 106(33), 98(6), 97(7), 93(19), 85(7), 83(6), 73(6), 71(10),
70(10), 69(8), 57(20), 55(15), 45(6), 43(18), 42(6), 41(17); IR (KBr), ν (cm -1 ) 3086 (m), 2962 (s),
2929(s), 2858 (m), 1705 (s), 1660(s), 1603 (m), 1579(m), 1456(m), 1379(m), 1338(s), 1261 (s), 1093(s),
1022(s), 876(m), 800(s), 768(m); HRMS(EI) exact mass calculated for C
31
H
33
N
3
O
4
511.2471, found
511.2467.
5

Synthesis of Pyr(CH
2
)
7
NDI (2c)
O N O
O O O
NH
2
(CH
2
)
4
N
DMF reflux
4f
O N O
O N
(CH
2
)
7
O
5
N
Pyr(CH
2
)
7
NDI
An oven-dried 15 mL one-necked round-bottom flask was fitted with a reflux condenser, nitrogen inlet, and magnetic stir bar. Solution of 5 (0.52 g, 1.36 mmol, 1.0 equv.) in dimethylformamide (3.0 mL) was added, and then flask was purged with nitrogen. A solution of 4-(7-aminoheptyl)pyridine 4c synthesized in three steps by the procedure reported by Govoni et al.. [7] (0.28 g, 1.5 mmol, 1.1 equiv.) in dimethylformamide (4.0 mL) was then added dropwise at 120°C via syringe to the stirred mixture over 15 minutes. The reaction mixture was refluxed at 120°C under nitrogen atmosphere for 12 hours.
After cooling to room temperature, the solvent was removed under reduced pressure to yield a brown solid. The product was purified by column chromatography (silica, EtOAc) to afford N-(2-ethylhexyl)-
N’-(7-(4-pyridyl)-heptyl)-1,4,5,8-naphthalenediimide as a yellowish solid
Pyr(CH
2
)
7
-NDI: 1 H NMR (300 MHz, CDCl
3
) δ 8.75 (s, 4H), 8.46 (d, J = 6.0 Hz, 2H), 7.09 (d, J = 6.0
Hz, 2H), 4.14 (m, 4H), 2.59 (t, J = 7.5 Hz, 2H), 1.94 (m, 1H), 1.73 (m, 2H), 1.64 (m, 2H), 1.35 (m,
14H), 0.91 (m, 6H); 13 C NMR (75 MHz, CDCl
3
) δ 163.3, 162.9, 151.7, 149.8, 131.1, 131.1, 126.8,
126.8, 126.7, 126.7, 124.0, 44.7, 41.0, 38.0, 35.3, 30.8, 30.3, 29.2, 29.1, 28.7, 28.1, 27.0, 24.2, 23.2,
14.2, 10.7; MS (EI), m/z 554 (M + + 1, 19), 553 (M + , 43), 483 (14), 442(11), 380(7), 379(9), 378(22),
281(10), 280(14), 279(10), 269(12), 268(9), 267(26), 249(10), 223(5), 222(6), 221(4), 193(5), 191(8),
178(7), 169(4), 166(4), 165(5), 163(7), 162(8), 153(6), 152(8), 151(11), 150(5), 149(22), 147(11),
141(6), 139(5), 137(8), 136(6), 135(12), 131(9), 129(31), 128(6), 127(8), 126(5), 125(13), 124(7),
6

123(12), 122(5), 121(8), 120(6), 119(11), 113(11), 112(20), 111(25), 110(10), 109(16), 107(13),
106(42), 105(22), 104(11), 99(11), 98(15), 97(32), 96(12), 95(23), 94(6), 93(18), 92(8), 91(11), 87(6),
85(32), 84(20), 83(38), 82(18), 81(26), 80(9), 79(11), 78(10), 77(10), 75(6), 73(10), 72(8), 71(47),
70(34), 69(68), 68(13), 67(20), 65(5), 60(13), 58(9), 57(89), 56(28), 55(76), 54(12), 53(12), 52(7),
51(13), 50(6), 45(16), 44(61), 43(100), 42(20), 41(70); IR (KBr), ν (cm -1 ) 3086(m), 2956(s), 2929(s),
2856(s), 1705(s), 1660(s), 1601(s), 1579(s), 1454(s), 1379(s), 1338(s), 1242(s), 1184(m), 1078(m),
978(m), 877(m), 800(m), 766(s), 715(m), 613(m), 598(m); HRMS(EI) exact mass calculated for
C
34
H
39
N
3
O
4
553.2941, found 553.2935.
Microwave power (mW)  early
(ns) t late
(µs) A(late)/A(early)
6.3
1.0
600
580
44
40
0.98
0.72
5.
6.
7.
0.2 660 41 0.86
Table S1 . Lifetimes of the early and late spectra of Al(OCOPh)TPP-Pyr(CH
2
)
7
NDI obtained by fitting kinetic traces at different microwave powers.
1.
2.
3.
4.
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6777 (1996).
Steinmetzer T., Schweinitz A., Stürzebecher A., Dönnecke D., Uhland K., Schuster O.,
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