Guest-Induced Multistep to Single-Step Spin-Crossover Switching in a 2-D Hofmann-Like Framework with an Amide-Appended Ligand

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dc.contributor.authorAhmed, M.
dc.contributor.authorArachchige, K.S.A.
dc.contributor.authorXie, Z.
dc.contributor.authorPrice, J.R.
dc.contributor.authorCruddas, J.
dc.contributor.authorClegg, J.K.
dc.contributor.authorPowell, B.J.
dc.contributor.authorKepert, C.J.
dc.contributor.authorNeville, S.M.
dc.date.issued2022
dc.description.abstractA detailed study of the two-dimensional (2-D) Hofmann like framework [Fe(furpy)2Pd(CN)4]·nG (furpy: N-(pyridin-4-yl)furan-2- carboxamide, G = H2O,EtOH (A·H2O,Et), and H2O (A·H2O)) is presented, including the structural and spin-crossover (SCO) implications of subtle guest modification. This 2-D framework is characterized by undulating Hofmann layers and an array of interlayer spacing environments --this is a strategic approach that we achieve by the inclusion of a ligand with multiple host−host and host−guest interaction sites. Variable temperature magnetic susceptibility studies reveal an asymmetric multistep SCO for A·H2O,Et and an abrupt single-step SCO for A·H2O with an upshift in transition temperature of ∼75 K. Single-crystal analyses show a primitive orthorhombic symmetry for A·H2O,Et characterized by a unique FeII centers the multistep SCO character is attributed to local ligand orientation. Counterintuitively, A·H2O shows a triclinic symmetry with two inequivalent FeII centers that undergo a cooperative single-step high-spin (HS)-to-low-spin (LS) transition. We conduct detailed structure−function analyses to understand how the guest ethanol influences the delicate balance between framework communication and, therefore, the local structure and spin-state transition mechanism.
dc.description.statementofresponsibilityManan Ahmed, Kasun S. A. Arachchige, Zixi Xie, Jason R. Price, Jace Cruddas, Jack K. Clegg, Benjamin J. Powell, Cameron J. Kepert, and Suzanne M. Neville
dc.identifier.citationInorganic Chemistry, 2022; 61(30):11667-11674
dc.identifier.doi10.1021/acs.inorgchem.2c01253
dc.identifier.issn0020-1669
dc.identifier.issn1520-510X
dc.identifier.urihttps://hdl.handle.net/2440/136283
dc.language.isoen
dc.publisherAmerican Chemical Society (ACS)
dc.relation.granthttp://purl.org/au-research/grants/arc/LE170100144
dc.rights© 2022 American Chemical Society
dc.source.urihttps://doi.org/10.1021/acs.inorgchem.2c01253
dc.titleGuest-Induced Multistep to Single-Step Spin-Crossover Switching in a 2-D Hofmann-Like Framework with an Amide-Appended Ligand
dc.typeJournal article
pubs.publication-statusPublished

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