Supporting Information © Wiley-VCH 2006

69451 Weinheim, Germany

S1

Chiral Porphyrin Homo-Aggregates Formation Assisted by an Induced

Helical Poly(phenylacetylene) Template and Their Chiral Memory

Hisanari Onouchi,† Toyoharu Miyagawa,

§ Kazuhide Morino,

‡ and Eiji Yashima*,‡,§

†Nagoya University Venture Business Laboratory and

‡Department of Molecular Design

and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya

464-8603, Japan, and §Yashima Super-structured Helix Project, Exploratory Research for

Advanced Technology (ERATO), Japan Science and Technology Agency (JST), 101

Creation Core Nagoya, 2266-22 Anagahora, Shimoshidami, Moriyama-ku, Nagoya 463-

0003, Japan

Experimental Section

Materials. Cis-transoidal poly-1–HCl was prepared according to the previously

reported method.[1]

The stereoregularity of poly-1–HCl was confirmed to be cis-

transoidal by Raman spectroscopy.[1,2]

The number-average molecular weight (Mn) and

its molecular weight distribution (Mw/Mn) of poly-1–HCl were 2.6 x 105 and 3.2,

respectively, as determined by size exclusion chromatography (SEC).

(S)- and (R)-1,1'-bi-2-naphthol (2) were obtained from Aldrich (Milwaukee, WI). Sodium

fluorescein (dye-3), sodium alizarinsulfonate (dye-4), and meso-tetrakis(4-

S2

sulfonatophenyl)porphine (TPPS) were purchased from Wako (Osaka, Japan) or Tokyo

Kasei (TCI, Tokyo, Japan) and used as received.

Instruments. The solution pH was measured with a B-211 pH meter (Horiba, Japan).

NMR spectra were taken on a Varian Mercury 300 operating at 300 MHz and a Varian

VXR-500S operating at 500 MHz for 1H. Laser Raman spectra were taken on a Jasco

RMP-200 spectrophotometer. The absorption and CD spectra were measured in a 0.2-,

0.5-, or 1.0-cm quartz cell on a Jasco V-570 spectrophotometer and a Jasco J-725 or J-820

spectropolarimeter, respectively. The temperature was controlled with a Jasco ETC 505T

(for absorption measurements) and a Jasco PTC-423L apparatus (for CD measurements).

The resonance light scattering (RLS) measurements were performed in a 1.0-cm quartz cell

on a Jasco FP-6500 spectrofluorimeter, adopting a synchronous scan of both the excitation

and emission monochromator with a right-angle geometry.[3]

Helicity Induction on Poly-1–HCl with (S)- and (R)-2 in Water. Deionized,

distilled water was degassed with nitrogen before use for all experiments. The

concentration of poly-1–HCl was calculated based on the monomer units and was 1 or 0.1

mg mL–1

unless otherwise stated. A typical experimental procedure is described below.

Stock solutions of poly-1–HCl (1 mg mL–1

, 4.0 mM monomer units) in water and (S)-2 (1.6

x 10–2

M) in chloroform were prepared in 5-mL flasks equipped with stopcocks,

respectively. A 0.5 mL aliquot of the (S)-2 solution was transferred to a vessel with a

screwcap and the solvent was evaporated by flushing with nitrogen gas. To the vessel was

added a 2 mL aliquot of the poly-1–HCl solution, and the resulting mixture was stirred at

ambient temperature (ca. 26 ˚C) for 30 min. The absorption and CD spectra of the solution

were then measured after filtration (Figure S1). The molar ratio of the bound (S)-2 to

S3

poly-1–HCl was estimated as follows. The solution of poly-1–HCl (3.9 mM) complexed

with (S)-2 was lyophilized, and the residue was dissolved in a small amount of methanol.

The methanol solution was poured into a large amount of ether, and the precipitated poly-

1–HCl containing no trace amount of (S)-2 was removed by centrifugation. The recovery of

the (S)-2 was estimated to be 1.7 x 10–4

mmol ([(S)-2]/[poly-1–HCl] = 0.022) based on the

UV-vis spectrum of the (S)-2 in ethanol ( 278 = 10000) after evaporating the solvent in the

supernatant containing (S)-2, followed by dilution with ethanol.

CD Measurements of Induced Helical Poly-1–HCl in the Presence of TPPS and Dyes.

A typical experimental procedure is described below. A stock solution of a helical poly-

1–HCl (0.2 mg mL–1

, 0.79 mM)) induced by (S)-2 ([(S)-2]/[poly-1–HCl] = 0.022) in 0.1 N

aqueous HCl was prepared in the same way as described above. A stock solution of

H4TPPS2–

in 0.1 N aqueous HCl (24 μM) was also prepared in a 100-mL flask equipped

with a stopcock. A 1 mL aliquot of the stock solution of poly-1–HCl with (S)-2 was

transferred to a vessel, and to this was added a 1 mL aliquot of the stock solution of

H4TPPS2–

and the absorption, CD (Figure 2), and RLS spectra (Figure S4) were taken.

