Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

STEP 1:
Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

MENDELEY PAIRING EXPIRED
Your Mendeley pairing has expired. Please reconnect
ACS Publications. Most Trusted. Most Cited. Most Read
Driving Barocaloric Effects in a Molecular Spin-Crossover Complex at Low Pressures

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Am. Chem. Soc. 2022, 144, 14, 6493-6503
    Article

    Driving Barocaloric Effects in a Molecular Spin-Crossover Complex at Low Pressures
    Click to copy article linkArticle link copied!

    • 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
      More by Jason D. Braun
      Orcidhttps://orcid.org/0000-0002-5850-8048
    • Vidhya M. Dev
      Vidhya M. Dev
      Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States
      More by Vidhya M. Dev
    • Jarad A. Mason*
      Jarad A. Mason
      Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States
      *Email: [email protected]
      More by Jarad A. Mason
      Orcidhttps://orcid.org/0000-0003-0328-7775
    Other Access OptionsSupporting Information (1)

    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2022, 144, 14, 6493–6503
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.2c01315
    Published March 31, 2022
    Copyright © 2022 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    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.

    Copyright © 2022 American Chemical Society

    Subjects

    what are subjects

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    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)

    Accession Codes

    CCDC 2149760–2149761 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.

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!

    This article is cited by 12 publications.

    1. Feixiang Long, Yuzhu Song, Fuyang Tian, Zibing Yu, Hao Lu, Chuanrui Huo, Tianyu Li, Minjun Ai, Chaokun Guo, Huaican Chen, Wen Yin, Fengxia Hu, Xianran Xing, Jun Chen. Excellent Barocaloric Effect by Modulating Geometrical Frustrations in Mn3Pt. Journal of the American Chemical Society 2024, 146 (40) , 27460-27467. https://doi.org/10.1021/jacs.4c07342
    2. Lei Yue, Zonglun Li, Linchao Yu, Kunbo Xu, Ran Liu, Chenyi Li, Yanchun Li, Dongliang Yang, Xiaodong Li, Quanjun Li, Bingbing Liu. Radical n–p Conduction Switching and Significant Photoconductivity Enhancement in NbOI2 via Pressure-Modulated Peierls Distortion. Journal of the American Chemical Society 2024, 146 (36) , 25245-25252. https://doi.org/10.1021/jacs.4c09361
    3. Sujit Kamilya, Bijoy Dey, Krishna Kaushik, Swapnil Shukla, Sakshi Mehta, Abhishake Mondal. Realm of Spin State Switching Materials: Toward Realization of Molecular and Nanoscale Devices. Chemistry of Materials 2024, 36 (10) , 4889-4915. https://doi.org/10.1021/acs.chemmater.3c02654
    4. 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
    5. 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
    6. 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
    7. 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
    8. 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
    9. 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
    10. 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
    11. 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
    12. 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
    Download PDF
    Go to Journal of the American Chemical Society
    Get e-Alerts
    Get e-Alerts

    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2022, 144, 14, 6493–6503
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.2c01315
    Published March 31, 2022
    Copyright © 2022 American Chemical Society
    Request reuse permissions

    Article Views

    4773

    Altmetric

    -

    Citations

    12
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.