On the influence of porphyrin π-π stacking on supramolecular chirality created in the porphyrin-based twisted tape structure

Article abstract of DOI:10.1039/b512128k

Achiral porphyrin derivatives 1-M form twisted supramolecular assemblies and the pitch of the twisted tape structure can be altered by changing the central metal. The Royal Society of Chemistry 2005.

Full text of DOI:10.1039/b512128k

Supplementary Information for
On the influence of porphyrin π-π stacking on supramolecular chirality created in the
porphyrin-based twisted tape structure
Masayuki Takeuchi,* Satoshi Tanaka and Seiji Shinkai*
Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University,
Fukuoka 812-8581, Japan
e-mail: taketcm@mbox.nc.kyushu-u.ac.jp, seijitcm@mbox.nc.kyushu-u.ac.jp
Experimental:
General. All starting materials and solvents were purchased from Tokyo Kasei Organic Chemicals,
1
Wako Organic Chemicals, or Aldrich and used as received. The H NMR spectra were recorded
either on a Brucker AC 250 (250 MHz) or Brucker DRX 600 (600 MHz) spectrometer. Chemical
shifts are reported in ppm downfield from tetramethylsilane as the internal standard. Mass spectral
data were obtained using a Perseptive Voyager RP MALDI TOF mass spectrometer and/or a JEOL
JMS HX110A high-resolution magnetic sector FAB mass spectrometer. UV-Vis spectra were
recorded with a Shimadzu UV-2500 PC spectrophotometer.
Powder X-ray Diffraction. The sample was prepared in a sample tube and frozen by liquid
nitrogen. The frozen specimen was evaporated by a vacuum pump at 0.6 mmHg for 1 day at room
temperature. The obtained xerogel was put into a glass capillary (Φ = 0.3 mm). X-ray
diffractograme was recorded on an imaging plate using Cu radiation (λ = 1.54178 Å at a distance of
15 cm).
SEM Observation. The sample was prepared in a sample tube and frozen by liquid nitrogen. The
frozen specimen was evaporated by a vacuum pump at 0.6 mmHg for 1 day at room temperature.
The obtained sample was shielded with platina. The accelerating voltage of SEM was 25 kV, and
the emission current was 10 µA.
TEM Observation. A piece of the sample was placed on a carbon-coated copper grid. The

specimen was evaporated by a vacuum pump at 0.6 mmHg for 1day at room temperature. The
accelerating voltage of TEM was 120 kV, and the beam current was 65 µA.
Synthesis. Compounds 1-2H, 1-Cu, and 1-Ni were synthesized according to Schemes S1 and S2
and identified by 1H NMR, high-resolution FAB-Mass measurements, and/or elemental analyses.
1-Cu
1-Ni
400
500 600
Wavelength / nm
700
800
400
500 600
Wavelength / nm
700
800
Fig. S1 UV-Vis spectra of 1-Cu (1.0 x10-6 M) and 1-Ni (1.0 x10-6 M) in THF (solid line) and
assembly of 1-Cu (1.00 wt %) and 1-Ni (1.00 wt %) prepared from t-butanol (dotted line) at 25 ˚C.
1.5 nm
1-Ni
1-Cu
1.8 nm
1.0 nm
0.79 nm
0.99 nm
0.42 nm
0.61 nm
0.47 nm
1.5 nm
1.9 nm
0.60 nm
0.42 nm
0.42 nm
0.81 nm
0.39 nm
0.38 nm
5
10
15
20
25
30
5
10
15
20
25
30
2! / ˚
2! / ˚
Fig. S2 XRD patterns of the freeze-dried suspended solids prepared from t-butanol of 1-Cu (1.00
wt %) and 1-Ni (1.00 wt %).

