Resolution of Low-Energy States in Spin-Exchange Transition-Metal Clusters: Case Study of Singlet States in [Fe(III)(4)S(4)] Cubanes

[Image: see text] Polynuclear transition-metal (PNTM) clusters owe their catalytic activity to numerous energetically low-lying spin states and stable oxidation states. The characterization of their electronic structure represents one of the greatest challenges of modern chemistry. We propose a theoretical framework that enables the resolution of targeted electronic states with ease and apply it to two [Fe(III)(4)S(4)] cubanes. Through direct access to their many-body wave functions, we identify important correlation mechanisms and their interplay with the geometrical distortions observed in these clusters, which are core properties in understanding their catalytic activity. The simulated magnetic coupling constants predicted by our strategy allow us to make qualitative connections between spin interactions and geometrical distortions, demonstrating its predictive power. Moreover, despite its simplicity, the strategy provides magnetic coupling constants in good agreement with the available experimental ones. The complexes are intrinsically frustrated anti-ferromagnets, and the obtained spin structures together with the geometrical distortions represent two possible ways to release spin frustration (spin-driven Jahn–Teller distortion). Our paradigm provides a simple, yet rigorous, route to uncover the electronic structure of PNTM clusters and may be applied to a wide variety of such clusters.