Three-Way Switchable Single-Crystal-to-Single-Crystal Solvatomorphic Spin Crossover in a Molecular Cocrystal

The Fe­(III) spin-switching complexes [Fe­(qsal-5-Y)2]­X (where Y = F, Cl, Br, I or OMe; X = NCS–, Cl–, OTf–, NO3 –, BF4 –, PF6 –, or BPh4 –) display a variety of thermal spin transition profiles, including abrupt, stepped, and hysteretic, with potential applications as temperature- or gas-dependent...

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Published in:Chemistry of materials 2020-12, Vol.32 (23), p.10076-10083
Main Authors: Zuluaga, Andrés Reyes, Brock, Aidan J, Pfrunder, Michael C, Phonsri, Wasinee, Murray, Keith S, Harding, Phimphaka, Micallef, Aaron S, Mullen, Kathleen M, Clegg, Jack K, Harding, David J, McMurtrie, John C
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container_end_page 10083
container_issue 23
container_start_page 10076
container_title Chemistry of materials
container_volume 32
creator Zuluaga, Andrés Reyes
Brock, Aidan J
Pfrunder, Michael C
Phonsri, Wasinee
Murray, Keith S
Harding, Phimphaka
Micallef, Aaron S
Mullen, Kathleen M
Clegg, Jack K
Harding, David J
McMurtrie, John C
description The Fe­(III) spin-switching complexes [Fe­(qsal-5-Y)2]­X (where Y = F, Cl, Br, I or OMe; X = NCS–, Cl–, OTf–, NO3 –, BF4 –, PF6 –, or BPh4 –) display a variety of thermal spin transition profiles, including abrupt, stepped, and hysteretic, with potential applications as temperature- or gas-dependent switches or memory/storage devices. Here, the complex [Fe­(qsal-OMe)2]­NCS is encased within discrete anionic supramolecular motifs in cocrystalline [Fe­(qsal-OMe)2]­[(1,3,5-triiodotrifluorobenzene)­(NCS)]·MeOH/H2O (1·IFB·solvent). The MeOH and H2O solvate within these robust crystals can be reversibly exchanged, giving an artificial triple hysteresis, with six different stable magnetic states and a ΔT 1/2 of 95 K (MeOH versus H2O solvatomorphs), which represent the workings of a stimulated logic gate that can be reset with heat or vacuum. Variable-temperature single-crystal X-ray diffraction (VT-SCXRD) elucidated the entire spin transition profile of the parent complex [Fe­(qsal-OMe)2]­(NCS)·MeCN (1·MeCN) and the anionic supramolecular framework-like adducts [Fe­(qsal-OMe)2]­[(1,3,5-triiodotrifluorobenzene)­(NCS)] (1·IFB), [Fe­(qsal-OMe)2]­[(1,3,5-triiodotrifluorobenzene)­(NCS)]·MeOH (1·IFB·MeOH) and [Fe­(qsal-OMe)2]­[(1,3,5-triiodotrifluorobenzene)­(NCS)]·H2O (1·IFB·H 2 O), with full structures collected every 5 or 10 K (total of 202 individual structures) over a temperature range of 100–450 K. The reversible solvent exchange and magnetic changes suggest that crystalline 1·IFB may be used as a specialized molecular magnetic sensor for MeOH and H2O.
doi_str_mv 10.1021/acs.chemmater.0c03396
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Here, the complex [Fe­(qsal-OMe)2]­NCS is encased within discrete anionic supramolecular motifs in cocrystalline [Fe­(qsal-OMe)2]­[(1,3,5-triiodotrifluorobenzene)­(NCS)]·MeOH/H2O (1·IFB·solvent). The MeOH and H2O solvate within these robust crystals can be reversibly exchanged, giving an artificial triple hysteresis, with six different stable magnetic states and a ΔT 1/2 of 95 K (MeOH versus H2O solvatomorphs), which represent the workings of a stimulated logic gate that can be reset with heat or vacuum. Variable-temperature single-crystal X-ray diffraction (VT-SCXRD) elucidated the entire spin transition profile of the parent complex [Fe­(qsal-OMe)2]­(NCS)·MeCN (1·MeCN) and the anionic supramolecular framework-like adducts [Fe­(qsal-OMe)2]­[(1,3,5-triiodotrifluorobenzene)­(NCS)] (1·IFB), [Fe­(qsal-OMe)2]­[(1,3,5-triiodotrifluorobenzene)­(NCS)]·MeOH (1·IFB·MeOH) and [Fe­(qsal-OMe)2]­[(1,3,5-triiodotrifluorobenzene)­(NCS)]·H2O (1·IFB·H 2 O), with full structures collected every 5 or 10 K (total of 202 individual structures) over a temperature range of 100–450 K. The reversible solvent exchange and magnetic changes suggest that crystalline 1·IFB may be used as a specialized molecular magnetic sensor for MeOH and H2O.</description><identifier>ISSN: 0897-4756</identifier><identifier>EISSN: 1520-5002</identifier><identifier>DOI: 10.1021/acs.chemmater.0c03396</identifier><language>eng</language><publisher>American Chemical Society</publisher><ispartof>Chemistry of materials, 2020-12, Vol.32 (23), p.10076-10083</ispartof><rights>2020 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a361t-d86452fd351ea597437457f8b8372a38150a8b1d725f86eb4b5c3770b266a40e3</citedby><cites>FETCH-LOGICAL-a361t-d86452fd351ea597437457f8b8372a38150a8b1d725f86eb4b5c3770b266a40e3</cites><orcidid>0000-0002-2270-7141 ; 0000-0001-8866-2401 ; 0000-0002-7253-316X ; 0000-0002-7140-5596 ; 0000-0003-4480-0985 ; 