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

Songlin Xue; Ningchao Liu; Peifeng Mei; Daiki Kuzuhara; Naoki Aratani; Fengxian Qiu; Hiroko Yamada

doi:10.1021/acs.inorgchem.1c02609

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

Inorg Chem. 2021 Nov 1;60(21):16070-16073. doi: 10.1021/acs.inorgchem.1c02609. Epub 2021 Oct 21.

Authors

Songlin Xue¹, Ningchao Liu¹, Peifeng Mei², Daiki Kuzuhara³, Naoki Aratani², Fengxian Qiu¹, Hiroko Yamada²

Affiliations

¹ School of Chemistry and Chemical Engineering, Jiangsu University, 301 Xuefu Road, Zhenjiang 212013, China.
² Division of Materials Science, Nara Institute of Science and Technology, 8916-5 Takayama-cho, Ikoma, Nara 630-0192, Japan.
³ Faculty of Science and Engineering, Iwate University, 4-3-5 Ueda, Morioka 020-8551, Japan.

PMID: 34672545
DOI: 10.1021/acs.inorgchem.1c02609

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.