The influence of the counteranion on the structure and the spin-transition properties of original 1D bis(tetrazole) Fe(II) systems, namely [Fe(btzx)(3)]X(2) (X=PF(6) (-) (1), CF(3)SO(3) (-) (2) and ClO(4) (-) (3); btzx=m-xylylenebis(tetrazole)) is studied. The X-ray crystal structures of compounds 1 and 2 are described in detail. These structures present a solvent molecule encapsulated within pockets formed by btzx ligands along the 1D coordination chains. Compound 2 is shown to be the first structurally characterised alternating HS-LS 1D spin-transition system (HS=high spin, LS=low spin). The magnetic susceptibility measurements of all three compounds are compared. The degree of completion and the transition temperature are both drastically influenced by the counterion used, while surprisingly, the cooperative nature of the transition is not affected by the choice of counterion. Compounds 1 and 2 are further studied by Mössbauer spectroscopy and their distinct LIESST properties are compared.
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http://dx.doi.org/10.1002/chem.200800990 | DOI Listing |
Dalton Trans
December 2024
Xi'an Rare Metal Materials Institute Co., Ltd, Xi'an 710016, P. R. China.
Spin-crossover (SCO) at room temperature is a pivotal goal within the field of molecular magnetism. Herein, we attempt to assemble Fe SCO complexes using a substituted Hqsal ligand, HL (-(8-quinolyl)-2,3-dihydroxybenzaldimine). Two complexes [Fe(HL)]·X·2MeCN (X = BF for 1 and X = ClO for 2) were obtained and characterized.
View Article and Find Full Text PDFChem Sci
December 2024
Department of Chemistry, Indian Institute of Science Education and Research Bhopal Elements Building, Bhauri, Bhopal By-pass Road Madhya Pradesh 462066 India
Angew Chem Int Ed Engl
November 2024
Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055, P. R. China.
Dynamic molecules with tunable chemical and physical properties in response to external stimuli hold great potential for applications in various fields such as information storage, smart molecular machines, and biomimetics. Among them, supramolecular springs and spin-crossover (SCO) complexes can both undergo visible macroscopic changes under heat or light stimulation. In this study, we synthesized a unique trinuclear Fe(II)-SCO complex, [(R-L)Fe{Au(CN)}] (R 1), using a chiral chelating ligand decorated with rotatable benzyl rings.
View Article and Find Full Text PDFSmall
November 2024
Departamento de Química Física, Universidad de Sevilla, c/ Prof. García González, s/n, Sevilla, 41012, Spain.
Dalton Trans
October 2024
LCC, CNRS and Université de Toulouse (UPS, INP), 205 Route de Narbonne, F-31077 Toulouse, France.
In this paper, we report the synthesis of six novel triazole-based heteroscorpionate ligands based on heterocycle metathesis reactions and their iron(II) complexes. Single crystal structure analyses were performed, the spectroscopic and magnetic properties of the obtained complexes were studied and their spin crossover-structural relationships were compared to those obtained for their pyrazole-based analogues reported in the literature. In particular, the amino derivative complex bis[hydrobis(pyrazol-1-yl)(3-amino-1,2,4-triazol-1-yl)]iron(II) obtained by post-synthetic catalytic nitro-group reduction under pressure of hydrogen in an autoclave presents a scarce gradual spin crossover behavior at room temperature.
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