The effect of methanol on the chiral H4TPPS2–

aggregates induced by the poly-

1–HCl—(R)-2 was investigated as follows. A stock solution of H4TPPS2–

(12 μM) in the

presence of poly-1–HCl—(R)-2 complex ([poly-1–HCl] = 0.4 mM, [(R)-2]/[poly-1–HCl] =

0.022) in 0.1 N aqueous HCl was prepared in a 10-mL vessel with a screwcap. After the

initial absorption and CD spectra were measured, a 1 mL aliquot of the stock solution was

transferred to a 10-mL vessel with a screwcap. To the vessel was added increasing

S4

volumes of methanol and the absorption and CD spectra were taken for each addition

(Figure S9A).

Optically active (H4TPPS2–

)* aggregates were prepared by stirring anticlockwisely a

solution of H4TPPS2–

(24 μM, 100 mL) in 0.1 N aqueous HCl for 5 days (Figure S6b)

according to a literature method.[4]

Solutions of optically active poly-1–HCls induced by

(S)- and (R)-2 ([poly-1–HCl] = 0.8 mM, [2]/[poly-1–HCl] = 0.022) were also prepared.

One mL aliquots of the stock solution were transferred to two 10-mL vessels separately,

and to these were added a 1 mL aliquot of the stock solution of the optically active

(H4TPPS2–

)* aggregates prepared above, respectively ([poly-1–HCl] = 0.4 mM and

[(H4TPPS2–

)*] = 12 μM), and the absorption and CD spectra were recorded for each sample

(Figure S6).

CD and Absorption Spectral Changes of Chiral Aggregates of H4TPPS2–

Induced by

a Helical Poly-1–HCl—(S)-2 Complex upon Addition of (R)-2. Stock solutions of

poly-1–HCl (0.8 mM) and H4TPPS2–

(24 μM) in 0.1 N aqueous HCl were prepared in 10-

and 100-mL flasks with stopcocks, respectively. Stock solutions of (S)- and (R)-2 (0.8

mM) in methanol were also prepared in 10-mL flasks. A 1 mL aliquot of the poly-1–HCl

solution was transferred to a vessel equipped with a screwcap, and to this were added a 90

μL aliquot of the (S)-2 solution and a 1 mL aliquot of the H4TPPS2–

solution, successively.

After the initial absorption and CD spectra were measured, a 90 μL aliquot of the stock

solution of (R)-2 was added to the vessel. This gave a poly-1—H4TPPS2–

complex

solution with a racemic 2. Further addition of a 90 μL of the (R)-2 solution was done and

S5

the absorption and CD spectra were taken for each addition to explore the changes in the

absorption and CD spectra (Figure 3).

S6

Supporting References

[1] a) E. Yashima, Y. Maeda, Y. Okamoto, Chem. Lett. 1996, 955-956; b) E. Yashima, Y.

Maeda, T. Matsushima, Y. Okamoto, Chirality 1997, 9, 593-600; c) K. Maeda, Y.

Takeyama, K. Sakajiri, E. Yashima, J. Am. Chem. Soc. 2004, 126, 16284-16285.

[2] a) H. Shirakawa, T. Ito, S. Ikeda, Polym. J. 1973, 4, 460-462; b) M. Tabata, Y.

Tanaka, Y. Sadahiro, T. Sone, K. Yokota, I. Miura, Macromolecules 1997, 30, 5200-

5204.

[3] a) R. F. Pasternack, C. Bustamante, P. J. Collings, A. Gianetto, E. J. Gibbs, J. Am.

Chem. Soc. 1993, 115, 5393-5399; b) R. F. Pasternack, P. J. Collings, Science 1995,

269, 935-939.

[4] a) O. Ohno, Y. Kaizu, H. Kobayashi, J. Chem. Phys. 1993, 99, 4128-4139; b) R.

Rubires, J.-A. Farrera, J. M. Ribó, Chem. Eur. J. 2001, 7, 436-446; c) J. M. Ribó, J.

Crusats, F. Sagués, J. Claret, R. Rubires, Science 2001, 292, 2063-2066.

S7

Figure S1. CD spectra of poly-1–HCl (1 mg mL–1) with (S)- and (R)-2 ([2]/[poly-

1–HCl] = 0.022) in water (pH 5.5) at 25 ˚C. The absorption spectra of poly-1–HCl

and poly-1–HCl with (S)-2 in water are also shown.

