Supplementary Material for Perkin Transactions 2
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Supplementary data
Supplementary Publication: Synthesis and photophysical
properties of porphyrins containing viologen units for ultrafast molecular photonics
Robert Laudien*, Iori Yoshida, Toshihiko Nagamura
Molecular Photonics Laboratory, Research Institute of Electronics, Shizuoka
University, 3-5-1 Johoku, Hamamatsu, 432-8011, Japan
* To whom correspondence should be addressed.
University of Potsdam, Institutes of Chemistry, Karl-Liebknecht-Str. 24-25, Haus
25, D-14476 Golm, Germany
e-mail: laudien@rz.uni-potsdam.de
Introduction
Herein we report a supplementary information refering to our published paper on
the synthesis and photophysical properties of porphyrins containing viologen units
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for ultrafast molecular photonics. Several 5,15-diarylporphyrins with anionic
groups in order to incorporate them into IPCT complexes with polymer viologen
should be synthesized, and their transient absorption behavior should be investigated upon fs laser excitation. However, the formation of these intermolecular
complexes did not succeed presumably due to steric reasons as will be discussed
in the following. Consequently, intramolecular complexes in which the porphyrin
and the viologen units are connected via alkyl chain spacers of different length
have been synthesized. Photoresponsive properties of the porphyrin-viologen
complexes have been investigated by excitation with a femtosecond laser at 400
nm, which are presented in the above mentioned paper.
Results and Discussion
The 5,15-diarylporphyrins without viologen unit were synthesized according to
the method of Osuka et al1 by condensation of the respective substituted benzaldehyde with 3,3’-diethyl-4,4’-dimethyl-2,2’-dipyrromethane 1. The synthetic
route is shown in Scheme 1 and described in detail in the experimenal section.
The transformation of the diarylporphyrins to porphyrin-viologen complexes
was involved with some difficulties. To form an intermolecular charge transfer
complex the porphyrin 3b substituted with anionic carboxylate groups should be
converted into an ion-pair complex with polymer viologen dichloride 4 (PV2+ 2Cl) containing 4,4’-bipyridinium ion as a part of the main chain. The latter has been
synthesized in our laboratory.2,3 The structure of this polymer is shown in Scheme
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2, the content of 4,4’-bipyridinium ions is 3.610-4 mol g-1. To form the complex
the porphyrin disodium salt 3b was stirred with an equimolar amount of the polymer 4 for 30 minutes in methanol, the solvent was evaporated, and the solid dissolved in chloroform to remove NaCl. No stable ion-pair complex, however,
could be obtained according to UV-Vis measurements.
The reason is most probably due to steric effects. Whereas in the diarylporphyrin two negative charges are separated by a relatively long distance, two positive
charges in the polymer viologen are situated quite close to each other. Consequently, positive and negative charges are not located complementary to each other to ensure tight electrostatic attraction between a diarylporphyrin and a polymer
viologen molecule. Another possibility of aggregation is that two negative charges
of the porphyrin attract two positive charges of different viologen molecules, but
in that case the bulky body of the porphyrin may prevent the build-up of a bigger
aggregate of ion-pair complexes. An indication for the reliability of that assumption is the successful formation of a stable ion-pair complex between polymer
viologen dichloride and mesoporphyrin 5. In that case the charges are located
complementary to each other to ensure tight electrostatic attraction as is illustrated
in Scheme 2.
An attempt to prepare diarylporphyrins with anionic groups in a somewhat
different position was to introduce sulfopropyloxy groups into p- and mhydroxybenzaldehyde by reacting these aldehydes with propanesultone followed
by condensation with dipyrromethane to synthesize the respective porphyrins (R =
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p- and m-O(CH2)3SO3Na in porphyrin 3). Propanesultone can be reacted with
nucleophilic compounds like aliphatic and aromatic amines, alcohols and carboxylic acids.4-7 However, the reaction of the benzaldehydes with propanesultone
delivered side products in appreciable amount besides the desired sulfopropyloxybenzaldehydes and it was notoriously difficult to isolate these products.
