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Drastic Effect of Lattice Propionitrile Molecules on the Spin-Transition Temperature of a 2,2′-Dipyridylamino/s-triazine-Based Iron(II) Complex

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    Drastic Effect of Lattice Propionitrile Molecules on the Spin-Transition Temperature of a 2,2′-Dipyridylamino/s-triazine-Based Iron(II) Complex
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    † Departament de Química Inorgànica, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Spain
    ‡ Materials Chemistry Research Unit, Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Khon Kaen University, Khon Kaen 40002, Thailand
    § Faculty of Sciences, Department of Chemistry, Arak University, Arak 38156-8-8349, Iran
    ∥ Dipartimento di Scienza e Alta Tecnologia and To.Sca.Lab, Università dell’Insubria, Via Valleggio 11, 22100 Como, Italy
    ⊥ Instituto de Ciencia de Materiales de Aragón (ICMA), CSIC and Universidad de Zaragoza, Plaza San Francisco s/n, 50009 Zaragoza, Spain
    # Advanced Light Source (ALS), Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States
    ∇ Institució Catalana de Recerca i Estudis Avançats (ICREA), Passeig Lluís Companys 23, 08010 Barcelona, Spain
    *(N.M.) E-mail: [email protected]
    *(O.R.) E-mail: [email protected]
    *(P.G.) E-mail: [email protected]
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2014, 53, 18, 9827–9836
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    https://doi.org/10.1021/ic501389s
    Published August 26, 2014
    Copyright © 2014 American Chemical Society
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    Abstract

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    Reaction of iron(II) selenocyanate (obtained from Fe(ClO4)2 and KNCSe) with 2-(N,N-bis(2-pyridyl)amino)-4,6-bis(pentafluorophenoxy)-(1,3,5)triazine (L1F) in propionitrile produces the compound [Fe(L1F)2(NCSe)2]·2CH3CH2CN (1NCSe·2PrCN), which shows spin-crossover (SCO) properties characterized by a T1/2 of 283 K and a ΔT80 (i.e., temperature range within which 80% of the transition considered occurs) of about 65 K. Upon air exposure, 1NCSe·2PrCN gradually converts to a new SCO species that exhibits different properties, as reflected by T1/2 = 220 K and ΔT80 = 70 K. Various characterization techniques, namely, IR spectroscopy, thermogravimetric analysis, and thermodiffractometric studies, reveal that the new phase is obtained through the loss of the lattice propionitrile molecules within several days upon air exposure or several hours upon heating above 390 K.

    Copyright © 2014 American Chemical Society

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    Supporting Information

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    Crystallographic data for 1NCSe·2PrCN at different temperatures with the corresponding coordination bond distances and angles, DSC traces for fresh and aged 1NCSe·2PrCN, χT vs T plots, TGA of fresh 1NCSe·2PrCN, IR spectra of 1NCSe·2PrCN and 1NCSe, XRPD data for 1NCSe, and crystal packing views of 1NCSe·2PrCN showing the location of the lattice solvent molecules. This material is available free of charge via the Internet at http://pubs.acs.org.

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    This article is cited by 14 publications.

    1. Izar Capel Berdiell, Rafal Kulmaczewski, and Malcolm A. Halcrow . Iron(II) Complexes of 2,4-Dipyrazolyl-1,3,5-triazine Derivatives—The Influence of Ligand Geometry on Metal Ion Spin State. Inorganic Chemistry 2017, 56 (15) , 8817-8828. https://doi.org/10.1021/acs.inorgchem.7b00699
    2. Humphrey L. C. Feltham, Chloe Johnson, Anastasia B. S. Elliott, Keith C. Gordon, Martin Albrecht, and Sally Brooker . “Tail” Tuning of Iron(II) Spin Crossover Temperature by 100 K. Inorganic Chemistry 2015, 54 (6) , 2902-2909. https://doi.org/10.1021/ic503040f
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    9. Paulo N. Martinho, Frederico F. Martins, Nuno A. G. Bandeira, Maria José Calhorda. Spin Crossover in 3D Metal Centers Binding Halide-Containing Ligands: Magnetism, Structure and Computational Studies. Sustainability 2020, 12 (6) , 2512. https://doi.org/10.3390/su12062512
    10. Shi Wang, Ya-Juan Li, Fei-Fei Ju, Wu-Tan Xu, Koichi Kagesawa, Yong-Hua Li, Masahiro Yamashita, Wei Huang. The molecular and supramolecular aspects in mononuclear manganese( iii ) Schiff-base spin crossover complexes. Dalton Transactions 2017, 46 (33) , 11063-11077. https://doi.org/10.1039/C7DT01718A
    11. Laurence J. Kershaw Cook, Rafal Kulmaczewski, Oscar Cespedes, Malcolm A. Halcrow. Different Spin‐State Behaviors in Isostructural Solvates of a Molecular Iron(II) Complex. Chemistry – A European Journal 2016, 22 (5) , 1789-1799. https://doi.org/10.1002/chem.201503989
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    14. Ivan Nemec, Radovan Herchel, Zdeněk Trávníček. The relationship between the strength of hydrogen bonding and spin crossover behaviour in a series of iron( iii ) Schiff base complexes. Dalton Transactions 2015, 44 (10) , 4474-4484. https://doi.org/10.1039/C4DT03400G
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2014, 53, 18, 9827–9836
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ic501389s
    Published August 26, 2014
    Copyright © 2014 American Chemical Society
    Request reuse permissions

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