Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
Yukitami Mizuno and Takuzo Aida*
Department of Chemistry and Biotechnology, School of Engineering,
The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
(Total 10 pages including this cover page)
Table of Contents
1. Experimental Procedures ..................................................................................... 2
2. Synthesis of precursor porphyrins 7–9 and cyclic dimer 2 . ................................. 3
3.
1 H NMR spectra of 2 and its mandelate complexes in CDCl
3
( Figure S1 ) ........ 8
4. Circular dichroism (CD) spectrum of a mandelate complex of 2 after dissolved in acetic acid ( Figure S2 ) ............................................................ 9
5. References ......................................................................................................... 10
1

Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
1. Experimental Procedures.
General: NMR spectroscopy was performed in CDCl
3
at 25 °C or 50 °C on a JEOL type
GSX-270 spectrometer operating at 270 MHz, where the chemical shifts were determined with respect to CHCl
3
(

7.28). Electronic absorption spectra were recorded on a JASCO type V-560 spectrophotometer. FAB-MS spectra were measured on a JEOL type
JMS-HX110 spectrometer using a 3-nitrobenzyl alcohol as a matrix. MALDI-TOF-MS spectra were recorded on a Bruker type ProteinTof mass spectrometer using
9-nitroanthracene (9NA) as a matrix.
Materials: CH
2
Cl
2
, CHCl
3
, 1,2-dichloroethane (DCE), and N , N -dimethylformamide
(DMF) were distilled from CaH
2
under N
2
. Ethylene glycol was distilled from CaSO
4 under reduced pressure. These solvents were stored under N
2
. Tetrahydrofuran (THF) was refluxed over sodium benzophenone ketyl under Ar and distilled just before use. BF
3 etherate (BF
3
•OEt) and benzaldehyde were distilled under reduced pressure and stored under N
2
. 18-Crown-6 ether was recrystallized from MeCN, dried overnight under reduced pressure, and then stored under N
2
. K
2
CO
3
was kept in an oven at 130 °C. p -Chloranil, Ni(OAc)
2
•4H
2
O,

,
 ’-dibromop -xylylene, MeOH, EtOH, and AcOH were used as received.
2

Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
2. Synthesis of precursor porphyrins 7–9 and cyclic dimer 2.
Me
O
NH HN
5
O
Me
+
CHO
OTs
6
1) BF
3
•OEt
2) p-Chloranil
MS4A, CH
2
Cl
2 r.t., under N
2
Me
O
O
Me
N
N
H
H
N
N
TsO
7
O
Me
OTs
O
Me
Ni(OAc)
2
•4H
2
O
CHCl
3
, MeOH, AcOH reflux, under N
2
NaOH
THF, EtOH reflux, under Air
Me
O
O
Me
N
N
Ni
N
N
HO
8
O
Me
OH
O
Me
Br
Br
, K
2
CO
3
, 18-crown-6
THF, reflux, under N
2
8 + 9
K
2
CO
3
DMF, r.t., under N
2
Br
Me
O
O
Me
N
N
Ni
N
N
O
9
O
Me
O
O
Me
HCl aq.
CHCl
3
, r.t., under Air
Cyclic dimer 2
Br
3

Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
Porphyrin 7: To a CH
2
Cl
2
(5 mL) solution of a mixture of
5-(2’,6’-dimethoxyphenyl)-2,3,7,8-tetramethylpyrromethane ( 5 , 150.3 mg, 0.4441 mmol),
3-(4’-toluenesulfonyloxy)-benzaldehyde ( 6 , 151.6 mg, 0.5487 mmol), and a dehydrating agent such as molecular sieves 4A (0.7 g) was added BF
3
•OEt (0.010 mL, 0.080 mmol), and the mixture was stirred under N
2
at room temperature.
1 After 3-h stirring, p -chloranil
(166.5 mg, 0.6772 mmol) was added to the reaction mixture. After stirred for 3 h, molecular sieves 4A were removed by filtration, and a black filtrate was shaken with aqueous Na
2
S
2
O
3
and extracted with CH
2
Cl
2
. The combined extract was washed with brine, and an organic phase separated was dried over Na
2
SO
4
and evaporated to dryness.
Then, the residue was chromatographed on alumina with CHCl
3
/hexane (5:1) containing
1% Et
3
N as eluent, where the second green band was collected and evaporated to give 7 in
11% yield (55.7 mg).
1 H NMR (25 °C): 
8.07–7.23 (m, 22H, Ar-H in porphyrin and Ts), 3.73 (s, 12H, OCH
3
),
2.27 (s, 6H, CH
3
in Ts), 2.05 (s, 12H, pyrrole-

