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Driving Barocaloric Effects in a Molecular Spin-Crossover Complex at Low Pressures

  • Jinyoung Seo
    Jinyoung Seo
    Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States
    More by Jinyoung Seo
  • Jason D. Braun
    Jason D. Braun
    Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States
  • Vidhya M. Dev
    Vidhya M. Dev
    Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States
  • , and 
  • Jarad A. Mason*
    Jarad A. Mason
    Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States
    *Email: [email protected]
Cite this: J. Am. Chem. Soc. 2022, 144, 14, 6493–6503
Publication Date (Web):March 31, 2022
https://doi.org/10.1021/jacs.2c01315
Copyright © 2022 American Chemical Society

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    Abstract

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    Barocaloric effects─thermal changes in a material induced by applied hydrostatic pressure─offer promise for creating solid-state refrigerants as alternatives to conventional volatile refrigerants. To enable efficient and scalable barocaloric cooling, materials that undergo high-entropy, reversible phase transitions in the solid state in response to a small change in pressure are needed. Here, we report that pressure-induced spin-crossover (SCO) transitions in the molecular iron(II) complex Fe[HB(tz)3]2 (HB(tz)3 = bis[hydrotris(1,2,4-triazol-1-yl)borate]) drive giant and reversible barocaloric effects at easily accessible pressures. Specifically, high-pressure calorimetry and powder X-ray diffraction studies reveal that pressure shifts as low as 10 bar reversibly induce nonzero isothermal entropy changes, and a pressure shift of 150 bar reversibly induces a large isothermal entropy change (>90 J kg–1 K–1) and adiabatic temperature change (>2 K). Moreover, we demonstrate that the thermodynamics of the SCO transition can be fine-tuned through systematic deuteration of the tris(triazolyl)borate ligand. These results provide new insights into pressure-induced SCO transitions and further establish SCO materials as promising barocaloric materials.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.2c01315.

    • Additional experimental details, high-pressure calorimetry data, entropy curves used to evaluate barocaloric effects, PXRD data, single-crystal XRD data, and summary of all the structural and thermodynamic data (PDF)

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    CCDC 21497602149761 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Cited By

    This article is cited by 9 publications.

    1. Jinyoung Seo, Rahil Ukani, Juanjuan Zheng, Jason D. Braun, Sicheng Wang, Faith E. Chen, Hong Ki Kim, Selena Zhang, Catherine Thai, Ryan D. McGillicuddy, Hao Yan, Joost J. Vlassak, Jarad A. Mason. Barocaloric Effects in Dialkylammonium Halide Salts. Journal of the American Chemical Society 2024, 146 (4) , 2736-2747. https://doi.org/10.1021/jacs.3c12402
    2. Ruixin Li, Georgiy Levchenko, Carlos Bartual-Murgui, Hennagii Fylymonov, Wei Xu, Zhaodong Liu, Quanjun Li, Bingbing Liu, Jose Antonio Real. Anomalous Pressure Response of Temperature-Induced Spin Transition and a Pressure-Induced Spin Transition in Two-Dimensional Hofmann Coordination Polymers. Inorganic Chemistry 2024, 63 (2) , 1214-1224. https://doi.org/10.1021/acs.inorgchem.3c03643
    3. Jett T. Janetzki, Maxim G. Chegerev, Gemma K. Gransbury, Robert W. Gable, Jack K. Clegg, Roger J. Mulder, Guy N. L. Jameson, Alyona A. Starikova, Colette Boskovic. Controlling Spin Crossover in a Family of Dinuclear Fe(III) Complexes via the Bis(catecholate) Bridging Ligand. Inorganic Chemistry 2023, 62 (38) , 15719-15735. https://doi.org/10.1021/acs.inorgchem.3c02598
    4. Damian Paliwoda, Laure Vendier, William Nicolazzi, Gábor Molnár, Azzedine Bousseksou. Pressure Tuning of Coupled Structural and Spin State Transitions in the Molecular Complex [Fe(H2B(pz)2)2(phen)]. Inorganic Chemistry 2022, 61 (40) , 15991-16002. https://doi.org/10.1021/acs.inorgchem.2c02286
    5. P. O. Ribeiro, B. P. Alho, E. P. Nobrega, V. S. R. de Sousa, A. M. G. Carvalho, P. J. von Ranke. Theoretical investigation of the barocaloric effect in spin-crossover systems upon first- and second-order phase transition conversion. Journal of Applied Physics 2023, 133 (12) , 125104. https://doi.org/10.1063/5.0142437
    6. Zhao Zhang, Xiaoming Jiang, Takanori Hattori, Xiong Xu, Min Li, Chenyang Yu, Zhe Zhang, Dehong Yu, Richard Mole, Shin-ichiro Yano, Jie Chen, Lunhua He, Chin-Wei Wang, Hui Wang, Bing Li, Zhidong Zhang. A colossal barocaloric effect induced by the creation of a high-pressure phase. Materials Horizons 2023, 10 (3) , 977-982. https://doi.org/10.1039/D2MH00905F
    7. Jieyu Zheng, Larissa K. S. von Krbek, Tanya K. Ronson, Jonathan R. Nitschke. Host Spin‐Crossover Thermodynamics Indicate Guest Fit. Angewandte Chemie 2022, 134 (50) https://doi.org/10.1002/ange.202212634
    8. Jieyu Zheng, Larissa K. S. von Krbek, Tanya K. Ronson, Jonathan R. Nitschke. Host Spin‐Crossover Thermodynamics Indicate Guest Fit. Angewandte Chemie International Edition 2022, 61 (50) https://doi.org/10.1002/anie.202212634
    9. Alejandro Salvatori, Philippe Negrier, Araceli Aznar, María Barrio, Josep Lluís Tamarit, Pol Lloveras. Colossal barocaloric effects in adamantane derivatives for thermal management. APL Materials 2022, 10 (11) , 111117. https://doi.org/10.1063/5.0127667

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