As the preparation of an IPCT complex between 5,15-diarylporphyrin and polymer viologen dichloride was involved with the above mentioned severe difficulties, we concentrated on the synthesis of molecular arrays in which the porphyrin
and the viologen units are connected by alkyl chains of different length. Into the
diarylporphyrins 3e-h the viologen unit was introduced by a quarternization reaction with N-pentyl-4(4’-pyridyl)pyridinium bromide 6 (Scheme 3). The parasubstituted porphyrins 3c and 3d, which were almost insoluble in DMF or other
common solvents, were not converted. After work-up, intramolecular porphyrinviologen complexes in yields between 15 and 23 % could be obtained except for
porphyrin 3e with the shortest alkyl chain length (n = 2) probably due to steric
hindrance. In the latter case only impure product according to UV-Vis measurements in a very low yield (4.5 %) was obtained.
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Experimental
Preparations
All starting materials as well as solvents, which were obtained commercially,
were applied without further purification. For the preparation of the diarylporphyrins dehydrated acetonitrile was used.
3,3’-Diethyl-4,4’-dimethyl-2,2’-dipyrromethane (1). Dibenzyl 3,3’-diethyl4,4’-dimethyldipyrromethane-5,5’-dicarboxylate8 (0.050 mole) was refluxed in a
mixture of ethanol (370 ml) and sodium hydroxide solution (10 %, 100 ml) for 5
hours. The ethanol was evaporated under reduced pressure, and hydrazine (0.65
ml) was added to the remaining aqueous solution, which was sealed in a stainless
steel pressure vessel and heated at 170 °C for 5 hours. After cooling, the reaction
mixture was poured into 500 ml of water and extracted with 250 ml of chloroform. The organic layer was separated, washed with water, dried over anhydrous
sodium sulfate, and evaporated. The residue was purified by silica-gel column
chromatography using chloroform as the eluant to give red brown crystals (78.9
%), m.p. 49-50 °C. 1H-NMR (CDCl3,  ppm): 7.35 (s(br), 2H, NH), 6.37 (m, 2H,
5,5’-H), 3.83 (s, 2H, -CH2-), 2.44 (q, 4H, -CH2CH3), 2.05 (s, 6H, -CH3), 1.10 (t,
6H, -CH2CH3). The dipyrromethane slowly darkens in the air but can be stored
indefinitely in a freezer. It contains a small amount of the disodium salt of 1 as a
white powder (mp 172-173 °C)9, which does not need to be removed for the following condensation.
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For the synthesis of the following aldehydes 2c-h the synthetic procedure of
Little10 has been modified.
Bromoalkyloxybenzaldehydes (2c-h)
p-(2-Bromoethyloxy)benzaldehyde
(2c).
p-Hydroxybenzaldehyde
(3.5
mmole), 1,2-dibromoethane (35 mmole) and potassium carbonate (35 mmole)
were stirred in 70 ml of DMF for 5 days in the dark. After the reaction the solid
(K2CO3) was removed by filtration and DMF as well as excess of dibromoethane
evaporated in vacuum. The residue was dissolved in chloroform and the solid
again removed. After evaporation of chloroform the crude product (liquid) was
purified by silica-gel column chromatography using chloroform as the eluant to
give a light yellow solid of 2c (73.9 %). 1H-NMR (CDCl3,  ppm): 9.93 (s, 1H, CHO), 7.88 (d, 2H, Ar), 7.03 (d, 2H, Ar), 4.40 (t, 2H, -OCH2CH2Br), 3.66 (t, 2H,
-OCH2CH2Br).
p-(3-Bromopropyloxy)benzaldehyde (2d). The aldehyde 2d was prepared by
the method given for 2c using 1,3-dibromopropane instead of 1,2-dibromoethane.
It was obtained as a light yellow liquid (61.1 %). 1H-NMR (CDCl3,  ppm): 9.94
(s, 1H, -CHO), 7.89 (d, 2H, Ar), 7.04 (d, 2H, Ar), 4.23 (t, 2H, -OCH2C2H4Br),
3.62 (t, 2H, -OC2H4CH2Br), 2.36 (qu, 2H, -OCH2CH2CH2Br).
m-(2-Bromoethyloxy)benzaldehyde (2e). The aldehyde 2e was prepared by
the method given for 2c using m-hydroxybenzaldehyde instead of p-hydroxybenzaldehyde. It was obtained as a light yellow liquid (52.6 %). 1H-NMR (CDCl3, 
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ppm): 10.03 (s, 1H, -CHO), 7.48 (4 signals, 4H, Ar), 4.39 (t, 2H, -OCH2CH2Br),
3.67 (t, 2H, -OCH2CH2Br).
m-(3-Bromopropyloxy)benzaldehyde (2f). The aldehyde 2f was prepared by
the method given for 2e using 1,3-dibromopropane instead of 1,2-dibromoethane.
