Supporting Information © Wiley-VCH 2006

69451 Weinheim, Germany

Conjugated Polymers Complexed With Helical Porphyrin Oligomers Create Micron-Sized Ordered Structures: Sequential Organization Through Supramolecular Twining

Masayuki Takeuchi,* Chiaki Fujikoshi, Yohei Kubo, Kenji Kaneko,† and Seiji Shinkai*

Contribution from Department of Chemistry and Biochemistry, Graduate School of Engineering,

Kyushu University, Fukuoka 819-0395, Japan, †HVEM Laboratory, Kyushu University, Fukuoka 812-8581, Japan

Measurements

(a) (b)[Por-12unit] =0

0.30 mM

Figure S1. (a) Fluorescence spectral changes of CP1 ([CP1unit] = 0.30 mM) recorded in the presence and absence of Por-12 for films cast from CDCl3 solution. Inset: Increase in the emission of the porphyrinatozinc units in the complex formed with CP1. The fluorescence intensity was normalized with respect to the absorption at 400 nm ( ex). (b) UV-Vis spectral changes of Por-12 ([Por-12unit] = 0.30 mM) recorded in the presence (red line, [CP1unit] = 0.30 mM) and the absence (blue line) of CP1 for films cast from CDCl3 solution.

50 μm Figure S2. (a) Optical microscopy image of the assembled Por-12/CP1 composite ([Por-12unit] = 0.020 mM; [CP1unit] = 0.036 mM). (b, c) Confocal fluorescence images of the assembled Por-12/CP1 composite excited at 370 nm; the emissions were collected in windows from (b) 400 to 440 nm and (c) 560 to 640 nm.

(a) (b) (C)

Figure S3. Electron micrographs (no staining) of the Por-12/CP1 composites. (a) HRTEM image of the Por-12/CP1 composites. (b) HRTEM image of the Por-12/CP1 composites after treatment with trifluoroacetic acid. (c) HRTEM image of the reconstituted Por-12/CP1 composites after treatment with NaOH.

[Por-12unit]

0

0.30 mM

(a) (b)

Figure S4. (a) UV-Vis spectral changes of Por-12 (0.013 mM unit) after addition of CP1 (0-0.030 mM unit). (b) Fluorescence spectral changes of CP2 ([CP1 unit] = 0.30 mM) in the presence ([Por-12 unit] = 0-0.30 mM) and absence of Por-12 for films cast from CDCl3 solution.

0

1

2

3

400 450 500 550 600

Abs

orba

nce

Wavelength / nm

0

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0 2 4 6 8 10

[poly(4-vinylpyridine)unit]/[Por-12unit]

Abs

. at 5

51 n

m

(a)

(b)

Figure S5. (a) UV-Vis spectral changes of Por-12 (0.016 mM unit) upon addition of the poly(4-vinylpyridine) (0-0.30 mM unit). (b) Plot of the absorbance change at 551 nm of Por-12 (0.016 mM unit) vs. [poly(4-vinylpyridine)unit].

(a) (b)

A

B C

(c) A

B C

Figure S6. (a) TEM image (obtained without staining) of the poly(4-vinylpyridine) (Mw = 60,000)/Por-12 composite. (b) Enlarged TEM image of (a) and an electron diffraction pattern indicating that the poly(4-vinylpyridine) (Mw 60,000)/Por-12 composite is crystalline. (c) Dark-field diffraction contrast images obtained using the reflections labeled in (b). These striped morphologies clearly indicate that thin 2D sheet should possess the periodic striped morphologies.

0

5

10

15

20

0 2 8 33 142 615 2669

Diameter (nm)

Inte

nsi

ty (

%)

Por-12CP1Por-12/CP1

Figure S7. DLS profiles of Por-12 (red), CP1 (yellow), and the Por-12/CP1 composite (blue) in CDCl3. [Por-12unit] = 0.020 mM unit; [CP1unit] = 0.018 mM; He-Ne laser (633 nm). The size distributions indicate the diameters of the major and minor axes of Por-12 and the composites. The diameters of the major and minor axes of the Por-12/CP1 composites appear to be larger than those of Por-12 and CP1 alone, but the diameter of the minor axis of the Por-12/CP1 composites is not sufficiently large to attribute for the sheet structure observed in the TEM studies, indicating that the Por-12/CP1 composites self-organize on the surface during the solidifying process to form 2D sheet-like assemblies.