0000-0003-3990-8617</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>315,786,790,27957,27958</link.rule.ids></links><search><creatorcontrib>Zuluaga, Andrés Reyes</creatorcontrib><creatorcontrib>Brock, Aidan J</creatorcontrib><creatorcontrib>Pfrunder, Michael C</creatorcontrib><creatorcontrib>Phonsri, Wasinee</creatorcontrib><creatorcontrib>Murray, Keith S</creatorcontrib><creatorcontrib>Harding, Phimphaka</creatorcontrib><creatorcontrib>Micallef, Aaron S</creatorcontrib><creatorcontrib>Mullen, Kathleen M</creatorcontrib><creatorcontrib>Clegg, Jack K</creatorcontrib><creatorcontrib>Harding, David J</creatorcontrib><creatorcontrib>McMurtrie, John C</creatorcontrib><title>Three-Way Switchable Single-Crystal-to-Single-Crystal Solvatomorphic Spin Crossover in a Molecular Cocrystal</title><title>Chemistry of materials</title><addtitle>Chem. Mater</addtitle><description>The Fe­(III) spin-switching complexes [Fe­(qsal-5-Y)2]­X (where Y = F, Cl, Br, I or OMe; X = NCS–, Cl–, OTf–, NO3 –, BF4 –, PF6 –, or BPh4 –) display a variety of thermal spin transition profiles, including abrupt, stepped, and hysteretic, with potential applications as temperature- or gas-dependent switches or memory/storage devices. Here, the complex [Fe­(qsal-OMe)2]­NCS is encased within discrete anionic supramolecular motifs in cocrystalline [Fe­(qsal-OMe)2]­[(1,3,5-triiodotrifluorobenzene)­(NCS)]·MeOH/H2O (1·IFB·solvent). The MeOH and H2O solvate within these robust crystals can be reversibly exchanged, giving an artificial triple hysteresis, with six different stable magnetic states and a ΔT 1/2 of 95 K (MeOH versus H2O solvatomorphs), which represent the workings of a stimulated logic gate that can be reset with heat or vacuum. Variable-temperature single-crystal X-ray diffraction (VT-SCXRD) elucidated the entire spin transition profile of the parent complex [Fe­(qsal-OMe)2]­(NCS)·MeCN (1·MeCN) and the anionic supramolecular framework-like adducts [Fe­(qsal-OMe)2]­[(1,3,5-triiodotrifluorobenzene)­(NCS)] (1·IFB), [Fe­(qsal-OMe)2]­[(1,3,5-triiodotrifluorobenzene)­(NCS)]·MeOH (1·IFB·MeOH) and [Fe­(qsal-OMe)2]­[(1,3,5-triiodotrifluorobenzene)­(NCS)]·H2O (1·IFB·H 2 O), with full structures collected every 5 or 10 K (total of 202 individual structures) over a temperature range of 100–450 K. 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Mater</addtitle><date>2020-12-08</date><risdate>2020</risdate><volume>32</volume><issue>23</issue><spage>10076</spage><epage>10083</epage><pages>10076-10083</pages><issn>0897-4756</issn><eissn>1520-5002</eissn><abstract>The Fe­(III) spin-switching complexes [Fe­(qsal-5-Y)2]­X (where Y = F, Cl, Br, I or OMe; X = NCS–, Cl–, OTf–, NO3 –, BF4 –, PF6 –, or BPh4 –) display a variety of thermal spin transition profiles, including abrupt, stepped, and hysteretic, with potential applications as temperature- or gas-dependent switches or memory/storage devices. Here, the complex [Fe­(qsal-OMe)2]­NCS is encased within discrete anionic supramolecular motifs in cocrystalline [Fe­(qsal-OMe)2]­[(1,3,5-triiodotrifluorobenzene)­(NCS)]·MeOH/H2O (1·IFB·solvent). The MeOH and H2O solvate within these robust crystals can be reversibly exchanged, giving an artificial triple hysteresis, with six different stable magnetic states and a ΔT 1/2 of 95 K (MeOH versus H2O solvatomorphs), which represent the workings of a stimulated logic gate that can be reset with heat or vacuum. Variable-temperature single-crystal X-ray diffraction (VT-SCXRD) elucidated the entire spin transition profile of the parent complex [Fe­(qsal-OMe)2]­(NCS)·MeCN (1·MeCN) and the anionic supramolecular framework-like adducts [Fe­(qsal-OMe)2]­[(1,3,5-triiodotrifluorobenzene)­(NCS)] (1·IFB), [Fe­(qsal-OMe)2]­[(1,3,5-triiodotrifluorobenzene)­(NCS)]·MeOH (1·IFB·MeOH) and [Fe­(qsal-OMe)2]­[(1,3,5-triiodotrifluorobenzene)­(NCS)]·H2O (1·IFB·H 2 O), with full structures collected every 5 or 10 K (total of 202 individual structures) over a temperature range of 100–450 K. The reversible solvent exchange and magnetic changes suggest that crystalline 1·IFB may be used as a specialized molecular magnetic sensor for MeOH and H2O.</abstract><pub>American Chemical Society</pub><doi>10.1021/acs.chemmater.0c03396</doi><tpages>8</tpages><orcidid>https://orcid.org/0000-0002-2270-7141</orcidid><orcidid>https://orcid.org/0000-0001-8866-2401</orcidid><orcidid>https://orcid.org/0000-0002-7253-316X</orcidid><orcidid>https://orcid.org/0000-0002-7140-5596</orcidid><orcidid>https://orcid.org/0000-0003-4480-0985</orcidid><orcidid>https://orcid.org/0000-0003-3990-8617</orcidid></addata></record>
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title Three-Way Switchable Single-Crystal-to-Single-Crystal Solvatomorphic Spin Crossover in a Molecular Cocrystal
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