Guest removal and external pressure variation induce spin crossover in halogen-functionalized 2-D Hofmann frameworks

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dc.contributor.authorBrennan, ATen_AU
dc.contributor.authorZenere, KAen_AU
dc.contributor.authorBrand, HEAen_AU
dc.contributor.authorPrice, JRen_AU
dc.contributor.authorBhadbhade, MMen_AU
dc.contributor.authorTurner, GFen_AU
dc.contributor.authorMoggach, SAen_AU
dc.contributor.authorValverde-Muñoz, FJen_AU
dc.contributor.authorReal, JAen_AU
dc.contributor.authorClegg, JKen_AU
dc.contributor.authorKepert, CJen_AU
dc.contributor.authorNeville, SMen_AU
dc.date.accessioned2021-10-29T03:48:29Zen_AU
dc.date.available2021-10-29T03:48:29Zen_AU
dc.date.issued2020-09-27en_AU
dc.date.statistics2021-10-25en_AU
dc.description.abstractThe effect of halogen functionalization on the spin crossover (SCO) properties of a family of 2-D Hofmann framework materials, [Fe(II)Pd(CN)4(thioX)2]·2H2O (X = Cl and Br; thioCl = (E)-1-(5-chlorothiophen-2-yl)-N-(4H-1,2,4-triazol-4-yl)methanimine) and thioBr = (E)-1-(5-bromothiophen-2-yl)-N-(4H-1,2,4-triazol-4-yl)methanimine)), is reported. Inclusion of both the chloro- and bromo-functionalized ligands into the Hofmann-type frameworks (1Cl·2H2O and 2Br·2H2O) results in a blocking of spin-state transitions due to internal chemical pressure effects derived by the collective steric bulk of the halogen atoms and guest molecules. Cooperative one-step SCO transitions are revealed by either guest removal or the application of external physical pressure. Notably, removal of solvent water reveals a robust framework scaffold with only marginal variation between the solvated and desolvated structures (as investigated by powder and single crystal X-ray diffraction). Yet, one-step complete SCO transitions are revealed in 1Cl and 2Br with a transition temperature shift between the analogues due to various steric, structural, and electronic considerations. SCO can also be induced in the solvated species, 1Cl·2H2O and 2Br·2H2O, with the application of physical pressure, revealing a complete one-step SCO transition above 0.62 GPa (as investigated by magnetic susceptibility and single crystal X-ray diffraction measurements). © 2020 American Chemical Societyen_AU
dc.identifier.citationBrennan, A. T., Zenere, K. A., Brand, H. E. A., Price, J. R., Bhadbhade, M. M., Turner, G. F., Moggach, S. A., Valverde-Muñoz, F. J., Real, J. A., Clegg, J. K., Kepert, C. J. & Neville, S. M. (2020). Guest removal and external pressure variation induce spin crossover in halogen-functionalized 2-D Hofmann frameworks. Inorganic Chemistry, 59(19), 14296-14305. doi:10.1021/acs.inorgchem.0c02092en_AU
dc.identifier.issn0020-1669en_AU
dc.identifier.issue19en_AU
dc.identifier.journaltitleInorganic Chemistryen_AU
dc.identifier.pagination14296-14305en_AU
dc.identifier.urihttps://doi.org/10.1021/acs.inorgchem.0c02092en_AU
dc.identifier.urihttps://apo.ansto.gov.au/dspace/handle/10238/12174en_AU
dc.identifier.volume59en_AU
dc.language.isoenen_AU
dc.publisherAmerican Chemical Societyen_AU
dc.subjectMonocrystalsen_AU
dc.subjectLigandsen_AU
dc.subjectLayersen_AU
dc.subjectCrystal structureen_AU
dc.subjectSolventsen_AU
dc.subjectSpinen_AU
dc.subjectX-ray diffractionen_AU
dc.subjectPressure dependenceen_AU
dc.subjectMagnetic susceptibilityen_AU
dc.titleGuest removal and external pressure variation induce spin crossover in halogen-functionalized 2-D Hofmann frameworksen_AU
dc.typeJournal Articleen_AU
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