Figure S2. Dependence of ICD intensities of the second Cotton effect of poly-

1–HCl ( 2nd) on pH (A) and NaCl concentration (pH 5.5—6.0) (B) during the

complexation of poly-1–HCl (1 mg mL–1) with (S)-2 ([(S)-2]/[poly-1–HCl] = 0.022) in

water. The pH was adjusted with HCl at room temperature.

JJ J J J J

0

5

10

15

0 20 40 60 80 100

J J J J J

0

5

10

15

0 2 4 6

2nd /M–1 cm–1

pH [NaCl]/[poly-1–Na]

(A) (B)

2nd /M–1 cm–1

300 400 500

20

10

0

–20

–101.0

0.5

0

/M–1 cm–1

/104 M–1 cm–1

poly-1–HCl—(S)-2 (—)

poly-1–HCl—(R)-2 (—)

/ nm

poly-1–HCl—(S)-2 (—)

poly-1–HCl (—)

S8

Figure S3. CD and absorption spectra of poly-1–HCl—(S)-2 complex ([(S)-

2]/[poly-1–HCl] = 0.022) with and without sodium fluorescein (dye-3) (A) and

sodium alizarinsulfonate (dye-4) (B) in a 1.0- (A) and 0.1-cm cell (B) in water at 25

˚C. Insets show expanded details of the CD spectra in the long wavelength

regions. The concentration of poly-1–HCl and the molar ratio of the dyes to

monomer units of poly-1–HCl are 0.1 mg mL–1 and 0.3 (A) and 1.0 mg mL–1 and 0.1

(B), respectively. The solution pH was 5.3 ± 0.1.

100

50

0

–50

–1002

1

0300 400 500 600 700

/ nm

CD /mdeg

O

O

OHOH

SO3Na

dye-3

200

100

0

–100

–200 2

1

0300 400 500 600

3 mdeg

O ONaO

CO2Na

dye-4

2 mdeg

withdye-3

without dye-3

with dye-3

without dye-3

with dye-4

without dye-4(A) (B)

without dye-3with dye-3

without dye-4

with dye-4

with dye-4

without dye-4

500 600 500 550

A

CD /mdeg

A

/ nm

S9

Figure S4. RLS spectra of H4TPPS2– aggregates (12 μM) formed in the presence

(a, red line) and absence (b, blue line) of helical poly-1–HCl—(S)-2 complex ([poly-

1–HCl] = 0.4 mM, [(S)-2]/[poly-1–HCl] = 0.022) in a 1.0-cm cell in 0.1 N HCl (pH 1.6)

at ambient temperature (ca. 25 ˚C). The band-pass was 3 nm and the scan speed

was 50 nm min–1.

400 500 600

0.1

0.08

0.06

0.04

0.02

0

a: poly-1•(S)-2—H4TPPS2– (—)b: H4TPPS2– (—)

/ nm

RelativeIntensity

0.12

S10

Figure S5. The calculated CD and absorption spectra of chiral H4TPPS2–

aggregates (12 μM) induced by helical poly-1–HCl—(R)-2 complex ([poly-1–HCl] =

0.1 mg mL–1 (0.4 mM monomer units), [(R)-2]/[poly-1–HCl] = 0.022) in 0.1 N HCl (pH

1.6) (a, red lines). The calculated CD and absorption spectra were obtained by

subtracting the spectra of poly-1–HCl in the presence of (R)-2 from those of

H4TPPS2– aggregates in the helical poly-1–HCl—(R)-2 system (see Figure 2). The

CD and absorption spectra of optically active H4TPPS2– aggregates [(H4TPPS2–)*]

(24 μM) prepared by stirring a H4TPPS2– solution anticlockwisely in 0.1 N HCl for 5

days at ambient temperature are also shown (b, blue lines). The molar

absorptivities are calculated based on the H4TPPS2– concentration.

43210

350 400 450 500 750

150

100

50

0

–50

–100

–150

a: Calculated (—)

BJ band

B band of H4TPPS2–

BH band

/M–1 cm–1

/105 M–1 cm–1

/ nm

b: (H4TPPS2–)* (—)

650

10

5

0

–5

/M–1 cm–1

S11

Figure S6. CD and absorption spectra of chiral H4TPPS2– aggregates (12 μM)

induced by helical poly-1–HCl—(S)- (a and d) and (R)-2 complexes (c) ([poly-

1–HCl] = 0.1 mg mL–1 (0.4 mM), [2]/[poly-1–HCl] = 0.022) in a 0.5-cm cell and

optically active H4TPPS2– aggregates [(H4TPPS2–)*] (24 μM) in a 0.2-cm cell (b and

e) in 0.1 N HCl (pH 1.6) at 25 ˚C. Insets show expanded details of the CD spectra

in the J-aggregated H4TPPS2– chromophore regions. The CD intensity of the

optically active (H4TPPS2–)* was normalized to that in a 0.5-cm cell. The optically

active (H4TPPS2–)* aggregates were prepared by stirring a H4TPPS2– solution

anticlockwisely in 0.1 N HCl for 5 days at room temperature (b and e), and this was

added to the helical poly-1–HCl induced by (S)- and (R)-2 (a and c, respectively).