Synthesis The polymers CP1 and CP2 were synthesized according to the method reported previously.[1] Por-12 and Por-6 were synthesized according to the procedures depicted in Scheme S1. Scheme S1

CHO

Br

CHO

Br

HOCHO

Br (CH2)10 BrBr

O O(CH2)10

CHO CHOO O(CH2)10

TMS TMS

TMS H

K2CO3 / KIDMF

2

Pd(PPh3)2Cl2 / CuITHF / NEt3

BF3 / CHCl3 / EtOHp-chloranil

1

3

NH NHN

N

O

O

(CH2)10

TMS

TMS N NNN Zn

O

O

(CH2)10

TMS

TMS

NNN

N Zn

O

O

(CH2)10

H

H

Zn(AcO)2 / MeOH

CHCl3

K2CO3 / MeOH

CH2Cl2

4

5

O

O I

I

C12H25C12H25 N

NN

N Zn

O

O

(CH2)10

O

O C12H25

H

C12H25

I

Por-12

6 n

NH

NH

NN

NN Zn

O

O

(CH2)10

O

O C6H13

H

C6H13

I

Por-6

n

Pd(PPh3)4 / CuITHF / (i-Pr)2NH

O

O I

I

C6H13C6H13

7

Pd(PPh3)4 / CuITHF / (i-Pr)2NH

1,10-Bis(2-formyl-4-bromophenyl)decane (1). A mixture of 5-bromosalicylaldehyde (6.0 g, 30

mmol) and K2CO3 (12 g, 60 mmol) in dry DMF (180 mL) was heated at 65 C under N2 for 1 h before 1,10-dibromodecane (3.0 g, 10 mmol) and KI (1.6 g, 10 mmol) were added. The resulting solution was heated at 65 °C under N2 for 4 h. Upon cooling, the reaction mixture was diluted in CH2Cl2, washed with water, and dried (anhydrous MgSO4). After purification through reprecipitation from CH2Cl2 in MeOH, a white powder was obtained (10 g, 98%). M.p. 103.0-104.2 °C. 1H NMR (600 MHz, CDCl3, TMS, rt) 1.35 (m, 8H), 1.46 (m, 4H), 1.84 (m, 4H),

4.06 (t, J = 6.2 Hz, 4H), 6.88 (d, J = 8.8 Hz, 2H), 7.60 (dd, J = 8.5, 1.7 Hz, 2H), 7.91, (d, J = 1.4 Hz, 2H), 10.42 (s, 2H). Anal. Calcd. for C24H28Br2O4: C, 53.35; H, 5.22. Found: C, 53.25; H, 5.25. 1,10-Bis(2-formyl-4-trimethylsilylethynylphenyl)decane (2) and compound 3. A mixture of 1 (11 g, 22 mmol), trimethylsilylacetylene (6.6 mL, 66 mmol), Pd(PPh3)2Cl2 (3.0 g, 4.4 mmol), and CuI (0.42 g, 2.2 mmol) in dry THF (50 mL) and dry triethylamine (50 mL) was heated under reflux for 10 h under N2. Upon cooling, the reaction mixture was filtered. The solution was evaporated to dryness and the residue was then dissolved in CH2Cl2, washed with saturated ammonium chloride and water, and dried (anhydrous MgSO4). After purification through column chromatography [SiO2; CH2Cl2/n-hexane, 1:1 (v/v)], a brown oil was obtained (9.2 g, 78%). Compound 2 was used for the synthesis of 3 without further purification. 1H NMR (600 MHz, CDCl3, TMS, rt): 0.29 (s, 18H), 1.36 (m, 8H), 1.48 (m, 4H), 1.84 (m, 4H), 4.08 (t, J = 6.3 Hz, 4H), 7.91 (d, J = 8.6 Hz, 2H), 7.60 (d, J = 8.5 Hz, 4H), 8.07 (s, 2H), 10.44 (s, 2H). A solution of 2,2’-dipyrrimethane (0.49 g, 3.4 mmol) and 2 (0.91 g, 1.7 mmol) in CHCl3 (680 mL) and ethanol (5.1 mL) was stirred under N2 for 5 min. BF3•Et2O (0.20 mL, 1.1 mmol) was added and the reaction mixture was stirred at room temperature. After 2 h, p-chloranil (1.4 g, 2.6 mmol) was

added and the resulting solution was stirred for 1 h. After purification through flash column chromatography (SiO2; CHCl3) and reprecipitation from CHCl3 in MeOH, a purple powder was obtained (0.55 g, 29%). M.p. 151.2-153.4 °C. 1H NMR (600 MHz, CDCl3) -3.12 (s, 2H), -1.62 (s,

