Interplay of Electronic and Geometric Structure Tunes Organic Biradical Character in Bimetallic Tetrathiafulvalene Tetrathiolate Complexes

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2022-06, Vol.126 (21), p.3329-3337
• Main Authors: Boyn, Jan-Niklas, McNamara, Lauren E., Anderson, John S., Mazziotti, David A.
• Format: Article
• Language: English
• Subjects: A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters; Bimetals; Energy; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ligands; Mathematical methods; Metals
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.2c01773

The synthesis and design of organic biradicals with tunable singlet–triplet gaps have become the subject of significant research interest, owing to their possible photochemical applications and use in the development of molecular switches and conductors. Recently, tetrathiafulvalene tetrathiolate (TTFtt) has been demonstrated to exhibit such organic biradical character in doubly ionized bimetallic complexes. In this article we use high-level ab initio calculations to interrogate the electronic structure of a series of TTFtt-bridged metal complexes, resolving the factors governing their biradical character and singlet–triplet gaps. We show that the degree of biradical character correlates with a readily measured experimental predictor, the central TTFtt C–C bond length, and that it may be described by a one-parameter model, providing valuable insight for the future rational design of TTFtt based biradical compounds and materials.