It was obtained as a light yellow liquid (79.0 %). 1H-NMR (CDCl3,  ppm): 10.03
(s, 1H, -CHO), 7.46 (4 signals, 4H, Ar), 4.20 (t, 2H, -OCH2C2H4Br), 3.63 (t, 2H, OC2H4CH2Br), 2.36 (qu, 2H, -OCH2CH2CH2Br).
m-(4-Bromobutyloxy)benzaldehyde (2g). The aldehyde 2g was prepared by
the method given for 2e using 1,4-dibromobutane instead of 1,2-dibromoethane.
1,4-dibromobutane could not be completely removed by vacuum distillation nor
by column chromatography. The obtained light yellow liquid of 2g and 1,4dibromobutane was applied for the next reaction step, where separation was completed. 1H-NMR (CDCl3,  ppm): 10.02 (s, 1H, -CHO), 7.44 (4 signals, 4H, Ar),
4.07 (t, 2H, -OCH2C3H6Br), 3.48 (m, -OC3H6CH2Br and BrCH2C2H4CH2Br), 2.07
(m, -OCH2C2H4CH2Br and BrCH2C2H4CH2Br).
m-(6-Bromohexyloxy)benzaldehyde (2h). The aldehyde 2h was prepared by
the method given for 2e using 1,6-dibromohexane instead of 1,2-dibromoethane.
The removal of 1,6-dibromohexane involved the same problems as above. The
light yellow liquid of 2h and 1,6-dibromohexane was applied for the next reaction
step. 1H-NMR (CDCl3,  ppm): 10.02 (s, 1H, -CHO), 7.43 (4 signals, 4H, Ar),
4.04 (t, 2H, -OCH2C5H10Br), 3.43 (t, -OC5H10CH2Br and BrCH2C4H8CH2Br),
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1.84 (m, -OCH2CH2C2H4CH2CH2Br and BrCH2CH2C2H4-CH2CH2Br), 1.61 (m, OC2H4C2H4C2H4Br and BrC2H4C2H4C2H4Br).
Porphyrins 3a-h
5,15-Bis(p-carboxylphenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphyrin (3a). p-Formylbenzoic acid (1.8 mmole) and 3,3’-diethyl-4,4’-dimethyl2,2’-dipyrromethane (1) (1.8 mmole) were dissolved in 20 ml of acetonitrile. Trichloroacetic acid (50 mg) was added, and the mixture was stirred for 5 hours in
the dark under nitrogen at room temperature. Then p-chloranil (720 mg) in 20 ml
of tetrahydrofuran was added, and the mixture was stirred again for 3 hours. The
solvent was evaporated, and the resulting solids were suspended in methanol, collected by filtration, and washed thoroughly with methanol. This crude product
was dissolved in chloroform, collected, and washed with chloroform to give the
desired violet porphyrin 3a (63.1 %). UV-Vis (DMF, max nm): 407, 505, 537,
574, 626. MS (DMF, m/e): 719.05 (M+H+). Elemental analysis: Found: C, 77.2;
H, 6.2; N, 7.5. C46H46N4O4 requires C, 76.85; H, 6.45; N, 7.8.
Porphyrin (3b). To convert the porphyrin 3a into its disodium salt it was suspended in methanol, and after addition of an equimolar amount of sodium hydroxide the reaction mixture was stirred for around 30 minutes. Any unreacted starting
material could be easily removed from the methanol-soluble disodium salt 3b by a
centrifuge before the solvent was evaporated. 1H-NMR (CD3OD,  ppm): 10.31
(s, 2H, meso), 8.42 (d, 4H, Ar), 8.07 (d, 4H, Ar), 4.05 (q, 8H, -CH2CH3), 2.54 (s,
12H, -CH3), 1.80 (t, 12H, -CH2CH3), broad NH-signal not detected. Elemental
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analysis: Found: C, 72.6; H, 6.0; N, 7.2. C46H44N4O4Na2 requires C, 72.4; H, 5.8;
N, 7.3.
5,15-Bis(p-(2-bromoethyloxy)phenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphyrin (3c). The porphyrin 3c was prepared in the same manner as 3a
starting from p-(2-bromoethyloxy)benzaldehyde (2c). Violet crystals were obtained (48.0 %). UV-Vis (CHCl3, max nm): 409, 507, 539, 574, 624. MS (CHCl3,
m/e): 878.24 (M+H+). Elemental analysis: Found: C, 66.05; H, 6.1; N, 6.1.
