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Thermodynamic Relationship between Structural Isomers of the Thermochromic Compound Bis(N-Isopropyl-5,6-benzosalicylideneiminato)nickel(II)

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Research Center for Molecular Thermodynamics, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, Department of Chemistry, Zhejiang University, Hangzhou 310027, China, Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan, Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan, and Department of Chemistry, Faculty of Science, Kanagawa University, Hiratsuka, Kanagawa 259-1205, Japan
* To whom correspondence should be addressed. E-mail: [email protected]
§Research Center for Molecular Thermodynamics, Osaka University.
¶Zhejiang University.
∥Department of Chemistry, Osaka University.
‡University of Tsukuba.
⊥Kanagawa University.
Cite this: J. Phys. Chem. B 2008, 112, 35, 11039–11048
Publication Date (Web):August 12, 2008
https://doi.org/10.1021/jp802684r
Copyright © 2008 American Chemical Society
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Abstract

A pair of structural isomers was isolated at room temperature for the thermochromic nickel complex bis(N-isopropyl-5,6-benzosalicylideneiminato)nickel(II); one is a diamagnetic green form with square-planar coordination geometry (G phase), and the other is a paramagnetic brown form with a tetrahedral geometry (B phase). However, a question as to which form is thermodynamically stable was left open. To solve this problem, thermal and magnetic properties of this complex were investigated by adiabatic heat capacity calorimetry in the 6−508 K temperature range and magnetic measurements in the 2−400 K region. In addition to the two forms previously reported, two metastable crystal forms (G′ and B′ phases) were found. The stable phase sequence was G phase, B phase, and then liquid upon heating. The supercooled B phase gave rise to a small phase transition with nonmagnetic origin at around 50 K. By rapidly cooling the liquid, a glassy liquid state was realized below ∼290 K. The order of thermodynamic stability at 298.15 K was revealed to be the G, B, G′, and then the B′ phase. The entropy, enthalpy, and Gibbs energy differences between the B and the G phases at 298.15 K were S°(B) − S°(G) = 32.8 J K−1 mol−1, H°(B) − H°(G) = 16.0 kJ mol−1, and G°(B) − G°(G) = 6.25 kJ mol−1, respectively.

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Molar heat capacities of Ni(5,6-benzo-Sal, iso-C3H7)2 determined by the calorimeters A and B are provided as Table S1 and Table S2, respectively. For normal heat capacity curves which separate the excess part due to a phase transition from the observed heat capacity, we adopted a linear function of temperature Cp(normal)/(J K−1 mol−1) = a(T/K) + b. Parameters a and b, together with the extrapolated temperature region, are summarized in Table S3. This material is available free of charge via the Internet at http://pubs.acs.org.

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This article is cited by 13 publications.

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  2. Katsunori Iwase, Yuta Nagano, Isao Yoshikawa, Hirohiko Houjou, Yasuhisa Yamamura, and Kazuya Saito . Cold Crystallization in Schiff-Base Nickel(II) Complexes Derived from Three Toluidine Isomers. The Journal of Physical Chemistry C 2014, 118 (48) , 27664-27671. https://doi.org/10.1021/jp5081516
  3. Michio Sorai, Yasuhiro Nakazawa, Motohiro Nakano, and Yuji Miyazaki . Update 1 of: Calorimetric Investigation of Phase Transitions Occurring in Molecule-Based Magnets. Chemical Reviews 2013, 113 (1) , PR41-PR122. https://doi.org/10.1021/cr300156s
  4. Obaid Ali Qamar, Cong Cong, Huaibo Ma. Solid state mononuclear divalent nickel spin crossover complexes. Dalton Transactions 2020, 49 (47) , 17106-17114. https://doi.org/10.1039/D0DT03421E
  5. Akinori Honda, Takashi Yoshida, Ayumi Shioda, Kuniharu Nomoto, Kazuo Miyamura. Cold Crystallization of Chiral Schiff-Base Nickel(II) Complex Having Alkyl Chains and a Characteristic Methyl Group. Bulletin of the Chemical Society of Japan 2019, 92 (11) , 1853-1858. https://doi.org/10.1246/bcsj.20190166
  6. Ayaka Kimijima, Akinori Honda, Kuniharu Nomoto, Kazuo Miyamura. Cold crystallization in the mixed system of adenine and thymine dodecyl derivatives. CrystEngComm 2019, 21 (20) , 3142-3145. https://doi.org/10.1039/C9CE00407F
  7. Katsunori Iwase, Yasuhiro Toyama, Isao Yoshikawa, Yasuhisa Yamamura, Kazuya Saito, Hirohiko Houjou. Insight into Structural Demand for Cold Crystallization of a Small Molecule. A Case Study for Schiff Base Compounds that Exhibit Prototropic Tautomerization. Bulletin of the Chemical Society of Japan 2018, 91 (4) , 669-677. https://doi.org/10.1246/bcsj.20170386
  8. Seyed Abolghasem Kahani, Fatemeh Abdevali. Mechanochemical synthesis and characterization of a nickel( ii ) complex as a reversible thermochromic nanostructure. RSC Advances 2016, 6 (6) , 5116-5122. https://doi.org/10.1039/C5RA22606F
  9. Katsunori Iwase, Isao Yoshikawa, Hirohiko Houjou, Yasuhisa Yamamura, Kazuya Saito. Structural Isomerization and Cold Crystallization of Bis[1-(2-propyl)iminomethylnaphthalen-2-olato]nickel(II) by Thermal Analysis, X-ray Diffraction, and FT-IR. Bulletin of the Chemical Society of Japan 2015, 88 (7) , 989-995. https://doi.org/10.1246/bcsj.20150071
  10. Suzanne W. Slayden, Joel F. Liebman. The Experimental Thermochemistry of Metal Phenolates. 2014,,, 1-40. https://doi.org/10.1002/9780470682531.pat0601
  11. . PATAI'S Chemistry of Functional Groups. 2009,,https://doi.org/
  12. Katsunori Iwase, Hirohiko Houjou, Yasuhisa Yamamura, Kazuya Saito. Cold Crystallization in Bis[1-(3-methylphenyl)iminomethylnaphthalen-2-olato]nickel(II) Studied by Thermal Analysis and X-ray Diffraction. Chemistry Letters 2013, 42 (9) , 1040-1042. https://doi.org/10.1246/cl.130409
  13. Michio Sorai. Molecular Thermodynamics for Functional Metal-Complexes. Bulletin of Japan Society of Coordination Chemistry 2013, 61 (0) , 17-37. https://doi.org/10.4019/bjscc.61.17

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