Controlling Spin Switching with Anionic Supramolecular Frameworks

  • Michael C. Pfrunder
    Michael C. Pfrunder
    School of Chemistry and Physics, Queensland University of Technology (QUT), 2 George Street, Brisbane, Queensland 4000, Australia
    Centre for Materials Science, Queensland University of Technology (QUT), 2 George Street, Brisbane, Queensland 4000, Australia
  • Jacob J. Whittaker
    Jacob J. Whittaker
    School of School of Chemistry and Molecular Biosciences, The University of Queensland, St Lucia, Queensland 4072, Australia
  • Simon Parsons
    Simon Parsons
    Centre for Science at Extreme Conditions and EaStCHEM School of Chemistry, The University of Edinburgh, King’s Buildings, West Mains Road, Edinburgh, Scotland EH9 3FD, U.K.
  • Boujemaa Moubaraki
    Boujemaa Moubaraki
    School of Chemistry, Monash University, Clayton, Victoria 3800, Australia
  • Keith S. Murray
    Keith S. Murray
    School of Chemistry, Monash University, Clayton, Victoria 3800, Australia
  • Stephen A. Moggach
    Stephen A. Moggach
    Centre for Science at Extreme Conditions and EaStCHEM School of Chemistry, The University of Edinburgh, King’s Buildings, West Mains Road, Edinburgh, Scotland EH9 3FD, U.K.
  • Neeraj Sharma
    Neeraj Sharma
    School of Chemistry, University of New South Wale, Sydney, New South Wales 2052, Australia
  • Aaron S. Micallef
    Aaron S. Micallef
    Central Analytical Research Facility, Queensland University of Technology (QUT), 2 George Street, Brisbane, Queensland 4000, Australia
    Centre for Materials Science, Queensland University of Technology (QUT), 2 George Street, Brisbane, Queensland 4000, Australia
  • Jack K. Clegg*
    Jack K. Clegg
    School of School of Chemistry and Molecular Biosciences, The University of Queensland, St Lucia, Queensland 4072, Australia
    *E-mail: [email protected] (J.K.C.).
  • , and 
  • John C. McMurtrie*
    John C. McMurtrie
    School of Chemistry and Physics, Queensland University of Technology (QUT), 2 George Street, Brisbane, Queensland 4000, Australia
    Centre for Materials Science, Queensland University of Technology (QUT), 2 George Street, Brisbane, Queensland 4000, Australia
    *E-mail: [email protected] (J.C.M.).
Cite this: Chem. Mater. 2020, 32, 7, 3229–3234
Publication Date (Web):March 4, 2020
https://doi.org/10.1021/acs.chemmater.0c00375
Copyright © 2020 American Chemical Society
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Abstract

Encasing the classic spin-crossover (SCO) complex cation [Co(terpy)2]2+ in different anionic supramolecular frameworks modulates its SCO behavior, tuning both its T1/2 (shift of up to 200 K) and the cooperativity of the system. The SCO behavior is influenced by the organization of the complex cations within supramolecular anionic frameworks comprising iodoperfluorobenzenes and iodide anions, with tighter packing of complexes leading to a more abrupt transition. This approach for the control of magnetic properties is applicable to any complex with suitable counterions and hence provides significant opportunity for further developing the properties of many such stimuli-responsive complexes, without requiring changes to their chemical structures. The magnetic properties of the materials presented herein are investigated through variable-temperature magnetic susceptibility measurements and variable-temperature and -pressure molecular structure studies.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.chemmater.0c00375.

  • Crystallographic information of reported structures (ZIP)

  • Details of synthesis, characterization, and crystallization; experimental details for SCXRD, PXRD, and magnetism measurements; typical “terpy embrace motif”; detailed descriptions of crystal packing and additional crystal structures; SCXRD refinement details; summary of halogen bond lengths and their normalized contacts for reported structures; detailed analysis of magnetic results including usage of SHAPE 2.1; comparison of coordination geometries with magnetic data; and histogram displaying results of the survey of the Cambridge Structural Database (PDF)

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This article is cited by 12 publications.

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  2. Andrés Reyes Zuluaga, Aidan J. Brock, Michael C. Pfrunder, Wasinee Phonsri, Keith S. Murray, Phimphaka Harding, Aaron S. Micallef, Kathleen M. Mullen, Jack K. Clegg, David J. Harding, John C. McMurtrie. Three-Way Switchable Single-Crystal-to-Single-Crystal Solvatomorphic Spin Crossover in a Molecular Cocrystal. Chemistry of Materials 2020, 32 (23) , 10076-10083. https://doi.org/10.1021/acs.chemmater.0c03396
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