C48H52N4O2Br2 requires C, 65.8; H, 6.0; N, 6.4.
5,15-Bis(p-(3-bromopropyloxy)phenyl)-2,8,12,18-tetraethyl-3,7,13,17tetramethylporphyrin (3d). The porphyrin 3d was prepared in the same manner
as 3a starting from p-(3-bromopropyloxy)benzaldehyde (2d). Violet crystals were
obtained (45.5 %). UV-Vis as for 3c. MS (CHCl3, m/e): 907.77 (M+H+). Elemental analysis: Found: C, 66.0; H, 6.1; N, 6.2. C50H56N4O2Br2 requires C, 66.4;
H, 6.2; N, 6.2.
5,15-Bis(m-(2-bromoethyloxy)phenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphyrin (3e). The porphyrin 3e was prepared in a similar manner as 3a
starting from m-(2-bromoethyloxy)benzaldehyde (2e), but a different purification
method had to be applied. After evaporation of the solvent, the resulting solids
were separated twice by silica-gel column chromatography using chloroform as
the eluant. The separated porphyrin was suspended in methanol, collected, and
washed with methanol to give 55.3 % of pure 3e. UV-Vis as for 3c. 1H-NMR
(CDCl3,  ppm): 10.23 (s, 2H, meso), 7.62 (4 signals, 8H, Ar), 4.43 (t, 4H, -
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OCH2CH2Br), 4.02 (q, 8H, -CH2CH3), 3.69 (t, 4H, -OCH2CH2Br), 2.56 (s, 12H, CH3), 1.77 (t, 12H, -CH2CH3), broad NH-signal not detected. Elemental analysis:
Found: C, 66.1; H, 5.9; N, 6.2. C48H52N4O2Br2 requires C, 65.8; H, 6.0; N, 6.4.
5,15-Bis(m-(3-bromopropyloxy)phenyl)-2,8,12,18-tetraethyl-3,7,13,17tetramethylporphyrin (3f). The porphyrin 3f was prepared in the same manner
as 3e starting from m-(3-bromopropyloxy)benzaldehyde (2f) to give 51.6 % of
pure 3f. UV-Vis as for 3c. 1H-NMR (CDCl3,  ppm): 10.23 (s, 2H, meso), 7.61 (4
signals, 8H, Ar), 4.25 (t, 4H, -OCH2C2H4Br), 4.02 (q, 8H, -CH2CH3), 3.64 (t, 4H,
-OC2H4CH2Br), 2.57 (s, 12H, -CH3), 2.37 (qu, 4H, -OCH2CH2CH2Br), 1.77 (t,
12H, -CH2CH3), broad NH-signal not detected. Elemental analysis: Found: C,
66.15; H, 6.0; N, 6.4. C50H56N4O2Br2 requires C, 66.4; H, 6.2; N, 6.2.
5,15-Bis(m-(4-bromobutyloxy)phenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphyrin (3g). The porphyrin 3g was prepared in the same manner as 3e
starting from the obtained mixture of m-(4-bromobutyloxy)benzaldehyde (2g) and
1,4-dibromobutane and 2.8 mmole of the dipyrromethane 1 (i.e. 80 % of the applied m-hydroxybenzaldehyde for the synthesis of 2g). The dibromobutane did
not take part in the condensation reaction. After purification in a similar manner
as 3e, 64.8 % of 3g relative to dipyrromethane 1 could be obtained. UV-Vis as for
3c. 1H-NMR (CDCl3,  ppm): 10.23 (s, 2H, meso), 7.61 (4 signals, 8H, Ar), 4.15
(t, 4H, -OCH2C3H6Br), 4.02 (q, 8H, -CH2CH3), 3.50 (t, 4H, -OC3H6CH2Br), 2.57
(s, 12H, -CH3), 2.06 (m, 8H, -OCH2C2H4CH2Br), 1.77 (t, 12H, -CH2CH3), broad
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NH-signal not detected. Elemental analysis: Found: C, 67.2; H, 6.5; N, 6.0.
C52H60N4O2Br2 requires C, 66.95; H, 6.5; N, 6.0.
