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Binuclear Rhodium(I) Complex of a Dimethylvinylene-Bridged Distorted Hexaphyrin(2.1.2.1.2.1)
Songlin Xue1, Ningchao Liu1, Peifeng Mei2
1School of Chemistry and Chemical Engineering, Jiangsu University, 301 Xuefu Road, Zhenjiang 212013, China.
Abstract:
A highly distorted binuclear rhodium(I) complex, 2Rh, was successfully synthesized from hexaphyrin(2.1.2.1.2.1) containing dimethylvinylene-bridges between dipyrrin units. IR spectroscopy, 1H NMR spectroscopy, and X-ray crystallography revealed that the complex 2Rh consists of two rhodium(I) ions coordinated to two dipyrrin units. Rh complexation induced a transformation from a trans-/cis-/trans- to trans-/cis-/cis-conformation on the dimethylvinylene-bridges. This is the first example of rhodium(I)-ion-induced cis-/trans-isomerization in the porphyrin derivatives. Theoretical calculations of 2Rh predicted the presence of intramolecular charge-transfer absorption due to the distorted molecular structure.
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