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Department of Chemistry, Graduate School of Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
; Fax: +81-3-5841-4489
; Tel: +81-3-5841-4348
Dalton Trans., 2012,41, 10123-10135
11 Apr 2012,
23 May 2012
First published online
13 Jun 2012
This Perspective addresses our recent studies relating to metalladithiolenes and their cluster complexes that exhibit peculiar electronic communication in mixed-valent (MV) states. Chapter 1 provides an introduction for the Perspective. Chapter 2 enumerates a series of phenylene-annulated π-conjugated trinuclear metalladithiolenes with intense electronic communication in the MV states. Chapter 3 treats heterometal cluster complexes synthesized by integrating zero-valent metal carbonyls on mononuclear metalladithiolenes, taking advantage of the coordination unsaturation of the latter. In the field of MV chemistry, their electronic communication through metal–metal bonds and potential inversion behavior are intriguing properties. Chapter 4 describes hexanuclear and nonanuclear heterometal cluster complexes created in combination with the methods introduced in Chapters 2 and 3. The resultant heterometal cluster complexes feature electronic communication through the vast phenylene-annulated π-conjugated trinuclear metalladithiolene frameworks, the intensity of which correlates with their planarity. Each chapter describes the synthesis, structural features, and electrochemical properties of the relevant compounds.
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