5,15-Bis(m-(6-bromohexyloxy)phenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphyrin (3h). The porphyrin 3h was prepared and purified in the same
manner as 3g starting from the mixture of m-(6-bromohexyloxy)benzaldehyde
(2h) and 1,6-dibromohexane. 57.7 % of pure 3g relative to dipyrromethane 1 was
obtained. UV-Vis as for 3c. 1H-NMR (CDCl3,  ppm): 10.23 (s, 2H, meso), 7.60
(4 signals, 8H, Ar), 4.11 (t, 4H, -OCH2C5H10Br), 4.02 (q, 8H, -CH2CH3), 3.38 (t,
4H, -OC5H10CH2Br), 2.58 (s, 12H, -CH3), 1.77 (t, 20H, -CH2CH3 and OCH2CH2C2H4-CH2CH2Br, 1.51 (m, 8H, -OC2H4C2H4C2H4Br), broad NH-signal
not detected. Elemental analysis: Found: C, 68.3; H, 6.75; N, 5.9. C56H68N4O2Br2
requires C, 68.0; H, 6.9; N, 5.7.
N-Pentyl-4(4’-pyridyl)pyridinium bromide (6). 4,4’-Bipyridine and pentyl
bromide in an equimolar ratio (50 mmole) were refluxed in 150 ml of 1,2dimethoxyethane (DME) with stirring for 3 days in the dark under nitrogen. The
precipitated solid was collected by filtration and washed with DME. Light yellow
crystals (55.9 %) were obtained. 1H-NMR (CDCl3,  ppm): 9.67, 8.87, 8.41 and
7.72 (d, 2H, Bipyr), 5.04 (t, 2H, -CH2C4H9), 2.04 (qu, 2H, -CH2CH2C3H7), 1.36
(m, 4H, -C2H4C2H4CH3), 0.88 (t, 3H, -C4H8CH3).
Porphyrin-viologen complexes (7f-h)
5,15-Bis(m-(N-pentyl-N’-propyloxy-4,4’-bipyridinium)phenyl)-2,8,12,18tetraethyl-3,7,13,17-tetramethylporphyrin tetrabromide (7f, n = 3). The por-
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phyrin 3f (0.3 mmole) and N-pentyl-4(4’-pyridyl)pyridinium bromide 6 (9
mmole, 15 times excess) were dissolved in 40 ml of DMF and stirred for 5 days at
80-90 °C in the dark under nitrogen. The solvent was evaporated, and the solids
were dissolved in chloroform (100 ml) and washed five times with an aqueous
sodium chloride solution (200 ml). After evaporation of chloroform the crude
product was separated by Sephadex LH-20 column chromatography using methanol as the eluant to get the pure porphyrin-viologen complex 7f (22.4 %). UV-Vis
(CH3OH, max nm): 265, 404, 504, 537, 572, 623. 1H-NMR (CD3OD,  ppm):
10.22 (s, 2H, meso), 9.29, 8.03, 7.40 and 7.28 (d, 4H, Bipyr), 7.60 (4 signals, 8H,
Ar), 4.96 (t, 4H, -CH2C4H9), 4.46 (qu, 4H, -CH2CH2C3H7), 4.34 (t, 4H, OCH2C2H4-), 4.24 (t, 4H, -OC2H4CH2-), 3.95 (q, 8H, -CH2CH3), 2.55 (qu, 4H, OCH2CH2CH2-), 2.52 (m, 8H, -C2H4C2H4CH3), 2.37 (s, 12H, -CH3), 1.71 (t, 12H,
-CH2CH3), 1.68 (t, 6H, -C4H8CH3), broad NH-signal not detected. Elemental
analysis: Found: C, 63.8; H, 6.7; N, 7.5. C80H94N8O2Br4 requires C, 63.25; H,
6.25; N, 7.4.
5,15-Bis(m-(N-pentyl-N’-butyloxy-4,4’-bipyridinium)phenyl)-2,8,12,18tetraethyl-3,7,13,17-tetramethylporphyrin tetrabromide (7g, n = 4). The porphyrin 7g was prepared in the same manner as 7f starting from porphyrin 3g. 15.2
% of the porphyrin-viologen complex were obtained. UV-Vis as for 7f. 1H-NMR
(CD3OD,  ppm): 10.23 (s, 2H, meso), 9.22, 7.99, 7.58 and 7.37 (d, 4H, Bipyr),
7.80 (4 signals, 8H, Ar), 4.78 (t, 4H, -CH2C4H9), 4.17 (m, 8H, -OCH2C3H6- and OC3H6CH2-), 3.92 (q, 8H, -CH2CH3), 2.43 (s, 12H, -CH3), 2.30 (m, 8H, -
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OCH2C2H4CH2-), 1.84 (m, 4H, -CH2CH2C3H7), 1.62 (t, 12H, -CH2CH3), 1.18 (m,
8H, -C2H4C2H4CH3), 0.79 (t, 6H, -C4H8CH3), broad NH-signal not detected. Elemental analysis: Found: C, 64.2; H, 6.7; N, 7.25. C82H98N8O2Br4 requires C,
63.65; H, 6.4; N, 7.2.