-CH
3
closed to C
6
H
3
(OMe)
2
), 1.74 (s, 12H, pyrrole-

-CH
3
closed to C
6
H
5
). FAB-MS calcd for C
70
H
67
N
4
O
10
S
2
(MH + ): 1187; obsd:
1187.
Porphyrin 8: To a CHCl
3
(20 mL) solution of 7 was added a AcOH/MeOH (1/9) solution of Ni(OAc)
2
/4H
2
O (1.0041 g, 4.0351 mmol), and the mixture was refluxed under
N
2
for 3 h, and then evaporated to dryness under reduced pressure.
2
The residue was poured into CHCl
3
, and the resulting suspension was filtered to remove an insoluble fraction (Ni(OAc)
2
). A black filtrate, thus obtained, was chromatographed on silica gel with CHCl
3
containing 1% AcOEt as eluent, where the first brown band was collected and evaporated to dryness, to give a Ni complex of 7 in 50% yield (52 mg).
4

Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
1 H NMR (25 °C): 
7.81 (d, 2H, J = 8.1 Hz, 6-H in C
6
H
4
(OTs)), 7.77 (d, 4H, J = 8.6 Hz,
Aro -H in Ts), 7.61 (t, 2H, J = 8.3 Hz, p -H in C
6
H
3
(OMe)
2
), 7.54 (s, 2H, 2-H in
C
6
H
4
(OTs)), 7.52 (m, 2H, 5-H in C
6
H
4
(OTs)), 7.38 (dd, 2H, J = 7.6, 1.7 Hz, 4-H in
C
6
H
4
(OTs)), 7.23 (d, 4H, J = 8.6 Hz, Arm -H in Ts), 6.84 (d, 4H, J = 8.1 Hz, Arm -H in
C
6
H
3
(OMe)
2
), 3.68 (s, 12H, OCH
3
), 2.30 (s, 6H, CH
3
in Ts), 2.00 (s, 12H, pyrrole-

-CH
3 closed to C
6
H
3
(OMe)
2
), 1.71 (s, 12H, pyrrole-

-CH
3
closed to C
6
H
5
). FAB-MS calcd for
C
70
H
64
N
4
O
10
S
2
Ni (M + ): 1242; obsd: 1242.
To a THF/EtOH (2 mL/2 mL) solution of the Ni complex of 7 (52.5 mg, 0.0422 mmol) was added NaOH (100 mg, 2.5 mmol), and the mixture was refluxed for 3 h.
3
The reaction mixture was poured into water and extracted with CH
2
Cl
2
. The organic phase separated was washed with brine, dried over anhydrous Na
2
SO
4
, and evaporated to dryness under reduced pressure. Then, the residue were chromatographed on silica gel with CH
2
Cl
2
as eluent, where the second brown band was collected and evaporated to dryness, to give 8 in 89% yield (35.2 mg).
1 H NMR (25 °C): 
7.59 (t, 2H, J = 8.6 Hz, Arp -H in C
6
H
3
(OMe)
2
), 7.53–7.41 (m, 6H,
2-/5-/6-H in C
6
H
4
(OH)), 7.10 (m, 2H, 4-H in C
6
H
4
(OH)), 6.86 (d, 4H, J = 8.1 Hz, Arm -H in C
6
H
3
(OMe)
2
), 3.67 (s, 12H, OCH
3
), 1.92 (s, 12H, pyrrole-

-CH
3
closed to
C
6
H
3
(OMe)
2
), 1.71 (s, 12H, pyrrole-

-CH
3
closed to C
6
H
5
). FAB-MS calcd for
C
56
H
52
N
4
O
6
Ni (M + ): 934; obsd: 934.
Porphyrin 9: 8 (11.0 mg, 0.0118 mmol),

,
 ’-dibromop -xylylene (70.3 mg, 0.266 mmol), and 18-crown-6 ether (6.0 mg, 0.023 mmol) were dissolved in dry THF (2 mL) containing K
2
CO
3
(11.7 mg, 0.0847 mmol), and the mixture was refluxed under N
2
for 12
5

Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002 h. The reaction mixture was evaporated to dryness, and the residue was chromatographed on silica gel with CHCl
3
as eluent, where the first brown band was collected and evaporated to dryness, to give 9 in 76% yield (11.6 mg).
1 H NMR (25 °C): 
7.61 (t, 2H, J = 8.3 Hz, Arp -H in C
6
H
3
(OMe)
2
), 7.57–7.32 (m, 16H,
Ar-H in C
6
H
4
(BrCH
2
C
6
H
4
CH
2
)), 6.88 (d, 4H, J = 8.6 Hz, Arm -H in C
6
H
3
(OMe)
2
), 5.20
(s, 4H, ArOCH
2
), 4.01 (s, 4H, CH
2
Br), 3.67 (s, 12H, OCH
3
), 2.01 (s, 12H, pyrrole-

