Details

Autor(en) / Beteiligte

• Fang, Yuanyuan
• Jiang, Xiaoqin
• Ou, Zhongping
• Michelin, Clément
• Desbois, Nicolas
• Gros, Claude P.
• Kadish, Karl M.

Titel

Redox properties of nitrophenylporphyrins and electrosynthesis of nitrophenyl-linked Zn porphyrin dimers or arrays

Ist Teil von

• Journal of porphyrins and phthalocyanines, 2014-08, Vol.18 (8n09), p.832-841

Ort / Verlag

Singapore: World Scientific Publishing Company

Erscheinungsjahr

2014

Beschreibungen/Notizen

• Five nitrophenylporphyrins were investigated as to their electrochemical properties in CH2Cl2 containing 0.1 M TBAP. The investigated compounds are represented as (NO2Ph)xPh4-xPorM, where Por represents the dianion of the porphyrin macrocycle, Ph is a phenyl group on meso-position of the macrocycle, NO2Ph is a meso-substituted nitrophenyl group, M = 2H, PdII or ZnII and x = 1 or 2. Each porphyrin undergoes an initial one electron reduction at E1/2 = -1.07 to -1.12 V where the added negative charge is almost totally localized on the meso-nitrophenyl group of the compound. This reversible reduction is then followed by one or more irreversible reductions of the nitrophenyl anion at more negative potentials which overlap with reduction of the conjugated porphyrin macrocycle. The initial one electron addition was monitored by thin-layer UV-vis spectroelectrochemistry which confirmed formation of a reduced nitrophenyl group in each case but also gave spectral evidence for a linkage of the one-electron reduction products in the case of the Zn derivatives, giving Zn porphyrin dimers or arrays which are characterized by a 14–15 nm red-shifted Soret band and two well-defined Q-bands, consistent with conversion from an unreduced four coordinate ZnII nitrophenylporphyrin to a five-coordinate ZnII complex with an unreduced porphyrin macrocycle. Five nitrophenylporphyrins were investigated as to their electrochemical properties in CH2Cl2 containing 0.1 M TBAP and the products of the first reduction examined by UV-visible spectroelectrochemistry.