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Guest-, light- and thermally-modulated spin crossover in [FeII2] supramolecular helicates

AuthorsDarawsheh, Mohanad; Barrios, L. A.; Roubeau, Olivier; Teat, Simon J.; Aromí, Guillem
KeywordsSupramolecular chemistry
Spin crossover
Coordination chemistry
Iron(II) helicates
Issue Date2016
CitationChemistry - A European Journal 22(25): 8635-8645 (2016)
AbstractA new bis(pyrazolylpyridine) ligand (HL) has been prepared to form functional [Fe(HL)]metallohelicates. Changes to the synthesis yield six derivatives, X@[Fe(HL)]X(PF)⋅xCHOH (1, x=5.7 and X=Cl; 2, x=4 and X=Br), X@[Fe(HL)]X(PF)⋅yCHOH⋅HO (1 a, y=3 and X=Cl; 2 a, y=1 and X=Br) and X@[Fe(HL)](I)⋅3 EtO (1 b, X=Cl; 2 b, X=Br). Their structure and functional properties are described in detail by single-crystal X-ray diffraction experiments at several temperatures. Helicates 1 a and 2 a are obtained from 1 and 2, respectively, by a single-crystal-to-single-crystal mechanism. The three possible magnetic states, [LS–LS], [LS–HS], and [HS–HS] can be accessed over large temperature ranges as a result of the structural nonequivalence of the Fecenters. The nature of the guest (Clvs. Br) shifts the spin crossover (SCO) temperature by roughly 40 K. Also, metastable [LS–HS] or [HS–HS] states are generated through irradiation. All helicates (X@[Fe(HL)])persist in solution.
Identifiersdoi: 10.1002/chem.201601080
e-issn: 1521-3765
issn: 0947-6539
Appears in Collections:(ICMA) Artículos
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