Metal bis(dithiolene) complexes with one dimensional structure: synthesis and application

Abstract

Metal bis(dithiolene) complexes have attracted considerable attention since their discovery, owing to their characteristic two-step redox behavior, square-planar coordination geometry, and strong metal–ligand dπ–pπ conjugation, which together endow them with remarkable physical and chemical properties. While early investigations focused on their fundamental coordination chemistry, recent efforts have shifted toward leveraging these complexes in functional organic materials, particularly in optoelectronics and thermoelectrics. This review begins by detailing the three pivotal stages in crafting one-dimensional metal bis(dithiolene) chains: (1) generation of the active dithiolene ligand, (2) metal–ligand coordination, and (3) oxidation. We offer a comparative analysis of the three principal ligand precursor classes: benzoin/benzil derivatives, 1,3-dithiol-2-one/1,3-dithiole-2-thione derivatives, and thiol/thioether derivatives, highlighting their synthetic considerations. Finally, we discuss the emerging applications of these complexes in organic thermoelectric devices (OTEs) and organic thin-film transistors (OTFTs), underscoring recent breakthroughs and charting future research directions.