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This occurs through a sequence of phase changes, which were monitored by powder diffraction in an earlier study. [Cu<jats:italic>L<\/jats:italic><jats:sub>2<\/jats:sub>][BF<jats:sub>4<\/jats:sub>]<jats:sub>2<\/jats:sub><jats:bold>\u22c5<\/jats:bold>2\u2009H<jats:sub>2<\/jats:sub>O and [Zn<jats:italic>L<\/jats:italic><jats:sub>2<\/jats:sub>][BF<jats:sub>4<\/jats:sub>]<jats:sub>2<\/jats:sub><jats:bold>\u22c5<\/jats:bold>2\u2009H<jats:sub>2<\/jats:sub>O are not perfectly isostructural but, unlike the iron compound, they undergo single\u2010crystal\u2010to\u2010single\u2010crystal dehydration upon annealing. All the annealed compounds initially adopt the same tetragonal phase but undergo a phase change near room temperature upon re\u2010cooling. The low\u2010temperature phase of [Cu<jats:italic>L<\/jats:italic><jats:sub>2<\/jats:sub>][BF<jats:sub>4<\/jats:sub>]<jats:sub>2<\/jats:sub> involves ordering of its Jahn\u2013Teller distortion, to a monoclinic lattice with three unique cation sites. The zinc compound adopts a different, triclinic low\u2010temperature phase with significant twisting of its coordination sphere, which unexpectedly becomes more pronounced as the crystal is cooled. Synchrotron powder diffraction data confirm that the structural changes in the anhydrous zinc complex are reproduced in the high\u2010spin iron compound, before the onset of spin\u2010crossover. This will contribute to the wide hysteresis in the spin transition of the iron complex. EPR spectra of copper\u2010doped [Fe<jats:sub>0.97<\/jats:sub>Cu<jats:sub>0.03<\/jats:sub><jats:italic>L<\/jats:italic><jats:sub>2<\/jats:sub>][BF<jats:sub>4<\/jats:sub>]<jats:sub>2<\/jats:sub> imply its low\u2010spin phase contains two distinct cation environments in a 2:1 ratio.<\/jats:p>","DOI":"10.1002\/chem.202000101","type":"journal-article","created":{"date-parts":[[2020,2,4]],"date-time":"2020-02-04T06:12:41Z","timestamp":1580796761000},"page":"4833-4841","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":14,"title":["Elucidating the Structural Chemistry of a Hysteretic Iron(II) Spin\u2010Crossover Compound From its Copper(II) and Zinc(II) Congeners"],"prefix":"10.1002","volume":"26","author":[{"given":"Christopher M.","family":"Pask","sequence":"first","affiliation":[{"name":"School of Chemistry University of Leeds  Woodhouse Lane Leeds LS2 9JT UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sam","family":"Greatorex","sequence":"additional","affiliation":[{"name":"School of Chemistry University of Leeds  Woodhouse Lane Leeds LS2 9JT UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rafal","family":"Kulmaczewski","sequence":"additional","affiliation":[{"name":"School of Chemistry University of Leeds  Woodhouse Lane Leeds LS2 9JT UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Amgalanbaatar","family":"Baldansuren","sequence":"additional","affiliation":[{"name":"School of Chemistry and Photon Science Institute University of Manchester  Oxford Road Manchester M13 9PL UK"},{"name":"current address: Chemistry and Chemical Biology, 120 Cogswell Rensselaer Polytechnic Institute  110 Eighth Street Troy NY 12180 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Eric J. 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