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https://doi.org/10.1039/d2dt00058j
Title: | Manipulating the spin crossover behaviour in a series of cyanide-bridged {(Fe2Fe2II)-Fe-III} molecular squares through NCE- co-ligands | Authors: | You, Maolin Nguyen, Giang T Shao, Dong Wang, Te Chang, Xiao-Yong Ungur, Liviu Zhang, Yuan-Zhu |
Keywords: | Science & Technology Physical Sciences Chemistry, Inorganic & Nuclear Chemistry THERMAL HYSTERESIS TRANSITION POLYMORPHISM COMPLEXES TEMPERATURES FAMILY TOOL |
Issue Date: | 10-Mar-2022 | Publisher: | ROYAL SOC CHEMISTRY | Citation: | You, Maolin, Nguyen, Giang T, Shao, Dong, Wang, Te, Chang, Xiao-Yong, Ungur, Liviu, Zhang, Yuan-Zhu (2022-03-10). Manipulating the spin crossover behaviour in a series of cyanide-bridged {(Fe2Fe2II)-Fe-III} molecular squares through NCE- co-ligands. DALTON TRANSACTIONS 51 (14) : 5596-5602. ScholarBank@NUS Repository. https://doi.org/10.1039/d2dt00058j | Abstract: | Manipulating the transition temperature (T1/2) of spin-crossover (SCO) complexes capable of fulfilling practical criteria through different synthetic strategies is one of the main focuses in the field of molecular magnetism. The reaction of the tricyanometallate precursor [(Tp*)FeIII(CN)3]− and Fe(ii) salt with the “facially” tridentate ligand tris(2-pyridyl)phosphine oxide (TPPO) and NCE− anions afforded three isostructural {FeIII2FeII2} square complexes {[(Tp*)FeIII(CN)3]2[FeII(TPPO)]2[NCE]2}·Sol (E = S, Sol = 2CH3OH·6H2O, 1; E = Se, Sol = 2MeCN·2CH2Cl2·2H2O, 2; E = BH3, Sol = 4CH3OH·2MeCN, 3). Detailed structural analysis, variable-temperature IR analysis, magnetic susceptibility measurements and DFT calculations revealed that all compounds exhibit complete and one-step SCO behaviour between the {FeIII,LS2FeII,HS2} and {FeIII,LS2FeII,LS2} electronic states. As the ligand field increases from NCS− to NCSe− to NCBH3−, T1/2 shifts dramatically from 214 to 250 to 288 K for 1, 2 and 3, respectively, demonstrating another effective way to tune the SCO properties of the [FeIII-CN-FeII] systems through the introduction of NCE− co-ligands. | Source Title: | DALTON TRANSACTIONS | URI: | https://scholarbank.nus.edu.sg/handle/10635/228915 | ISSN: | 14779226 14779234 |
DOI: | 10.1039/d2dt00058j |
Appears in Collections: | Elements Staff Publications |
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