Elucidating the Correlation Between the Redox Potential, Spin State, and Crystal Structure in a Series of Ferrous Complexes with Redox‐Active Ligands
Abstract
Abstract Accurately predicting the spin crossover (SCO) temperature ( T 1/2 ) in spin crossover compounds remains a significant challenge due to their extreme sensitivity to minor variations in ligand and crystal structure. In this study, we uncover a critical link between the redox potential of ligands and SCO behavior within Hofmann‐type clathrates {Fe(R‐pbpy⁺)₂[μ₂‐M(CN)₄]₂} (R = electron‐donating or electron‐withdrawing groups, M = Pd or Pt). Through precise tuning of the ligands' electronic properties, we establish a correlation between redox potential, space group, and SCO temperature, explained by an adaptation of Marcus theory of electron transfer. These findings not only provide a deeper understanding of the factors governing SCO behavior but also present a promising strategy for the rational design of SCO materials with tailored properties.
Article Details
Authors (10)
Livia Getzner
LCC, CNRS and Université de Toulouse, UPS, INP
Yasmine Remili
LCC, CNRS and Université de Toulouse, UPS, INP
Zakaria Ziani
LCC: Laboratoire de Chimie de Coordination CNRS France
Laure Vendier
LCC, CNRS and Université de Toulouse, UPS, INP
William Nicolazzi
LCC: Laboratoire de Chimie de Coordination CNRS France
Aurelian Rotaru
Department of Electrical Engineering and Computer Science and MANSiD Research Center, “Stefan Cel Mare” University, University Street, 13, Suceava 720229, Romania
Haizhu Yu
Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Institutes of Physical Science and Information Technology and Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Anhui University 1 , Hefei, Anhui 230601,
Gábor Molnár
LCC, CNRS and Université de Toulouse, UPS, INP
Saioa Cobo
LCC, CNRS and Université de Toulouse, UPS, INP
Azzedine Bousseksou
LCC, CNRS and Université de Toulouse, UPS, INP