A
B
non coplanar
Fig. S3 (A) Structure of the N-methylaminomethyl moiety estimated from computational
energy-minimization (Insight II, Discover-3). (b) Molecular models for the mirror image of the
N-methylaminomethyl moiety.
Synthesis
Scheme S1
Br
11
O
O
OH
OH
11
11
O
H
O
H
K2CO3, KI
DMF
2
Ar
NH
Ar
NH
O
Zn(OAc)2•2H2O
CHCl3
N
11
N
NBS
DDQ
TFA
O
H
Br
Br
+
N
H
N
H
HN
N
CHCl3, pyridine
CH2Cl2
HN
N
O
11
Ar
4
Ar
3
H
N
9
O
Ar
H
N
Ar
O
Pd(PPh3)2Cl2, CuI
NEt3
Pd(PPh3)2Cl2, CuI
N
Zn
N
N
N
N
Zn
N
N
N
N
O
O
Br
Br
Br
NEt3
Ar
Ar
5
6
Ar
Ar
NH
TFA
CH2Cl2
N
N
Zn
N
N
N
O
O
N
N
O
N
HN
Ar
N
N
O
Ar
8
7
Ar
NH
O
O
N
KOH
THF, MeOH, H2O
11
11
N
OH
O
N
Ar=
HN
Ar
N
1-2H

Scheme S2
Ar
Ar
NH
N
N
Cu(OAc)2•H2O
CHCl3
N
N
OH
O
Cu
N
N
OH
O
N
N
N
N HN
Ar
Ar
Ar
1-Cu
1-2H
Ar
N
N
N
Ni(OAc)2•4H2O
CHCl3
NH
N
N
O
O
Ni
N
N
O
O
N
N
HN
Ar
N
Ar
8-Ni
8
Ar
N
N
N
KOH
THF, MeOH, H2O
O
O
N
OH
Ni
N
11
11
N
Ar=
O
Ar
1-Ni
5,15-Bis(3,5-di-n-dodecyloxyphenyl)porphyrin (3). 2,2’-Dipyrromethane (1.64 g, 11.2 mmol)
and 2 (5.32 g, 11.2 mmol) were dissolved in CH2Cl2 (2.2 L). After addition of trifluoroacetic acid
(0.60 ml), the solution was stirred for 4 h at room temperature under N2 in the dark. Then, DDQ
(3.26 g, 14.4 mmol) was added to the solution and the reaction mixture was stirred for 30 min. The
reaction mixture was passed through silica pad [CHCl3] directly. Further purification by column
chromatography [silica gel, CHCl3/n-hexane = 1:1 (v/v)] was gave 3 in 36 % (2.41 g) as purple
solid: mp. 73.1-73.4 ˚C; 1H-NMR (250 MHz, CDCl3, TMS, rt) d -3.16 (s, 2H), 0.85 (t, J = 6.0, 12H),
1.24 (m, 64H), 1.51 (m, 8H), 1.88 (m, 8H), 4.15 (t, J = 6.5, 8H), 6.92 (s, 2H), 7.42 (d, J = 2.0, 4H),
9.19 (d, J = 4.6, 4H), 9.37 (d, J = 4.7, 4H), 10.29 (s, 2H); MALDI-TOF-MS [dithranol] m/z calcd
for [M+H]+ = 1200.92, found 1200.82; Anal. Calcd for C80H118N4O4: C, 80.08; H, 9.91; N, 4.67.
Found: C, 79.99; H, 9.88; N, 4.61.
5,15-Dibromo-10,20-bis(3,5-di-n-dodecyloxyphenyl)porphyrinatozinc (5). Compound 3 (2.0 g,
1.67 mmol) was dissolved in CHCl3 (400 ml), and cooled to 0 ˚C. NBS (594 mg, 3.34 mmol) and
pyridine (1.5 ml) were added to the solution, and the mixture was stirred for 15 min at 0 ˚C. The
reaction progress was monitored by TLC [silica gel, CHCl3 /n-hexane = 1:1 (v/v)]. The reaction was

