Lattice solvent- and substituent-dependent spin-crossover in isomeric iron(ii) complexes

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dc.contributor.authorSenthil Kumar, Kuppusamycs
dc.contributor.authorMizuno, Asatocs
dc.contributor.authorKämmerer, Leacs
dc.contributor.authorSalamon, Somacs
dc.contributor.authorHeinrich, Benoîtcs
dc.contributor.authorBailly, Corinnecs
dc.contributor.authorŠalitroš, Ivancs
dc.contributor.authorWende, Heikocs
dc.contributor.authorRuben, Mariocs
dc.coverage.issue26cs
dc.coverage.volume53cs
dc.date.accessioned2025-02-03T14:50:54Z
dc.date.available2025-02-03T14:50:54Z
dc.date.issued2024-07-02cs
dc.description.abstractSpin-state switching in iron(ii) complexes composed of ligands featuring moderate ligand-field strength-for example, 2,6-bi(1H-pyrazol-1-yl)pyridine (BPP)-is dependent on many factors. Herein, we show that spin-state switching in isomeric iron(ii) complexes composed of BPP-based ligands-ethyl 2,6-bis(1H-pyrazol-1-yl)isonicotinate (BPP-COOEt, L1) and (2,6-di(1H-pyrazol-1-yl)pyridin-4-yl)methylacetate (BPP-CH2OCOMe, L2)-is dependent on the nature of the substituent at the BPP skeleton. Bi-stable spin-state switching-with a thermal hysteresis width (Delta T-1/2) of 44 K and switching temperature (T-1/2) = 298 K in the first cycle-is observed for complex 1<middle dot>CH3CN composed of L1 and BF4- counter anions. Conversely, the solvent-free isomeric counterpart of 1<middle dot>CH3CN-complex 2a, composed of L2 and BF4- counter anions-was trapped in the high-spin (HS) state. For one of the polymorphs of complex 2b<middle dot>CH3CN-2b<middle dot>CH3CN-Y, Y denotes yellow colour of the crystals-composed of L2 and ClO4- counter anions, a gradual and non-hysteretic SCO is observed with T-1/2 = 234 K. Complexes 1<middle dot>CH3CN and 2b<middle dot>CH3CN-Y also underwent light-induced spin-state switching at 5 K due to the light-induced excited spin-state trapping (LIESST) effect. Structures of the low-spin (LS) and HS forms of complex 1<middle dot>CH3CN revealed that spin-state switching goes hand-in-hand with pronounced distortion of the trans-N{pyridyl}-Fe-N{pyridyl} angle (phi), whereas such distortion is not observed for 2b<middle dot>CH3CN-Y. This observation points that distortion is one of the factors making the spin-state switching of 1<middle dot>CH3CN hysteretic in the solid state. The observation of bi-stable spin-state switching with T-1/2 centred at room temperature for 1<middle dot>CH3CN indicates that technologically relevant spin-state switching profiles based on mononuclear iron(ii) complexes can be obtained.en
dc.formattextcs
dc.format.extent1-16cs
dc.format.mimetypeapplication/pdfcs
dc.identifier.citationDalton Transactions. 2024, vol. 53, issue 26, p. 1-16.en
dc.identifier.doi10.1039/d4dt00429acs
dc.identifier.issn1477-9234cs
dc.identifier.orcid0000-0003-3856-0399cs
dc.identifier.other189998cs
dc.identifier.researcheridI-4417-2012cs
dc.identifier.urihttps://hdl.handle.net/11012/249997
dc.language.isoencs
dc.publisherRoyal Society of Chemistrycs
dc.relation.ispartofDalton Transactionscs
dc.relation.urihttps://pubs.rsc.org/en/content/articlelanding/2024/dt/d4dt00429acs
dc.rightsCreative Commons Attribution 4.0 Internationalcs
dc.rights.accessopenAccesscs
dc.rights.sherpahttp://www.sherpa.ac.uk/romeo/issn/1477-9234/cs
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/cs
dc.subjectroom-temperature ferroelectricityen
dc.subjectmagnetic bistabilityen
dc.subjecttransitionen
dc.titleLattice solvent- and substituent-dependent spin-crossover in isomeric iron(ii) complexesen
dc.type.driverarticleen
dc.type.statusPeer-revieweden
dc.type.versionpublishedVersionen
sync.item.dbidVAV-189998en
sync.item.dbtypeVAVen
sync.item.insts2025.02.03 15:50:54en
sync.item.modts2025.02.03 10:32:11en
thesis.grantorVysoké učení technické v Brně. Středoevropský technologický institut VUT. Magneto-Optická a THz Spektroskopiecs
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