Syntheses and photophysical behavior of porphyrin isomer sn(iv) complexes

Daisuke Maeda, Hisashi Shimakoshi, Masaaki Abe, Yoshio Hisaeda

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

2,3,6,7,12,13,16,17-Octaethylhemlporphycenato Sn(IV) chloride, [Sn IV(OEHPc)CI2], and 2,3,6,7,12,13,16,17- octaethylporphycenato Sn(IV) chloride, [Sn (OEPc)CI2], were synthesized in high yields and fully characterized by various spectroscopic methods. The X-ray crystal structures of the Sn(IV) complexes with porphycene and hemiporphycene were determined for the first time. The photophysical and photochemical properties of the singlet state of the Sn(IV) porphycene and hemiporphycene complexes, structural isomers of porphyrin, have been investigated by fluorescence and phosphorescence spectroscopies. The relatively strong emission and long fluorescence lifetime of the Sn(IV) porphycene complexes indicated by the fluorescence quantum yield and lifetime measurement were observed in the case of the Sn(IV) porphycene ([SnIV(OEPc) CI2], φF = 0.125, τS = 2681 ps; [SnIV(OEP)CI2], φF=0.010, τs=438 ps; [SnIV(OEHPc)CI2], φF=0.027, τS=733 ps). The triplet state of the Sn(IV) complexes was investigated by transient absorption spectroscopy. It became clear that the triplet lifetime of the Sn(IV) porphycene (τT = 49.9μs) was longer when compared to those of the Sn(IV) porphyrin (τT = 32.6 μs) and hemiporphycene complexes (τT = 28.3 μs). These porphyrin isomer Sn(IV) complexes showed the high singlet oxygen generating ability, and the photo-oxidation of the 1,5-hydroxynaphthalene mediated by the Sn(IV) porphycene was the most effective among the complexes. This result Is due to its more effective light absorption In the visible region and indicated that the porphycene is an excellent candidate as a photosensitizer.

Original languageEnglish
Pages (from-to)9853-9860
Number of pages8
JournalInorganic chemistry
Volume48
Issue number20
DOIs
Publication statusPublished - Nov 6 2009

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Porphyrins
porphyrins
Isomers
isomers
life (durability)
fluorescence
synthesis
chlorides
photooxidation
phosphorescence
electromagnetic absorption
Fluorescence
atomic energy levels
absorption spectroscopy
Chlorides
crystal structure
Naphthols
Phosphorescence
oxygen
Singlet Oxygen

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Syntheses and photophysical behavior of porphyrin isomer sn(iv) complexes. / Maeda, Daisuke; Shimakoshi, Hisashi; Abe, Masaaki; Hisaeda, Yoshio.

In: Inorganic chemistry, Vol. 48, No. 20, 06.11.2009, p. 9853-9860.

