Exploring spin states and ligand field splitting in metal complexes: a theoretical analysis of spin–orbital interactions and magnetic properties

Abstract

Metal complexes are pivotal in diverse fields due to their wide array of functionalities, including magnetism, conductivity, and photoresponsiveness. These functionalities are intricately linked to the phenomenon of ligand field splitting, yet controlling the magnitude of this splitting within metal complexes presents a significant challenge. This study aims to address this challenge by developing a novel 2D spectrochemical series, integrating two critical parameters: metal ions and ligands. Employing the DV-Xα molecular orbital method, we directly calculated ligand field splitting width, enabling a detailed assessment of energy splitting trends. Our results reveal that the magnitude of ligand field splitting, encompassing 17 metal types and 29 ligand types, can be precisely controlled. This represents a significant advancement over traditional spectrochemical series, such as those proposed by R. Tsuchida, which predominantly focus on either ligands or metals in isolation. Additionally, our study extends to the calculation of spin states in these metal complexes, contributing valuable insights for the development of magnetic materials. We demonstrate that the relative ligand field splitting and spin polarization can be used to predict spin states, offering a new perspective in material design and functionality. These findings not only enhance our understanding of ligand field splitting in metal complexes but also provide a comprehensive framework for predicting their electronic and magnetic properties, paving the way for innovative applications in material science and coordination chemistry.