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Cold Crystallization in Schiff-Base Nickel(II) Complexes Derived from Three Toluidine Isomers

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Department of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan
DENSO CORPORATION, 500-1 Minamiyama, Komenoki-cho, Nisshin, Aichi 470-0111, Japan
§ Institute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 153-8505, Japan
Cite this: J. Phys. Chem. C 2014, 118, 48, 27664–27671
Publication Date (Web):November 13, 2014
https://doi.org/10.1021/jp5081516
Copyright © 2014 American Chemical Society
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Abstract

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To test metal complexes as potential compounds for heat-storage materials, two Schiff-base Ni(II) complexes derived from two differently N-substituted toluidine isomers were examined. Comparing the behavior with that of a similar complex previously reported, it was found that the cold crystallization was realized in polymorphic complexes. The activation energy for crystallization estimated by using differential scanning calorimetry was well correlated to the ease of supercooling necessary for the cold crystallization. DFT calculations of molecular energy suggested that the cold crystallization phenomenon is closely related to a molecular flexibility that prevents normal crystallization during cooling. The molecular flexibility controls the ease in the supercooling of liquid and the nucleation–growth process of crystallization by altering the activation energy for crystallization.

Supporting Information

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DSC charts for analyses of phase relation of the ortho complex, those for Kissinger plots of three complexes, atomic coordinates of fully optimized ortho and para molecules in vacuum, and CIF files of crystallographic data. CIF files can be obtained free of charge via http://www.ccdc.cam.ac.uk/data_request/cif, by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax +44 1223 336033. The deposition numbers of the studied complexes, Oa, Ob, Od, Oe, and P are CCDC 1001697, 1001698, 1001699, 1013355, and 1001701, respectively. This material is available free of charge via the Internet at http://pubs.acs.org.

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