5,15-Bis(m-(N-pentyl-N’-hexyloxy-4,4’-bipyridinium)phenyl)-2,8,12,18tetraethyl-3,7,13,17-tetramethylporphyrin tetrabromide (7h, n = 6). The porphyrin 7h was prepared in the same manner as 7f starting from porphyrin 3h. 16.9
% of the porphyrin-viologen complex were obtained. UV-Vis as for 7f. 1H-NMR
(CD3OD,  ppm): 10.20 (s, 2H, meso), 8.72, 8.34, 7.50 and 7.32 (d, 4H, Bipyr),
7.80 (4 signals, 8H, Ar), 4.78 (t, 4H, -CH2C4H9), 4.04 (m, 8H, -OCH2C5H10- and
4H, -OC5H10CH2-), 3.94 (q, 8H, -CH2CH3), 2.49 (s, 12H, -CH3), 1.87 (m, 4H, CH2CH2C3H7), 1.68 (t, 12H, -CH2CH3), 1.57-1.34 (m, 16H, -OCH2C4H8CH2-),
1.18 (m, 8H, -C2H4C2H4CH3), 0.80 (t, 6H, -C4H8CH3), broad NH-signal not detected. Elemental analysis: Found: C, 64.9; H, 6.9; N, 6.8. C86H106N8O2Br4 requires C, 64.4; H, 6.7; N, 7.0.
Transient absorption measurements
Cyclohexanone solutions of the porphyrins and porphyrin-viologen complexes in
a 4 mm cell were excited by the second harmonics (400 nm) of a Ti:sapphire laser
with a 10 Hz regenerative amplifier at room temperature. Absorbance at 400 nm
was about 2.0 for these solutions. The amplified Ti:sapphire laser delivered pulses
with a full width at half-maximum (FWHM) of 200-250 fs, 10 Hz repetition, and
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a maximum power of 6 mJ/pulse at 800 nm. The amplified output was frequency
doubled by a BBO crystal to generate 400 nm light, which was used as a pump
source (60-120 µJ/pulse). A probe white light was obtained by focusing the residual 800 nm light after passing through a BBO crystal into a 1 cm cell containing a
D2O/H2O (2:1) mixture. The transient absorption and the decay dynamics were
measured by a dual photodiode array system (Hamamatsu Photonics C6140PMA) using an optical delay (2 µm/step). The intensities of the probe light, with
and without the pump pulse, were averaged by 20 times. A block diagram of the
femtosecond transient absorption measurement setup is shown in Figure 1.
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+
NH
R
HN
1
CCl3COOH
(CH3CN)
2a,c-h
NH
R
OHC
NH
HN
HN
R
p-Chloranil
(THF)
R
NH
N
N
HN
3a-h
R
R
a
p-COOH
e
m-O(CH2)2Br
b
p-COONa
f
m-O(CH2)3Br
Scheme S1
16
c
p-O(CH2)2Br
g
m-O(CH2)4Br
d
p-O(CH2)3Br
h
m-O(CH2)6Br
R
Supplementary Material for Perkin Transactions 2
This journal is © The Royal Society of Chemistry 2002
((CH2)4O)x N +
+ N
2Cl
-
y
4
-
N
+
-
+
N
CO2
N
NH
HN
N
CO2
((CH2)4)x
5
4
Scheme S2
17
y
Supplementary Material for Perkin Transactions 2
This journal is © The Royal Society of Chemistry 2002
NH
N
N
HN
Por 3e-h
+
(DMF)
N
+
R
R
N C5H11
-
Br
6
R=
O(CH2)n
+ N C5H11
N +
-
2 Br
7e-h
Scheme S3
18
Supplementary Material for Perkin Transactions 2
This journal is © The Royal Society of Chemistry 2002
Fig. S1. Block diagram of a fs transient absorption measurement setup.
Dual
Photodiode
array
Variable
Delay Line
(2 μm / step)
Blue
Filter
sample
400 nm
100 μJ
White
Light
800 nm
4 mJ, 200 fs
BBO
19
D2O/H2O
cell