Pyridyl-thioethers as capping ligands for the design of heteroleptic Fe(II) complexes with spin-crossover behavior


Üngör Ö. Igimbayeva D. Dragulescu-Andrasi A. Yergeshbayeva S. Delgado T. Greer S.M. Donalson G. Jo M. Erkasov R. Shatruk M.
October 2021MDPI

Magnetochemistry
2021#7Issue 10

Mononuclear heteroleptic complexes [Fe(tpma)(bimz)](ClO4)2 (1a), [Fe(tpma)(bimz)](BF4)2 (1b), [Fe(bpte)(bimz)](ClO4)2 (2a), and [Fe(bpte)(bimz)](BF4)2 (2b) (tpma = tris(2-pyridylme-thyl)amine, bpte = S,S′-bis(2-pyridylmethyl)-1,2-thioethane, bimz = 2,2′-biimidazoline) were pre-pared by reacting the corresponding Fe(II) salts with stoichiometric amounts of the ligands. All complexes exhibit temperature-induced spin crossover (SCO), but the SCO temperature is substan-tially lower for complexes 1a and 1b as compared to 2a and 2b, indicating the stronger ligand field afforded by the N2S2-coordinating bpte ligand relative to the N4-coordinating tpma. Our findings suggest that ligands with mixed N/S coordination can be employed to discover new SCO complexes and to tune the transition temperature of known SCO compounds by substituting for purely N-coordinating ligands.

Heteroleptic complexes , Mössbauer spectroscopy , Spin crossover , Thioether ligands

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Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way, Tallahassee, 32306, FL, United States
Department of Chemistry, L.N. Gumilyov Eurasian National University, 5 Munaitpasov Str, Astana, 010008, Kazakhstan
Department of Chemistry, University of Idaho, Moscow, 83844, ID, United States
Départment de Chimie Physique, Université de Genève, Quai Ernest Ansermet, 30, Genève, 1211, Switzerland
National High Magnetic Field Laboratory, 1800 E Paul Dirac Dr, Tallahassee, 32310, FL, United States
Department of Physical & Environmental Sciences, Colorado Mesa University, 1100 North Ave, Grand Junction, 81501, CO, United States

Department of Chemistry and Biochemistry
Department of Chemistry
Department of Chemistry
Départment de Chimie Physique
National High Magnetic Field Laboratory
Department of Physical & Environmental Sciences

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