SUPPORTING INFORMATION

Synthesis

CH3I was purchased from Tokyo Chemical Industry, and used without further purification.

SbCl5, 5,10,15,20-tetraphenylporphine (TPP) and 5,10,15,20-tetrakis(4-pyridinyl)porphine

(TPyP) were purchased from Aldrich, and used without further purification. 5,10-diphenyl-

15,20-di(4-pyridinyl)porphine (DPyP) was purchased from Frontier Scientific, and used whitout

further purification. All syntheses were carried out under nitrogen atmosphere.

1
H-NMR spectra in D2O were recorded on a Bruker B-500.

Synthesis of [SbV(TPP)(OH)2]Cl

Dihydroxo(5,10,15,20-tetraphenylporphyrinato)antimony(V) chloride ( [SbV(TPP)(OH)2]Cl )

was synthesized as below. SbCl5 (1 mL) was added to a solution of TPP (100 mg) in pyridine (50

mL). The reaction mixture was refluxed for 30 hours. The solution was added to dropwise CHCl3

(500 mL) and undissolved materials were removed by filtration. The red-violet solvent was

evaporated and the residue was solved in CH2Cl2 (50 mL). The CH2Cl2 solution was washed

three times with 50mL portions of H2O. After H2O (150 mL) was added to the CH2Cl2 solution,

the solution was stirred for 24 hours and the red-colored aqueous phase was extracted four times.

The counter ion (antimony complex anion) was exchanged to Cl- by the use of ion-exchange

resin (Organo, Amberlite Resin IRA-400) to give dihydroxo[5,10,15,20-

tetraphenylporphyrinato]antimony(V) chloride ( [SbV(TPP)(OH)2]Cl ) in ca. 11% yield.

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1
H-NMR ((CD3)2CO /ppm) δ 8.01 (8H, t, m-Phenyl), 8.07 (4H, t, p-Phenyl), 8.48 (8H, d, o-

Phenyl), 9.60 (8H, d, β-Pyrrole).

Synthesis of [SbV(DMPyP)(OH)2]Cl3

Dihydroxo[5,10-diphenyl-15,20-di(N-methyl-pyridinium-4-yl)porphyrinato]antimony(V)

trichloride ( [SbV(DMPyP)(OH)2]Cl3 ) was synthesized as below. SbCl5 (1 mL) was added to a

solution of DPyP (50.0 mg) in pyridine (30 mL). The reaction mixture was refluxed for 33 hours.

H2O (3 mL) was added to the solution. The solution was filtrated and undissolved materials were

removed. The solvent was evaporated and the residue was solved in Water (50 mL). The aqueous

solution was filtrated again. CHCl3 (50 mL) was added to the aqueous solution and red violet

CHCl3 solution was extracted. The CHCl3 solution was washed three times with 50mL portions

of H2O. After evaporation, the product was dissolved in H2O and the counter ion (antimony

complex anion) was exchanged to Cl- by the use of ion-exchange resin (Organo, Amberlite Resin

IRA-400) to give dihydroxo[5,10-diphenyl-15,20-di(4-pyridyl)porphyrinato]antimony(V)

chloride ( [SbV(DPyP)(OH)2]Cl ). 1
H-NMR (D2O /ppm) δ 8.01 (4H, t, m-Ph), 8.08 (4H, t, p-

Ph), 8.46 (4H, d, o-Ph), 8.87 (4H, d, m-Py), 9.30 (4H, d, o-Py) , 9.70 (2H, d, β-Pyrr), 9.75 (2H, s,

β-Pyrr), 9.79 (2H, s, β-Pyrr),9.83 (2H, d, β-Pyrr).

[SbV(DPyP)(OH)2]Cl was dissolved in acetone-H2O (15:1 v/v 32 mL). CH3I (1 mL) was added

and the reaction mixture was heated for 6 days at 40 ○C. After evaporation of the solvent, the

counter ion (I-) was exchanged to Cl- by the use of ion-exchange resin to give dihydroxo[5,10-

diphenyl-15,20-di(N-methyl-pyridinium-4-yl)-porphyrinato]antimony(V) trichloride

( [SbV(DMPyP)(OH)2]Cl3 ) in ca. 13% yield. 1

H-NMR (D2O / ppm) δ 4.87 (6H, s, N-Me), 8.01

2
(4H, t, m-Ph), 8.07 (4H, t, p-Ph), 8.47 (4H, d, o-Ph), 9.15 (4H, d, m-Py), 9.46 (4H, d, o-Py) , 9.64

(2H, d, β-Pyrr), 9.70 (2H, s, β-Pyrr), 9.79 (2H, s, β-Pyrr),9.84 (2H, d, β-Pyrr).

Synthesis of [SbV(TMPyP)(OH)2]Cl5

Dihydroxo[5,10,15,20-tetrakis(N-methyl-pyridinium-4-yl)porphyrinato]antimony(V)

pentachloride ( [SbV(TMPyP)(OH)2]Cl5 ) was synthesized as below. SbCl5 (1 mL) was added to

a solution of TPyP (200 mg) in pyridine (50 mL). The reaction mixture was refluxed for 30 hours.

The solution was added to dropwise CHCl3 (500 mL) and undissolved materials were removed

by filtration. The red solvent was evaporated and the residue was solved in CH2Cl2 (50 mL). The

CH2Cl2 solution was washed three times with 50mL portions of H2O. After H2O (150 mL) was

added to the CH2Cl2 solution, the solution was stirred for 24 hours and the red-colored aqueous

phase was extracted four times. The counter ion (antimony complex anion) was exchanged to Cl-

by the use of ion-exchange resin (Organo, Amberlite Resin IRA-400) to give

dihydroxo[5,10,15,20-tetrakis(4-pyridyl)porphyrinato]antimony(V) chloride

( [SbV(TPyP)(OH)2]Cl ). 1H-NMR (D2O / ppm) δ 8.92 (8H, d, m-Py), 9.34 (8H, d, o-Py) , 9.84

(8H, s, β-Pyrr).

[SbV(TPyP)(OH)2]Cl was dissolved in acetone-H2O (6:1 v/v 35 mL). CH3I (1 mL) was added

and the reaction mixture was heated for 9 days at 40 ○C. The red violet solid of was

reprecipitated from acetone (1.5 L). The counter ion (I-) was exchanged to Cl- by the use of ion-

exchange resin to give hygroscopic dihydroxo[5,10,15,20-tetrakis(N-methyl-pyridinium-4-

yl)porphyrinato]antimony(V) pentachloride ( [SbV(TMPyP)(OH)2]Cl5 ) in ca. 9% yield. 1H-NMR

(D2O / ppm) δ 4.87 (12H, s, N-Me), 9.17 (8H, d, m-Py), 9.46 (8H, d, o-Py) , 9.65 (8H, d, β-Pyrr).

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 0.12

0.10
s-polarized light

Absorbance
0.08
p-polarized light
0.06

0.04

0.02

0.00
380 430 480 530
Wavelength / nm

Figure S1. Absorption spectra obtained with s- and p-polarized light for SbVTPP on the quartz

waveguide in water.