30

10

0

–10

–30480 500 520

c

a

CD /mdeg

a: poly-1•(S)-2—H4TPPS2–

b: (H4TPPS2–)*c: poly-1•(R)-2—H4TPPS2–

d: poly-1•(S)-2—H4TPPS2–

e: (H4TPPS2–)* (—)

(—)(—)(—)

2

1

0

–1

–2650 700 750

c(H4TPPS2–)*

a

100

50

0

–50

–100

CD /mdeg

300 400 500 600 700 / nm

0

1

2

(H4TPPS2–)*

(—)

A

CD /mdeg

S12

Figure S7. CD and absorption spectral changes of chiral H4TPPS2– aggregates

(12 μM) induced by helical poly-1–HCl—(S)-2 complex ([poly-1–HCl] = 0.1 mg mL–1

(0.4 mM), [(S)-2]/[poly-1–HCl] = 0.022) in 0.1 N HCl (pH 1.6) with temperature.

Inset shows expanded detail of the CD spectra in the J-aggregated H4TPPS2–

chromophore region.

at 25 ˚Cat 50at 70at 90

(—)(—)(—)(—)

100

50

0

–50

CD /mdeg

0

1

2

300 400 500 600 700 / nm

40

20

0

–20

–40480 500 520

CD /mdeg

A

S13

Figure S8. CD spectral changes of poly-1–HCl (1 mg mL–1) with (S)-2 ([(S)-

2]/[poly-1–HCl] = 0.022) in water (pH 5.5) at 25 ˚C upon addition of increasing

volumes of methanol. The absorption spectrum of poly-1–HCl with (S)-2 in

water–methanol (25/75, v/v) is also shown.

300 400 500 / nm

20

10

0

–20

–10

1.0

0.5

0

/104 M–1 cm–1

/M–1 cm–1

water/methanol (v/v)100/0. (—) 67/33 (—) 50/50 (—) 25/75 (—)

=

S14

Figure S9. CD spectral changes of chiral H4TPPS2– aggregates ([H4TPPS2–]0 = 12

μM) induced by helical poly-1–HCl—(R)-2 (A) and helical poly-1–HCl—(S)-2 (B)

complexes ([poly-1–HCl]0 = 0.1 mg mL–1 (0.4 mM), [(R)-2 or (S)-2]/[poly-1–HCl] =

0.022) in 0.1 N HCl (pH 1.6) at 25 ˚C upon addition of increasing volumes of

methanol. The CD intensities in 0.1 N HCl–methanol (67/33 and 25/75, v/v) were

normalized to those at the initial concentration. Insets show expanded details of the

CD spectra in the J-aggregated H4TPPS2– chromophore region. The absorption

spectra of the ternary mixtures in 0.1 N HCl–methanol (25/75, v/v) are also shown.

300 400 500 600 700 / nm

30

15

0

–15

–30

480 500 520

CD /mdeg

0.1 N HCl/methanol (v/v)100/0. (—) 67/33 (—) 25/75 (—)

=50

0

–100

CD /mdeg

–50

0

0.4

0.8

A

400 500 600 700 / nm

50

0CD /mdeg

0

0.4

0.8

A

100

–50

0.1 N HCl/methanol (v/v)100/0. (—) 67/33 (—) 25/75 (—)

=

300

30

15

0

–15

–30480 500 520

CD /mdeg

(A)

(B)

S15

Figure S10. Absorption spectral changes of H4TPPS2– aggregates formed in the

absence of poly-1–HCl template in 0.1 N HCl (pH 1.6) with temperature ([H4TPPS2–]

= 24 μM) (A) and upon addition of increasing volumes of methanol ([H4TPPS2–]0 =

120 μM) (B).

1

0

2

350 450400 500 600 700

0.25

0

0.5

100/0 (—) 67/33 (—) 50/50 (—)

0.1 N HCl/methanol (v/v)(A) (B)=

350 450400 500 600 700 / nm

at 25 ˚C (—)at 50 ˚C (—)at 70 ˚C (—)at 90 ˚C (—)

0.75

AA

/ nm