quenched with acetone (30 ml) and the solution was concentrated under reduced pressure. The
resulting residue was subjected to column chromatography [silica gel, CHCl3/n-hexane = 1:1 (v/v)]
1
to give 4 as purple solid. After confirming the formation of 4 by H-NMR and MALDI-TOF-MS,
we used 4 for the synthesis of 5. Compound 4 was dissolved in CHCl3 (400 ml). After addition of
the methanol solution (100 ml) of Zn(OAc)2•2H2O (3.67 g, 16.7 mmol), the mixture was stirred for
1 h at room temperature. The solution was concentrated under reduced pressure and the resulting
residue was washed with water. The organic layer was dried over anhydrous Na2SO4 and
concentrated under reduced pressure to give 5 in 94 % from 3 (2.24 g) as purple solid: 4;1H-NMR
(250 MHz, CDCl3,TMS, rt ) d -2.76 (s, 2H), 0.85 (t, J = 6.9, 12H), 1.24 (m, 64H), 1.53 (m, 8H),
1.87 (m, 8H), 4.12 (t, J = 6.6, 8H), 6.90 (s, 2H), 7.31 (d, J = 2.1, 4H), 8.95 (br, 4H), 9.60 (d, J = 4.5,
4H); MALDI-TOF-MS [dithranol] m/z calcd for [M+H]+ = 1358.77, found 1358.61. 5; mp.
1
192.0-195.4 ˚C; H-NMR (250 MHz, CDCl3, TMS, rt) d 0.85 (m, 12H), 1.23 (m, 64H), 1.49 (m,
8H), 1.87 (m, 8H), 4.12 (t, J = 6.6, 8H), 6.89 (s, 2H), 7.31 (s, 4H), 9.07 (d, J = 4.7, 4H), 9.72 (d, J =
4.7, 4H); MALDI-TOF-MS [dithranol] m/z calcd for [M+H]+ = 1421.69, found 1421.98.; Anal.
Calcd for C80H114Br2N4O4Zn: C, 67.62; H, 8.09; N, 3.94. Found: C, 67.76; H, 8.21; N, 3.93.
Compound 6. Compound 5 (1.31 g, 0.92 mmol), 9[1] (129 mg, 0.46 mmol), Pd(PPh3)2Cl2 (64.7 mg,
92.2 mmol), and CuI (26.3 mg, 0.14 mmol) were mixed in dry triethylamine (70 ml). The mixture
was stirred for 3 h at room temperature under N2. The reaction progress was monitored by TLC
[silica gel, CHCl3]. The solution was concentrated under reduced pressure and the resulting residue
was washed with saturated ammonium chloride and water. The organic layer was dried over
anhydrous Na2SO4 and concentrated under reduced pressure. The resulting residue was subjected to
column chromatography [silica gel, CHCl3] to give 6 in 25 % (374 mg) as green soild: mp.
190.0-191.0 ˚C; 1H-NMR (600 MHz, CDCl3, TMS, rt) d 0.84 (t, J = 6.9, 12H), 1.23-1.31 (m, 56H),
1.37 (m, 8H), 1.50 (m, 8H), 1.87 (m, 8H), 3.08 (s, 3H), 3.89 (s, 3H), 4.13 (t, J = 6.6, 8H), 4.58 (s,
2H), 6.65 (d, J = 8.3, 2H), 6.89 (s, 2H), 7.29 (d, J = 8.1, 2H), 7.34 (d, J = 1.7, 4H), 7.64 (d, J = 8.3,
2H), 8.00 (d, J = 8.2, 2H), 9.02 (m, 4H), 9.65 (d, J = 4.6, 2H), 9.69 (d, J = 4.4, 2H);
MALDI-TOF-MS [dithranol] m/z calcd for [M+H]+ = 1620.75, found 1620.40.; Anal. Calcd for

