Issue 38, 2010

Photodynamics in stable complexes composed of a zinc porphyrin tripod and pyridyl porphyrins assembled by multiple coordination bonds

Abstract

A tripod zinc porphyrin (TPZn3) forms a stable 1 ∶ 1 complex with gold(III) tetra(4-pyridyl)porphyrin (AuTPyP+) and free-base tris(4-pyridyl)porphyrin (2H-Py3P) in nonpolar solvents. The strong binding of TPZn3 with AuTPyP+ or 2H-Py3P results from the encapsulation of AuTPyP+ or 2H-Py3P inside the cavity of TPZn3 through multiple coordination bonds, as indicated by UV-vis-NIR, ESI-MS, 1H NMR, electrochemistry and computational studies. The binding constants of monomer zinc porphyrin (MPZn) with AuTPyP+ and 2H-Py3P drastically decrease as compared with TPZn3. Detailed photophysical studies have been carried out on these composites using laser flash photolysis as well as emission spectroscopy. The efficient quenching of the singlet excited state of TPZn3 occurs via a photoinduced electron-transfer pathway in the TPZn3AuTPyP+ complex. In contrast, energy transfer occurs in the TPZn32H-Py3P complex due to the smaller driving force of the photoinduced electron-transfer pathway. Neither electron transfer nor energy transfer occurs from MPZn to AuTPyP+ under the same experimental conditions due to the small association constant of the monomer zinc porphyrin.

Graphical abstract: Photodynamics in stable complexes composed of a zinc porphyrin tripod and pyridyl porphyrins assembled by multiple coordination bonds

Supplementary files

Article information

Article type
Paper
Submitted
23 Apr 2010
Accepted
03 Jul 2010
First published
11 Aug 2010

Phys. Chem. Chem. Phys., 2010,12, 12160-12168

Photodynamics in stable complexes composed of a zinc porphyrin tripod and pyridyl porphyrins assembled by multiple coordination bonds

A. Takai, C. P. Gros, J. Barbe and S. Fukuzumi, Phys. Chem. Chem. Phys., 2010, 12, 12160 DOI: 10.1039/C0CP00329H

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