Tuning spin crossover properties in Hofmann-type framework by guest-adaptive deformation

Tuning spin crossover properties in Hofmann-type framework by guest-adaptive deformation | Authorea try { document.documentElement.classList.add('js'); } catch (e) { } var _gaq = _gaq || []; _gaq.push(['_setAccount', 'G-8VDV14Y67G']); _gaq.push(['_trackPageview']); (function() { var ga = document.createElement('script'); ga.type = 'text/javascript'; ga.async = true; ga.src = ('https:' == document.location.protocol ? 'https://ssl' : 'http://www') + '.google-analytics.com/ga.js'; var s = document.getElementsByTagName('script')[0]; s.parentNode.insertBefore(ga, s); })(); Skip to main content Preprints Collections Wiley Open Research IET Open Research Ecological Society of Japan All Collections About About Authorea FAQs Contact Us Quick Search anywhere Search for preprint articles, keywords, etc. Search Search ADVANCED SEARCH SCROLL Chinese Journal of Chemistry This is a preprint and has not been peer reviewed. Data may be preliminary. 14 January 2025 V1 Latest version Share on Tuning spin crossover properties in Hofmann-type framework by guest-adaptive deformation Authors : Kai-Ping Xie 0009-0002-4582-7792 [email protected] , Hai-Ling Wang , Ze-Yu Ruan , Pei-Yu Liao , Guang Yang , Zi-Cheng Xiao , Yi-Fei Deng , Si-Guo Wu , Yan Shi , and Ming-Liang Tong 0000-0003-4725-0798 Authors Info & Affiliations https://doi.org/10.22541/au.173682006.64773251/v1 Published Chinese Journal of Chemistry Version of record Peer review timeline 439 views 229 downloads Contents Abstract Supplementary Material Information & Authors Metrics & Citations View Options References Figures Tables Media Share Abstract Three three-dimensional Hofmann-type metal-organic frameworks (MOFs) [Fe(bpn){Ag(CN) 2 } 2 ]·Ph 2 S ( 1·Ph 2 S , bpn = 1,4-di(pyridin-4-yl)naphthalene, Ph 2 S = diphenylsulfide), [Fe(bpn){Ag(CN) 2 } 2 ]·Ph 2 SO ( 1·Ph 2 SO , Ph 2 SO = diphenylsulfoxide) and [Fe(bpn){Ag(CN) 2 } 2 ]·Ph 2 SO 2 ( 1·Ph 2 SO 2 , Ph 2 SO 2 = diphenylsulfone) were synthesized by employing sulfur-containing aromatic guests varying in oxidation states. 1·Ph 2 S performed a complete four-step spin crossover (SCO) behavior with the sequence of HS↔LS 1/3 HS 2/3 ↔LS 1/2 HS 1/2 ↔LS 2/3 HS 1/3 ↔LS, while an incomplete two-step SCO profile with the sequence of HS↔LS 1/3 HS 2/3 ↔LS 2/3 HS 1/3 and a faint SCO behavior at low temperature for 1·Ph 2 SO and 1·Ph 2 SO₂ . Photomagnetic experiments indicate the light-induced excited spin-state trapping (LIESST) effect in 1·Ph 2 S and the bi-directional LIESST effect for 1·Ph 2 SO and 1·Ph 2 SO₂ . Variable-temperature structural analyses reveal the evolution of host-guest synergy and highlight the mechanism of adaptive deformation of guests mediated by phenyl rotation amid spin transition. As the oxidation state of sulfur-containing guests increases, the host-guest cooperation within the lattice is limited by the steric effect, which stabilizes the high-spin state and consequently diminishes the SCO capability in this system. These results demonstrated herein open a new perspective on host-guest chemistry within SCO frameworks. Supplementary Material File (cjc.docx) Download 6.81 MB Information & Authors Information Version history V1 Version 1 14 January 2025 Peer review timeline Published Chinese Journal of Chemistry Version of Record 8 Mar 2025 Published Copyright This work is licensed under a Non Exclusive No Reuse License. Collection Chinese Journal of Chemistry Keywords guest-adaptive deformation iron light-induced excited spin-state trapping (liesst) metal-organic frameworks (mofs) spin crossover Authors Affiliations Kai-Ping Xie 0009-0002-4582-7792 [email protected] Huizhou University View all articles by this author Hai-Ling Wang Guangxi University Guangxi Key Laboratory of Electrochemical Energy Materials View all articles by this author Ze-Yu Ruan Sun Yat-sen University School of Chemistry View all articles by this author Pei-Yu Liao Sun Yat-sen University School of Chemistry View all articles by this author Guang Yang Sun Yat-sen University School of Chemistry View all articles by this author Zi-Cheng Xiao Huizhou University View all articles by this author Yi-Fei Deng Southern University of Science and Technology Department of Chemistry View all articles by this author Si-Guo Wu Sun Yat-sen University School of Chemistry View all articles by this author Yan Shi Huizhou University View all articles by this author Ming-Liang Tong 0000-0003-4725-0798 Sun Yat-sen University School of Chemistry View all articles by this author Metrics & Citations Metrics Article Usage 439 views 229 downloads .FvxKWukQNSOunydq8rnd { width: 100px; } Citations Download citation Kai-Ping Xie, Hai-Ling Wang, Ze-Yu Ruan, et al. 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