C98H130BrN5O6Zn: C, 72.68; H, 8.09; N, 4.32. Found: C, 72.68; H, 8.15; N, 4.30.
Compound 8. Compound 6 (350 mg, 0.22 mmol), 4-ethynylpyridine (66.8 mg, 0.65 mmol),
Pd(PPh3)2Cl2 (15.2 mg, 21.6 mmol), and CuI (6.2 mg, 32 mmol) were mixed in dry triethylamine
(15 ml). The mixture was stirred for 12 h at 70 ˚C under N2. The reaction progress was monitored
by TLC (silica gel, CHCl3). The solution was concentrated under reduced pressure and the resulting
residue was washed with saturated ammonium chloride and water. The organic layer was dried over
anhydrous Na2SO4, and concentrated under reduced pressure. The resulting residue was subjected to
column chromatography [silica gel, CHCl3 /n-hexane = 3:1 (v/v)] to give 7 in 86 % yield (306 mg)
as green solid. Compound 7 (300 mg, 0.18 mmol) was dissolved in CH2Cl2 (80 ml). After addition
of TFA (0.80 ml), the solution was stirred for 1 h at room temperature. The reaction mixture was
washed with 5 % aqueous NH4OH and water and the organic layer was dried over anhydrous
Na2SO4. The solution was concentrated under reduced pressure. The resulting residue was subjected
to column chromatography on silica gel (CHCl3) to give 8 (234 mg, 81 %) as green solid. 7;
1H-NMR (600 MHz, pyridine-d5, TMS, rt) d 0.84 (t, J = 6.9, 12H), 1.23-1.30 (m, 56H), 1.36 (m,
8H), 1.55 (m, 8H), 1.93 (m, 8H), 3.07 (s, 3H), 3.84 (s, 3H), 4.23 (t, J = 6.4, 8H), 4.71 (s, 2H), 7.03
(d, J = 8.7, 2H), 7.35 (s, 2H), 7.41 (t, J = 8.2, 2H), 7.76 (d, J = 2.0, 4H), 7.97 (d, J = 5.6, 2H), 8.17
(d, J = 8.5, 2H), 8.19 (d, J = 8.3, 2H), 8.95 (d, J = 5.5, 2H), 9.36 (d, J = 4.4, 2H), 9.42 (d, J = 4.4,
2H), 10.08 (d, J = 4.5, 2H), 10.17 (d, J = 4.4, 2H); MALDI-TOF-MS [dithranol] m/z calcd for
[M+H]+ = 1642.95, found1642.61. 8; mp. 131.2-132.1 ˚C; 1H-NMR (600 MHz, CDCl3, TMS, rt) d
-1.88 (s, 2H), 0.84 (t, J = 6.9, 12H), 1.23-1.31 (m, 56 H), 1.37 (m, 8H), 1.51 (m, 8H), 1.88 (m, 8H),
3.22 (s, 3H), 3.93 (s, 3H), 4.14 (t, J = 6.6, 8H), 4.74 (s, 2H), 6.88 (d, J = 8.7, 2H), 6.90 (s, 2H), 7.34
(d, J = 1.6, 4H), 7.36 (d, J = 8.2, 2H), 7.85 (d, J = 5.3, 2H), 7.88 (d, J = 8.9, 2H), 8.05 (d, J = 8.2,
2H), 8.82 (d, J = 5.0, 2H), 8.91 (d, J = 4.2, 2H), 8.96 (d, J = 4.3, 2H), 9.58 (d, J = 4.6, 2H), 9.64 (d,
J = 4.5, 2H); HR-FAB [NBA] m/z calcd for [M]+ = 1577.0521, found 1577.0427.
1-2H. Compound 8 (130 mg, 82.4 mmol) was dissolved in THF (20 ml). KOH (2.0 ml, 2 M in
H2O/MeOH = 4:1 (v/v)) was added and the mixture was refluxed for 24 h. The reaction progress
was monitored by TLC [silica gel, CHCl3/MeOH = 25:1 (v/v)]. After cooling the mixture to room

temperature, the solution was concentrated under reduced pressure. The resulting residue was
washed with water. The organic layer was dried over anhydrous Na2SO4 and concentrated under
reduced pressure. The resulting residue was subjected to column chromatography [silica gel,
CHCl3/MeOH = 25:1 (v/v)] to give 1-2H in 84 % (108 mg) as green solid: mp. 166.7-168.0 ˚C;
1H-NMR (600 MHz, CD2Cl2 / pyridine-d5, TMS, rt) d -1.69 (s, 2H), 0.83 (t, J = 6.9, 12H), 1.23-1.35
(m, 56H), 1.37 (m, 8H), 1.52 (m, 8H), 1.89 (m, 8H), 3.12 (s, 3H), 4.17 (t, J = 6.5, 8H), 4.69 (s, 2H),
6.93 (d, J = 8.6, 2H), 7.08 (s, 2H), 7.37 (d, J = 8.2, 2H), 7.46 (d, J = 1.8, 4H), 7.85 (d, J = 5.5, 2H),
7.97 (d, J = 8.5, 2H), 8.26 (d, J = 8.2, 2H), 8.82 (d, J = 5.4, 2H), 9.03 (d, J = 4.4, 2H), 9.08 (d, J =
4.5, 2H), 9.73 (d, J = 4.7, 2H), 9.81 (d, J = 4.6, 2H); HR-FAB [NBA] m/z calcd for [M]+ =
1563.0365, found 1563.0363.
1-Cu. Compound 1-2H (98 mg, 63 mmol) was dissolved in CHCl3 (20 ml). After addition of the
methanol solution (5 ml) of Cu(OAc)2•H2O (126 mg, 0.63 mmol), the solution was stirred for 5 h at
room temperature. The mixture was concentrated under reduced pressure and the resulting residue
was washed with saturated ammonium chloride aqueous solution and water. The organic layer was
dried over anhydrous Na2SO4 and concentrated under reduced pressure. The resulting residue was
subjected to column chromatography [silica gel, CHCl3/MeOH = 10:1 (v/v)] to give 1cp-Cu in
29 % (30 mg) as green solid: mp. 235.6-236.9 ˚C; HR-FAB [NBA] m/z calcd for [M]+ = 1618.9562,
found 1618.9531; Anal. Calcd for C104H132CuN6O6•0.50H2O: C, 76.41; H,8.20; N, 5.14. Found: C,
76.12; H, 8.20; N, 5.03.
Compound 8-Ni. Compound 8 (98 mg, 63 mmol) was dissolved in CHCl3 (65 ml). After addition
of the methanol solution (50 ml) of Ni(OAc)2•4H2O (1.24 g, 5.08 mmol), the mixture was refluxed
for 6 days. The solution was concentrated under reduced pressure and the resulting residue was
washed with saturated sodium hydrogen carbonate aqueous solution and sodium chloride aqueous
solution. The organic layer was dried over anhydrous Na2SO4 and concentrated under reduced
pressure. The resulting residue was subjected to column chromatography (silica gel, CHCl3) to give
8-Ni in 97 % (201 mg) as green solid: mp. 130.0-133.0 ˚C; 1H-NMR (600 MHz, CDCl3, TMS, rt) d
0.85 (t, J = 6.9, 12H), 1.23-1.30 (m, 56 H), 1.36 (m, 8H), 1.48 (m, 8H), 1.85 (m, 8H), 3.19 (s, 3H),