-CH
3 closed to C
6
H
3
(OMe)
2
), 1.82 (s, 12H, pyrrole-

-CH
3
closed to C
6
H
5
). FAB-MS calcd for
C
72
H
67
N
4
O
6
Br
2
Ni (MH
+
): 1299; obsd: 1301.
Cyclic dimer 2: 8 (70.7 mg, 0.0756 mmol) and 9 (98.7 mg, 0.0758 mmol) were dissolved in dry DMF (160 mL) containing K
2
CO
3
(69.1 mg, 0.500 mmol), and the mixture was stirred for 28 h under N
2
at room temperature. The reaction mixture was evaporated to dryness, and the residue was chromatographed on silica gel with CH
2
Cl
2
as eluent, where the first brown band was collected and evaporated to dryness, to give a Ni complex of cyclic dimer 2 in 33% yield (51.9 mg).
1 H NMR (50 °C): 
7.5–6.3 (br, 36H, Ar-H in Ni complex of 2 ), 5.2 (s, 8H, CH
2
), 3.2 (br,
24H, OCH
3
), 1.9 (s, 24H, pyrrole-

-CH
3
closed to C
6
H
3
(OMe)
2
), 1.7 (s, 24H, pyrrole-

-CH
3
closed to C
6
H
5
). MALDI-TOF-MS calcd for C
128
H
116
N
8
O
12
Ni
2
(M + ):
2073; obsd: 2073.
To a CHCl
3
(1.10 mL) solution of the Ni complex of cyclic dimer 2 was added 35% hydrochloric acid (0.2 mL, 2 mmol), and the mixture was stirred at room temperature.
4
After 3 h, the reaction mixture was neutralized with aqueous NaHCO
3
and extracted with
CHCl
3
. The organic phase separated was evaporated under reduced pressure, and the
6

Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002 residue was chromatographed on alumina with CH
2
Cl
2
containing 1% Et
2
NH as eluent, where the green band was collected and evaporated to dryness, to give 2 in 37% yield
(2.63 mg).
1
H NMR (25 °C):

8.0–6.7 (m, 36H, Ar-H in 2 ), 5.4–5.1 (m, 8H, ArOCH
2
), 3.8–3.2 (m,
24H, OCH
3
), 2.0–1.3 (m, 48H, pyrrole-

-CH
3
). HRMS (FAB) calcd for C
128
H
121
N
8
O
12
(MH
+
): 1961.9104; obsd: 1961.9093. UV/vis (DCE):
 max
, nm: 440 (

= 3.2 x 10
5
dm
3 mol
-1
cm
-1
), 542, and 685.
7

Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
3. 1 H NMR spectra of 2 and its mandelate complexes in CDCl
3
.
Ar-H H b
H a
H b
Pyrrole-

-CH
3
H a
H c
OCH
3
ArOCH
2
H c
OH
CO
2
H
[MA]/[2] = 6.3
H a
H b
H c
[MA]/[2] = 2.8
[MA]/[2] = 0
9 8 7 6 5 4

in ppm
3 2 1 0
Figure S1 1 H NMR spectra of cyclic dimer 2 and its mandelate complexes in CDCl
3
at 25
°C. The assignment was made on the basis of the 1 H NMR spectrum of the bis(mandelate) complex of 1 .
8

Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
4. Circular dichroism (CD) spectrum of a mandelate complex of 2 after dissolved in acetic acid.
100
50
0
 
i n d m m o l
- 1
c m
- 1
-50
-100
400 450
Wavelength in nm
500
Figure S2 Circular dichroism (CD) spectrum in acetic acid at 23 °C of a protonated form of cyclic dimer 2 , derived from the ( S )-mandelate complex formed at [(S)-MA]/[ 2 ] = 2.
9

Supplementary Material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2002
5. References
1. Y. Furusho, T. Kimura, Y. Mizuno and T. Aida, J. Am. Chem. Soc.
, 1997, 119 , 5267;
Y. Mizuno, T. Aida and K. Yamaguchi, J. Am. Chem. Soc.
, 2000, 122 , 5278.
2. M. L. Wolfrom, E. W. Koos and H. B. Bhat, J. Org. Chem.
, 1967, 32 , 1058.
3. J. W. Buchler, In The Porphyrins ; D. Dolphin, Ed.; Academic Press: New York,
1978, vol.1, pp. 389.
4. J. W. Buchler, In Porphyrins and Metalloporphyrins ; K. M. Smith, Ed.; Elsevier:
Amsterdam, 1975, 199.
10