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Mechanism of Peripheral Substituent Effects on Adsorption-Aggregation Behaviors of Cationic Porphyrin Dyes on tungsten(VI) Oxide Nanocolloid Particles

Mechanism of Peripheral Substituent Effects on Adsorption-Aggregation Behaviors of Cationic Porphyrin Dyes on tungsten(VI) Oxide Nanocolloid Particles

Naoya Kanetada, Chiyoe Matsumura, Suzuko Yamazaki, Kenta Adachi

ACS Appl Mater Interfaces. 2013 Dec 26;5(24):12991-9.

PMID: 24298877

Abstract:

The adsorption and aggregation behaviors of the cationic porphyrin derivatives such as 5,10,15,20-tetrakis(4-pyridyl)porphyrin [TPyP], 5,10,15,20-tetrakis(N-methyl-4-pyridyl)porphyrin [TMPyP], 5,10,15,20-tetrakis(N-ethyl-4-pyridyl)porphyrin [TEPyP], and 5,10,15,20-tetrakis(N-n-propyl-4-pyridyl)porphyrin [TPPyP] (hereafter called "TPyP derivatives") in the tungsten(VI) oxide (WO3) colloid aqueous solution at weak acidic pH were studied by UV-vis spectroscopy. The TPyP derivatives were strongly adsorbed as monolayer onto the WO3 surface via the electrostatic interaction between their peripheral cationic substituents and negatively surface-charged WO3 colloid particles, and most of the ones adsorbed eventually formed J-type dimers aligned in the head-to-tail fashion. These different dimerization states were effectively analyzed by the change of ratios among the intensities of exciton split Soret bands (H- and J-bands). Judging from the exciton coupling theory and adsorption measurements, we concluded that the J-dimer geometry of the TPyP derivatives adsorbed on the WO3 colloid particle surface is strongly dependent on the presence and difference of peripheral substituents. The results described here indicate a new and promising way of designing surface supramolecular structures combination of two principles, the self-association of organic dyes, and the steric repulsive interaction between the peripheral substituents and the inorganic semiconductor surfaces.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP1314358	Tungsten(VI) oxide		1314-35-8	Price

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