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Gold dipyrrin-bisphenolates: a combined experimental and DFT study of metal–ligand interactions†
Kolle E. Thomas,Nicolas Desbois,Simon J. Teat,Claude P. Gros,Abhik Ghosh
RSC Advances Pub Date : 01/02/2020 00:00:00 , DOI:10.1039/C9RA09228E
Abstract

Given that noninnocent and metalloradical-type electronic structures are ubiquitous among dipyrrin-bisphenolate (DPP) complexes, we synthesized the gold(III) derivatives as potentially innocent paradigms against which the properties of other metallo-DPP derivatives can be evaluated. Electronic absorption spectra, electrochemical studies, a single-crystal X-ray structure, and DFT calculations all suggest that the ground states of the new complexes indeed correspond to an innocent AuIII–DPP3−, paralleling a similar description noted for Au corroles. Interestingly, while DFT calculations indicate purely ligand-centered oxidations, reduction of AuDPP is predicted to occur across both the metal and the ligand.

Graphical abstract: Gold dipyrrin-bisphenolates: a combined experimental and DFT study of metal–ligand interactions
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