Synthesis and Properties of Rhodium(III) Porphyrin Cyclic Tetramer and Cofacial Dimer

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• 作者：Keiko Fukushima ; Kenji Funatsu ; Akio Ichimura ; Yoichi Sasaki ; Masamitsu Suzuki ; Tetsuaki Fujihara ; Kiyoshi Tsuge ; and Taira Imamura
• 刊名：Inorganic Chemistry
• 出版年：2003
• 出版时间：May 19, 2003
• 年：2003
• 卷：42
• 期：10
• 页码：3187 - 3193
• 全文大小：203K
• 年卷期：v.42,no.10(May 19, 2003)
• ISSN：1520-510X

文摘

Rhodium(III) porphyrin complexes, [Rh(4-PyT₃P)Cl]₄ (1) and [Rh(2-PytB₃P)Cl]₂ (2) (4-PyT₃P = 5-(4-pyridyl)-10,15,20-tritolylporphyrinato dianion, 2-PytB₃P = 5-(2-pyridyl)-10,15,20-tri(4-tert-butyl)phenylporphyrinato dianion), wereself-assembled and characterized by ¹H nuclear magnetic resonance spectroscopy, infrared spectroscopy, andelectron spray ionization-mass spectroscopy methods. The spectroscopic results certified that the rhodium porphyrincomplexes 1 and 2 have a cyclic tetrameric structure and a cofacial dimeric structure, respectively. The X-raystructure analysis of 1 confirmed the cyclic structure of the complex. The Soret bands of both oligomers weresignificantly broadened by excitonic interactions between the porphyrin units, compared to those observed for acorresponding analogue of Rh(TTP)(Py)Cl (TTP = 5,10,15,20-tetratolylporphyrinato dianion, Py = pyridine). Stepwiseoxidation of the porphyrin rings in the oligomers was observed by cyclic voltammetry. The oligomers 1 and 2 arevery stable in solution, and they slowly undergo reactions with pyridine to give corresponding monomer complexesonly at high temperatures (~80 C).