Supporting Information

© Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2006

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Synthesis, Structures, and Properties of Meso-Phosphorylporphyrins:

Self-Organization through P–oxo-to-Zinc Coordination

Yoshihiro Matano,*[a] Kazuaki Matsumoto,[a] Yukiko Terasaka,[a] Hiroki Hotta,[b]

Yasuyuki Araki,[c] Osamu Ito,[c] Motoo Shiro,[d] Takahiro Sasamori,[e]

Norihiro Tokitoh,[e] and Hiroshi Imahori[a]

[a] Department of Molecular Engineering, Graduate School of Engineering

Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan)

Fax: (+81)75-383-2571, E-mail: matano@scl.kyoto-u.ac.jp

[b] Department of Chemistry, Faculty of Engineering

Gunma University, Kiryu 376-8515 (Japan)

[c] Institute of Multidisciplinary Research for Advanced Materials

Tohok u University, Aoba-ku, Sendai, 980-8577 (Japan)

[d] Rigaku Corporation, Akishima-shi, Tokyo 196-8666 (Japan)

[e] Institute of Chemical Research, Kyoto University, Uji, Kyoto 611-0011 (Japan)

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Figure S1. 1H NMR spectra of 2H2 in CDCl3.

Figure S2. 1H NMR spectra of 3H2 in CDCl3.

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Figure S3. 1H NMR spectra of 2Zn in CDCl3. [2Zn] = ca. 2 mM.

Figure S4. 1H NMR spectra of 3Zn in CD2Cl2. [3Zn] = ca. 4 mM.

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Figure S5. 1H NMR spectra of 2Zn in CD3OD/CDCl3 (v/v = 7/1).

Figure S6. 1H NMR spectra of 2Zn in CDCl3 in the presence of excess pyridine.

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ef

gm-Ph

p-Phec d b

g h a

fg

e

c da bh

δ / ppm

0 °C

20 °C

–20 °C

–40 °C

–60 °C

9.5 9 8.5 8 7.5 7 6.5 6

CDCl3 : CD3OD = 1 : 3

p-Ph m-Ph

o-Ph

(a)

(b)

Figure S7. Temperature dependence of 1H NMR spectra of 3Zn in chlorinated solvents. (a) Measuredin CD3OD–CDCl3 (v/v = 3/1) at 25 °C. (b) Measured in CD2Cl2 (1.3 × 10–3 M) from 20 °C to –60 °C.The abbreviations: a = 3,7-β; b = 2,8-β; c = 12,18-β; d = 13,17-β; e = 10,20-Ho and -Ho’; f = 10,20-Hp;g = 15-Ho and -Ho’; h = 15-Hp. For the numbering, see Chart 1.

( a ) ( b )

Wavelength / nm550 650

0450350

1.0

2.0

3.0

500 550 600 6500

0.5

1.0

1.5

2.0

Wavelength / nm

Abso

rban

ce

Abs

orba

nce

Figure S8. UV-visible absorption spectra of 2Zn in toluene at various concentrations. (a) 350–650 nm:solid line, 2.0 × 10–5 M; dashed line, 5.0 × 10–6 M; dotted line, 1.0 × 10–6 M. (b) 500–650 nm: solid line,1.0 × 10–3 M; dashed line, 5.0 × 10–4 M; dotted line, 5.0 × 10–5 M. The spectra are normalized forcomparison.

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Figure S9. (a) UV-visible absorption spectra of 2Zn (1.0 × 10–3 M) in toluene on successive additionsof Ph3PO (1.0 × 10–3 ~ 1.3 × 10–1 M) at 25°C. (b) The circles are experimental values monitored at λmax

= 565 nm. The solid line is a fitted titration curve.

Figure S10. (a) UV-visible absorption spectra of 3Zn (1.0 × 10–6 M) in toluene on successive additionsof Ph3PO (3.6 × 10–4 ~ 2.3 × 10–2 M) at 25°C. (b) The circles are experimental values monitored at λmax

= 435 nm. The solid line is a fitted titration curve.

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Figure S11. Fluorescence spectra of (a) 2Zn and (b) 3Zn in toluene at 25 °C. (a) solid line, 1.0 × 10–7

M (λex = 422 nm); dashed line, 1.0 × 10–4 M (λex = 512 nm). (b) solid line, 1.0 × 10–7 M (λex = 422 nm);dashed line, 1.0 × 10–5 M (λex = 512 nm).

Figure S12. Fluorescence decay curves for 2Zn in toluene, monitored at 615±10 nm (λex= 400 nm). (a)[2Zn] = 1.0 × 10–4 M: τf = 2.66 ns. (b) [2Zn] = 3.4 × 10–7 M: τf = 2.69 ns.

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Figure S13. (a), (b) Cyclic voltammograms for 2Zn. (c), (d) Differential pulse voltammograms for2Zn. Measured in CH2Cl2.[2Zn] = 1.0 × 10–3 M. [TBAP] = 0.1 M. Scan rate = 20 mV s–1. Asteriskindicates the Fc/Fc+ couple. (a), (c) In the absence of Ph3PO. (b), (d) In the presence of Ph3PO: [Ph3PO]= 5.0 × 10–3 M.