Research output: Contribution to journalArticle

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abstract = "2,3,6,7,12,13,16,17-Octaethylhemlporphycenato Sn(IV) chloride, [Sn IV(OEHPc)CI2], and 2,3,6,7,12,13,16,17- octaethylporphycenato Sn(IV) chloride, [Sn (OEPc)CI2], were synthesized in high yields and fully characterized by various spectroscopic methods. The X-ray crystal structures of the Sn(IV) complexes with porphycene and hemiporphycene were determined for the first time. The photophysical and photochemical properties of the singlet state of the Sn(IV) porphycene and hemiporphycene complexes, structural isomers of porphyrin, have been investigated by fluorescence and phosphorescence spectroscopies. The relatively strong emission and long fluorescence lifetime of the Sn(IV) porphycene complexes indicated by the fluorescence quantum yield and lifetime measurement were observed in the case of the Sn(IV) porphycene ([SnIV(OEPc) CI2], φF = 0.125, τS = 2681 ps; [SnIV(OEP)CI2], φF=0.010, τs=438 ps; [SnIV(OEHPc)CI2], φF=0.027, τS=733 ps). The triplet state of the Sn(IV) complexes was investigated by transient absorption spectroscopy. It became clear that the triplet lifetime of the Sn(IV) porphycene (τT = 49.9μs) was longer when compared to those of the Sn(IV) porphyrin (τT = 32.6 μs) and hemiporphycene complexes (τT = 28.3 μs). These porphyrin isomer Sn(IV) complexes showed the high singlet oxygen generating ability, and the photo-oxidation of the 1,5-hydroxynaphthalene mediated by the Sn(IV) porphycene was the most effective among the complexes. This result Is due to its more effective light absorption In the visible region and indicated that the porphycene is an excellent candidate as a photosensitizer.",
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N2 - 2,3,6,7,12,13,16,17-Octaethylhemlporphycenato Sn(IV) chloride, [Sn IV(OEHPc)CI2], and 2,3,6,7,12,13,16,17- octaethylporphycenato Sn(IV) chloride, [Sn (OEPc)CI2], were synthesized in high yields and fully characterized by various spectroscopic methods. The X-ray crystal structures of the Sn(IV) complexes with porphycene and hemiporphycene were determined for the first time. The photophysical and photochemical properties of the singlet state of the Sn(IV) porphycene and hemiporphycene complexes, structural isomers of porphyrin, have been investigated by fluorescence and phosphorescence spectroscopies. The relatively strong emission and long fluorescence lifetime of the Sn(IV) porphycene complexes indicated by the fluorescence quantum yield and lifetime measurement were observed in the case of the Sn(IV) porphycene ([SnIV(OEPc) CI2], φF = 0.125, τS = 2681 ps; [SnIV(OEP)CI2], φF=0.010, τs=438 ps; [SnIV(OEHPc)CI2], φF=0.027, τS=733 ps). The triplet state of the Sn(IV) complexes was investigated by transient absorption spectroscopy. It became clear that the triplet lifetime of the Sn(IV) porphycene (τT = 49.9μs) was longer when compared to those of the Sn(IV) porphyrin (τT = 32.6 μs) and hemiporphycene complexes (τT = 28.3 μs). These porphyrin isomer Sn(IV) complexes showed the high singlet oxygen generating ability, and the photo-oxidation of the 1,5-hydroxynaphthalene mediated by the Sn(IV) porphycene was the most effective among the complexes. This result Is due to its more effective light absorption In the visible region and indicated that the porphycene is an excellent candidate as a photosensitizer.

AB - 2,3,6,7,12,13,16,17-Octaethylhemlporphycenato Sn(IV) chloride, [Sn IV(OEHPc)CI2], and 2,3,6,7,12,13,16,17- octaethylporphycenato Sn(IV) chloride, [Sn (OEPc)CI2], were synthesized in high yields and fully characterized by various spectroscopic methods. The X-ray crystal structures of the Sn(IV) complexes with porphycene and hemiporphycene were determined for the first time. The photophysical and photochemical properties of the singlet state of the Sn(IV) porphycene and hemiporphycene complexes, structural isomers of porphyrin, have been investigated by fluorescence and phosphorescence spectroscopies. The relatively strong emission and long fluorescence lifetime of the Sn(IV) porphycene complexes indicated by the fluorescence quantum yield and lifetime measurement were observed in the case of the Sn(IV) porphycene ([SnIV(OEPc) CI2], φF = 0.125, τS = 2681 ps; [SnIV(OEP)CI2], φF=0.010, τs=438 ps; [SnIV(OEHPc)CI2], φF=0.027, τS=733 ps). The triplet state of the Sn(IV) complexes was investigated by transient absorption spectroscopy. It became clear that the triplet lifetime of the Sn(IV) porphycene (τT = 49.9μs) was longer when compared to those of the Sn(IV) porphyrin (τT = 32.6 μs) and hemiporphycene complexes (τT = 28.3 μs). These porphyrin isomer Sn(IV) complexes showed the high singlet oxygen generating ability, and the photo-oxidation of the 1,5-hydroxynaphthalene mediated by the Sn(IV) porphycene was the most effective among the complexes. This result Is due to its more effective light absorption In the visible region and indicated that the porphycene is an excellent candidate as a photosensitizer.

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