Automated prediction of ground state spin for transition metal complexes†

Abstract

Exploiting crystallographic data repositories for large-scale quantum chemical computations requires the rapid and accurate extraction of the molecular structure, charge and spin from the crystallographic information file. Here, we develop a general approach to assign the ground state spin of transition metal complexes, in complement to our previous efforts on determining metal oxidation states and bond order within the cell2mol software. Starting from a database of 31k transition metal complexes extracted from the Cambridge Structural Database with cell2mol, we construct the TM-GSspin dataset, which contains 2063 mononuclear first row transition metal complexes and their computed ground state spins. TM-GSspin is highly diverse in terms of metals, metal oxidation states, coordination geometries, and coordination sphere compositions. Based on TM-GSspin, we identify correlations between structural and electronic features of the complexes and their ground state spins to develop a rule-based spin state assignment model. Leveraging this knowledge, we construct interpretable descriptors and build a statistical model achieving 98% cross-validated accuracy in predicting the ground state spin across the board. Our approach provides a practical way to determine the ground state spin of transition metal complexes directly from crystal structures without additional computations, thus enabling the automated use of crystallographic data for large-scale computations involving transition metal complexes.