Multinuclear metalladithiolenes: focusing on electronic communication in mixed-valent states

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.