dc.date.accessioned | 2023-03-10T17:55:07Z | |
dc.date.available | 2023-03-10T17:55:07Z | |
dc.date.created | 2022-12-01T15:11:17Z | |
dc.date.issued | 2022 | |
dc.identifier.citation | Roberts, Thomas D. Pask, Christopher M. Capel Berdiell, Izar Tuna, Floriana Halcrow, Malcolm A. . Exploring the influence of counterions on a hysteretic spin-transition in isomorphous iron(ii) complex salts. Journal of Materials Chemistry C. 2022(43) | |
dc.identifier.uri | http://hdl.handle.net/10852/101229 | |
dc.description.abstract | [FeL2]X2·2H2O (L = 2,6-bis{5-methyl-1H-pyrazol-3-yl}pyridine; X− = BF4− or ClO4−) are readily dehydrated upon mild heating. Anhydrous [FeL2][BF4]2 exhibits an abrupt spin-transition at T1/2 = 205 K, with a 65 K thermal hysteresis loop which narrows upon repeated scanning. The isomorphous ClO4− salt remains high-spin on cooling, however, which is investigated further in this study. Unlike the iron complex, [ZnL2][ClO4]2·2H2O undergoes single-crystal-to-single-crystal dehydration; the tetragonal anhydrous crystals transform to a new triclinic phase upon cooling. The phase change is apparently sluggish and transition temperatures between 268 K and <200 K were measured by different techniques, implying it depends on the measurement conditions or sample history. Powder diffraction shows the zinc complex is a good model for the structural chemistry of [FeL2][ClO4]2. The spin states of mixed-anion salts of the iron complex [FeL2][BF4]z[ClO4]2−z (z = 1.5 and 1.0) are also investigated. Their spin-transitions evolve more slowly on repeated scanning, as z decreases, and efficient thermally induced kinetic trapping is observed below 120 K when z = 1.0. Taken together, these data imply structural rearrangements in the anhydrous materials during thermal cycling occur more slowly in the presence of the larger ClO4− ion. Hence, rather than reflecting any structural differences with the SCO-active BF4− salt, the high-spin nature of [FeL2][ClO4]2 is probably caused by kinetic inhibition of its putative spin-transition. | |
dc.language | EN | |
dc.rights | Attribution 3.0 Unported | |
dc.rights.uri | https://creativecommons.org/licenses/by/3.0/ | |
dc.title | Exploring the influence of counterions on a hysteretic spin-transition in isomorphous iron(ii) complex salts | |
dc.title.alternative | ENEngelskEnglishExploring the influence of counterions on a hysteretic spin-transition in isomorphous iron(ii) complex salts | |
dc.type | Journal article | |
dc.creator.author | Roberts, Thomas D. | |
dc.creator.author | Pask, Christopher M. | |
dc.creator.author | Capel Berdiell, Izar | |
dc.creator.author | Tuna, Floriana | |
dc.creator.author | Halcrow, Malcolm A. | |
cristin.unitcode | 185,15,17,0 | |
cristin.unitname | Senter for materialvitenskap og nanoteknologi | |
cristin.ispublished | true | |
cristin.fulltext | original | |
cristin.qualitycode | 1 | |
dc.identifier.cristin | 2087264 | |
dc.identifier.bibliographiccitation | info:ofi/fmt:kev:mtx:ctx&ctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Journal of Materials Chemistry C&rft.volume=&rft.spage=&rft.date=2022 | |
dc.identifier.jtitle | Journal of Materials Chemistry C | |
dc.identifier.volume | 10 | |
dc.identifier.issue | 43 | |
dc.identifier.startpage | 16353 | |
dc.identifier.endpage | 16362 | |
dc.identifier.pagecount | 0 | |
dc.identifier.doi | https://doi.org/10.1039/d2tc03654a | |
dc.type.document | Tidsskriftartikkel | |
dc.type.peerreviewed | Peer reviewed | |
dc.source.issn | 2050-7526 | |
dc.type.version | PublishedVersion | |
dc.relation.project | NFR/301619 | |