3.92 (s, 3H), 4.08 (t, J = 6.6, 8H), 4.72 (s, 2H), 6.88 (m, 2H+2H), 7.14 (d, J = 2.0, 4H), 7.34 (d, J =
8.2, 2H), 7.76 (d, J = 5.5, 2H), 7.78 (d, J = 8.6, 2H), 8.04 (d, J = 8.2, 2H), 8.77 (br, 2H), 8.81 (d, J =
4.9, 2H), 8.85 (d, J = 4.8, 2H), 9.44 (d, J = 4.9, 2H), 9.50 (d, J = 4.9, 2H); HR-FAB [NBA] m/z
calcd for [M]+ = 1632.9718, found 1632.9725.
1-Ni. Compound 8-Ni (100 mg, 61.2 mmol) was dissolved in THF (16 ml). KOH (1.6 ml, 2 M in
H2O/MeOH = 4:1 (v/v)) was added and the mixture was refluxed for 12 h. The reaction progress
was monitored by TLC [silica gel, CHCl3/MeOH = 10:1 (v/v)]. After cooling the mixture to room
temperature, the solution was concentrated under reduced pressure. The resulting residue was
washed with water. The organic layer was dried over anhydrous Na2SO4 and concentrated under
reduced pressure. The resulting residue was subjected to column chromatography [silica gel,
CHCl3/MeOH = 10:1 (v/v)] to give 1-Ni in 87 % (86 mg) as green solid: mp. 198.0-200.0 ˚C;
1H-NMR (600 MHz, THF-d8, TMS, rt) d 0.74 (t, J = 6.9, 12H), 1.15-1.26 (m, 56H), 1.29 (m, 8H),
1.41 (m, 8H), 1.72 (m, 8H), 3.08 (s, 3H), 4.00 (t, J = 6.5, 8H), 4.67 (s, 2H), 6.76 (s, 2H), 6.81 (d, J
= 8.8, 2H), 7.08 (d, J = 2.0), 7.25 (d, J = 8.2, 2H), 7.67 (d, J = 8.6, 2H), 7.74 (d, J = 4.5, 2H), 7.89
(d, J = 8.2, 2H), 8.66 (br, 2H), 8.80 (d, J = 4.8, 2H), 8.85 (d, J = 4.8, 2H), 9.50 (d, J = 4.7, 2H), 9.52
(d, J = 4.9, 2H); HR-FAB [NBA] m/z calcd for [M]+ = 1623.9504, found 1623.9515.
References
[1] S. Tanaka, M. Shirakawa, K. Kaneko, M. Takeuchi, S. Shinkai, S. Langmuir 2005, 21,
2163-2172.