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Binuclear Rhodium(I) Complex of a Dimethylvinylene-Bridged Distorted Hexaphyrin(2.1.2.1.2.1)

Authors :
Naoki Aratani
Ningchao Liu
Fengxian Qiu
Hiroko Yamada
Peifeng Mei
Daiki Kuzuhara
Songlin Xue
Source :
Inorganic Chemistry. 60:16070-16073
Publication Year :
2021
Publisher :
American Chemical Society (ACS), 2021.

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.

Details

ISSN :
1520510X and 00201669
Volume :
60
Database :
OpenAIRE
Journal :
Inorganic Chemistry
Accession number :
edsair.doi.dedup.....aece37b9992a38a34d3f76a20de43003
Full Text :
https://doi.org/10.1021/acs.inorgchem.1c02609