Structural and photophysical properties of self-assembled porphyrin nanoassemblies organized by ethylene glycol derivatives

Atula S.D. Sandanayaka; Yasuyuki Araki; Takehiko Wada; Taku Hasobe

doi:10.1021/jp805202y

Structural and photophysical properties of self-assembled porphyrin nanoassemblies organized by ethylene glycol derivatives

Atula S.D. Sandanayaka, Yasuyuki Araki, Takehiko Wada, Taku Hasobe

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

49 Citations (Scopus)

Abstract

We demonstrate an ability to control the structures and photodynamics of porphyrin-based nanoassemblies via solvent mixture technique. Surfactants such as ethylene glycol (EG) derivatives with different chain lengths are employed to control the sizes and shapes of nanoparticles composed of meso-substituted tetracarboxyphenyl porphyrin [H₂P(CO₂H)₄] in mixed H₂O/THF solvent. With increasing the chain lengths, the diameters of H₂P(CO₂H)₄/EG composite nanoparticles systematically increase in the range of 90-350 nm. In contrast with H₂P(CO₂H)₄/EG composite nanoparticles, pristine H₂P(CO₂H)₄ assemblies show long rod-shaped assemblies with micrometer scales. The porphyrin nanoparticles are stable in solution without precipitation for several days. The nanoparticles exhibit the following optical properties: a large bathochromic shift in the absorption spectra and an increase of the fluorescence quenching properties relative to those for the monomer porphyrin solution. The hierarchical clustering of H₂P(CO₂H)₄ molecules within nanoparticles is caused by the hydrogen bonding and p-stacking effects. The efficient fluorescence quenching of H₂P(CO₂H)₄ is mainly due to the effect of singlet-singlet annihilation of H ₂P(CO₂H)₄ moieties within nanoassemblies. We further report the quenching processes of the excited triplet states of H ₂P(CO₂H)₄ nanoassemblies. Efficient quenching properties of the excited triplet states of H₂P(CO₂H) ₄ moieties are observed in the range of lifetime 26-100 ns, which is largely dependent on the sizes of nanoparticles. These quenching processes can be also analyzed by triplet-triplet annihilation theory.

Original language	English
Pages (from-to)	19209-19216
Number of pages	8
Journal	Journal of Physical Chemistry C
Volume	112
Issue number	49
DOIs	https://doi.org/10.1021/jp805202y
Publication status	Published - 2008 Dec 11

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
Energy(all)
Physical and Theoretical Chemistry
Surfaces, Coatings and Films

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10.1021/jp805202y

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title = "Structural and photophysical properties of self-assembled porphyrin nanoassemblies organized by ethylene glycol derivatives",

abstract = "We demonstrate an ability to control the structures and photodynamics of porphyrin-based nanoassemblies via solvent mixture technique. Surfactants such as ethylene glycol (EG) derivatives with different chain lengths are employed to control the sizes and shapes of nanoparticles composed of meso-substituted tetracarboxyphenyl porphyrin [H2P(CO2H)4] in mixed H2O/THF solvent. With increasing the chain lengths, the diameters of H2P(CO2H)4/EG composite nanoparticles systematically increase in the range of 90-350 nm. In contrast with H2P(CO2H)4/EG composite nanoparticles, pristine H2P(CO2H)4 assemblies show long rod-shaped assemblies with micrometer scales. The porphyrin nanoparticles are stable in solution without precipitation for several days. The nanoparticles exhibit the following optical properties: a large bathochromic shift in the absorption spectra and an increase of the fluorescence quenching properties relative to those for the monomer porphyrin solution. The hierarchical clustering of H2P(CO2H)4 molecules within nanoparticles is caused by the hydrogen bonding and p-stacking effects. The efficient fluorescence quenching of H2P(CO2H)4 is mainly due to the effect of singlet-singlet annihilation of H 2P(CO2H)4 moieties within nanoassemblies. We further report the quenching processes of the excited triplet states of H 2P(CO2H)4 nanoassemblies. Efficient quenching properties of the excited triplet states of H2P(CO2H) 4 moieties are observed in the range of lifetime 26-100 ns, which is largely dependent on the sizes of nanoparticles. These quenching processes can be also analyzed by triplet-triplet annihilation theory.",

author = "Sandanayaka, {Atula S.D.} and Yasuyuki Araki and Takehiko Wada and Taku Hasobe",

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AU - Sandanayaka, Atula S.D.