4H), -0.96 (m, 8H), 0.32 (s, 18H), 3.71 (t, J = 4.7 Hz, 4H), 7.20 (d, J = 8.6 Hz, 2H), 7.91 (d, J = 8.3 Hz, 2H), 8.51 (s, 2H), 8.98 (d, J = 4.2 Hz, 4H), 9.32 (d, J = 4.3 Hz, 4H), 10.22 (s, 2H). MALDI-TOF-MS [dithranol] m/z calcd., 824.54; found, 824.39. Anal. Calcd. for C52H56N4O2Si2: C, 75.69; H, 6.84; N, 6.79. Found: C, 75.27; H, 6.84; N, 6.74. Compound 4. A solution of 3 (0.55 g, 0.67 mmol) in CHCl3 (30 mL) was added to a solution of Zn(AcO)2•H2O (1.5 g, 6.7 mmol) in MeOH (20 mL) and then stirred at room temperature for 30 min. The mixture was diluted with CHCl3, washed with water, and dried (anhydrous Na2SO4). After concentration in vacuo, a purple powder was obtained (0.59 mg, 99%). M.p. 320.0-323.3 °C (dec). 1H NMR (600 MHz, CDCl3) -1.74 (s, 4H), -1.03 (m, 4H), 0.30 (s, 4H), 0.58 (s, 4H), 3.07 (t, J =5.0

Hz, 4H), 7.27 (d, J = 8.7 Hz, 2H), 7.93 (dd, J = 8.4, 1.1 Hz, 2H), 8.51 (d, J = 1.1 Hz, 2H), 9.08 (d, J = 4.2 Hz, 4H), 9.41 (d, J = 4.1 Hz, 4H), 10.28 (s, 2H). MALDI-TOF-MS [dithranol] m/z calcd., 886.37; found, 886.31. Anal. Calcd. for C52H54N4O2Si2Zn: C; 70.29, H; 6.13, N; 6.31. Found: C; 69.48, H; 6.12, N; 6.22. Compound 5. A solution of 4 (0.64 mg, 0.72 mmol) in CH2Cl2 (30 mL) was added to a solution of K2CO3 (1.4 g, 7.2 mmol) in MeOH (20 mL) and then stirred at room temperature for 3 h. The mixture was diluted with CH2Cl2, washed with water, and dried (anhydrous Na2SO4). After concentration in vacuo, a purple powder was obtained (0.52 mg, 97%). M.p, 306.8-308.5 °C (dec). 1H NMR (600 MHz, CDCl3) -1.74 (s, 4H), -1.03 (m, 4H), -0.94 (s, 4H), 0.57 (m, 4H), 3.71 (s, 2H),

3.71 (t, J =5.1 Hz, 4H), 7.22 (d, J = 8.6 Hz, 2H), 7.94 (dd, J = 8.5, 1.1 Hz, 2H), 8.53 (d, J = 1.1 Hz, 2H), 9.08 (d, J = 4.2 Hz, 4H), 9.41 (d, J = 4.3 Hz, 4H), 10.29 (s, 2H); HR-FAB [NBA] m/z calcd. for [M]+ = 742.2286, found 742.2287. Por-12. A mixture of 5 (110 mg, 0.15 mmol), 6 (210 mg, 0.30 mmol), Pd(PPh3)4 (68 mg, 60 mol), and CuI (5.6 mg, 30 mol) in dry THF (2 mL) and dry diisopropylamine (5 mL) was heated under reflux for 6 h. A second portion of 5 (55 mg, 74 mol) was then added and the mixture was again heated under reflux for 6 h. A third portion of 5 (20 mg, 27 mol) was then added and the mixture

was again heated under reflux for 6 h. A fourth portion of 5 (10 mg, 13 mol) was then added and the mixture was again heated under reflux for 6 h. Finally, a second portion of 6 (30 mg, 43 mmol) was added and the mixture was again heated under reflux for 3 h. After purification through gel permeation chromatography (GPC; JAIGEL 2.5 H + JAIGEL 3H; CHCl3) to remove the low-molecular-weight fraction and reprecipitation from CHCl3 in MeOH, a red powder was obtained (23 mg, 13%). M.p. 318.0-325.3 °C (dec). Por-6. A mixture of 5 (0.11 g, 0.15 mmol), 7 (0.16 g, 0.30 mmol), Pd(PPh3)4 (68 mg, 60 mmol), and CuI (5.6 mg, 30 mmol) in dry THF (2 mL) and dry diisopropylamine (5 mL) was heated under reflux for 3 h. A second portion of 5 (55 mg, 74 mmol) was then added and the mixture was again heated under reflux for 3 h. A third portion of 5 (27 mg, 37 mmol) was then added and the mixture was again heated under reflux for 3 h. A fourth portion of 5 (13 mg, 18 mmol) was then added and the mixture was again heated under reflux for 3 h. A fifth portion of 5 (30 mg, 43 mmol) was then

added and the mixture was again heated under reflux for 3 h. After purification through GPC (JAIGEL 2.5 H + JAIGEL 3H; CHCl3) to remove the low-molecular-weight fraction and reprecipitation from CHCl3 in MeOH, a red powder was obtained (8.0 mg, 12%). M.p. 312.2-321.1 °C (dec).

Reference [1] Kubo, Y.; Kitada, Y.; Wakabayashi, R.; Kishida, T.; Ayabe, M.; Kaneko, K.; Takeuchi, M.; Shinkai, S. Angew. Chem. Int. Ed. 2006, 45, 1548-1553.