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

TL;DR

This study uses high-level ab initio calculations to analyze how electronic and geometric factors influence the biradical character of TTFtt-bridged metal complexes, aiding future design of such materials.

Contribution

It introduces a one-parameter model linking biradical character to TTFtt C-C bond length, enhancing rational design of TTFtt-based biradicals.

Findings

Biradical character correlates with TTFtt C-C bond length.

A one-parameter model describes the biradical character.

Electronic structure insights guide future material design.

Abstract

The synthesis and design of organic biradicals with tunable singlet-triplet gaps has 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 {\em 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.