AU - Araki, Yasuyuki

AU - Wada, Takehiko

AU - Hasobe, Taku

PY - 2008/12/11

Y1 - 2008/12/11

N2 - We demonstrate an ability to control the structures and photodynamics of porphyrin-based nanoassemblies via solvent mixture technique. Surfactants such as ethylene glycol (EG) derivatives with different chain lengths are employed to control the sizes and shapes of nanoparticles composed of meso-substituted tetracarboxyphenyl porphyrin [H2P(CO2H)4] in mixed H2O/THF solvent. With increasing the chain lengths, the diameters of H2P(CO2H)4/EG composite nanoparticles systematically increase in the range of 90-350 nm. In contrast with H2P(CO2H)4/EG composite nanoparticles, pristine H2P(CO2H)4 assemblies show long rod-shaped assemblies with micrometer scales. The porphyrin nanoparticles are stable in solution without precipitation for several days. The nanoparticles exhibit the following optical properties: a large bathochromic shift in the absorption spectra and an increase of the fluorescence quenching properties relative to those for the monomer porphyrin solution. The hierarchical clustering of H2P(CO2H)4 molecules within nanoparticles is caused by the hydrogen bonding and p-stacking effects. The efficient fluorescence quenching of H2P(CO2H)4 is mainly due to the effect of singlet-singlet annihilation of H 2P(CO2H)4 moieties within nanoassemblies. We further report the quenching processes of the excited triplet states of H 2P(CO2H)4 nanoassemblies. Efficient quenching properties of the excited triplet states of H2P(CO2H) 4 moieties are observed in the range of lifetime 26-100 ns, which is largely dependent on the sizes of nanoparticles. These quenching processes can be also analyzed by triplet-triplet annihilation theory.

AB - We demonstrate an ability to control the structures and photodynamics of porphyrin-based nanoassemblies via solvent mixture technique. Surfactants such as ethylene glycol (EG) derivatives with different chain lengths are employed to control the sizes and shapes of nanoparticles composed of meso-substituted tetracarboxyphenyl porphyrin [H2P(CO2H)4] in mixed H2O/THF solvent. With increasing the chain lengths, the diameters of H2P(CO2H)4/EG composite nanoparticles systematically increase in the range of 90-350 nm. In contrast with H2P(CO2H)4/EG composite nanoparticles, pristine H2P(CO2H)4 assemblies show long rod-shaped assemblies with micrometer scales. The porphyrin nanoparticles are stable in solution without precipitation for several days. The nanoparticles exhibit the following optical properties: a large bathochromic shift in the absorption spectra and an increase of the fluorescence quenching properties relative to those for the monomer porphyrin solution. The hierarchical clustering of H2P(CO2H)4 molecules within nanoparticles is caused by the hydrogen bonding and p-stacking effects. The efficient fluorescence quenching of H2P(CO2H)4 is mainly due to the effect of singlet-singlet annihilation of H 2P(CO2H)4 moieties within nanoassemblies. We further report the quenching processes of the excited triplet states of H 2P(CO2H)4 nanoassemblies. Efficient quenching properties of the excited triplet states of H2P(CO2H) 4 moieties are observed in the range of lifetime 26-100 ns, which is largely dependent on the sizes of nanoparticles. These quenching processes can be also analyzed by triplet-triplet annihilation theory.

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Structural and photophysical properties of self-assembled porphyrin nanoassemblies organized by ethylene glycol derivatives

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