Running in the family: molecular factors controlling spin crossover of iron(II) complexes with schiff-base like ligands

  • Tailoring of spin state energetics of transition metal complexes and even the correct prediction of the resulting spin state is still a challenging task, both for the experimentalist and the theoretician. Apart from the complexity in the solid state imposed by packing effects, molecular factors of the spin state ordering are required to be identified and quantified on equal rights. In this work we experimentally record the spin states and SCO energies within an eight-member substitution-series of N4O2 ligated iron(II) complexes both in the solid state (SQUID magnetometry and single-crystal X-ray crystallography) and in solution (VT-NMR). The experimental survey is complemented by exhaustive theoretical modelling of the molecular and electronic structure of the open-chain N4O2 family and its macrocyclic N6 congeners through density-functional theory methods. Ligand topology is identified as the leading factor defining ground-state multiplicity of the corresponding iron(II) complexes. Invariably the low-spin state is sterically trapped in the macrocycles, whereas subtle substitution effects allow for a molecular fine tuning of the spin state in the open-chain ligands. Factorization of computed relative SCO energies holds promise for directed design of future SCO systems.

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Author:Sophie Schönfeld, Wolfgang Bauer, Sebastian ThallmairORCiD, Gerald Hörner, Birgit Weber
Parent Title (English):Zeitschrift für anorganische und allgemeine Chemie : ZAAC = Journal of inorganic and general chemistry
Place of publication:Weinheim
Document Type:Article
Date of Publication (online):2020/12/03
Date of first Publication:2020/12/03
Publishing Institution:Universitätsbibliothek Johann Christian Senckenberg
Release Date:2021/07/26
Tag:density functional theory; iron; schiff base; spin crossover
Page Number:10
First Page:905
Last Page:914
Institutes:Wissenschaftliche Zentren und koordinierte Programme / Frankfurt Institute for Advanced Studies (FIAS)
Dewey Decimal Classification:5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften
Licence (German):License LogoCreative Commons - Namensnennung 4.0