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Spin Crossover Quenching by “Racemization” in a Family of trans-1,2-Di(tetrazol-1-yl)cyclopentane-Based Fe(II) 1D Coordination Polymers
Autorzy
Rok wydania
2024
Czasopismo
Numer woluminu
63
Strony
17762-17773
DOI
10.1021/acs.inorgchem.4c02671
Kolekcja
Język
Angielski
Typ publikacji
Artykuł
Optically pure (RR)- and racemic (RR/SS)-trans-1,2-di(tetrazol-1-yl)cyclopentane were synthesized and used to prepare homo- and heterochiral Fe(II) coordination compounds. [Fe((RR/SS)-C7H10N8)2(CH3CN)2](BF4)2 (1A), [Fe((RR/SS)-C7H10N8)2(C2H5CN)2](BF4)2 (2A), [Fe((RR)-C7H10N8)2(CH3CN)2](BF4)2·2CH3CN (1B·solv), and [Fe((RR)-C7H10N8)2(C2H5CN)2](BF4)2 (2B) form a family of one-dimensional coordination polymers. Fe(II) cations in these complexes are characterized by a heteroleptic coordination environment: the neighboring metal centers are bridged by two 1,2-di(tetrazol-1-yl)cyclopentane molecules, while the nitrile molecules (acetonitrile or propionitrile, respectively) occupy the axial positions. Independently of the kind of nitrile coligands, an ability to thermally induce spin crossover (SCO) is governed by chirality. 1B·solv and 2B exhibit abrupt and complete SCO occurring at T1/2 = 144 K and T1/2 = 228 K, respectively. Desolvated form, 1B (of the same stoichiometry as 2B), also exhibits SCO (T1/2 = 215 K). In contrast, an exchange within the polymeric chain of half of the RR molecules with the SS enantiomeric form results in formation of 1A and 2A, which remain in stable high-spin (HS) form down to 10 K. It has been shown that moving from a homochiral to a heterochiral system changes the structure of the polymeric unit (while maintaining the same polymer dimensionality and bridging fashion) that leads to the deep reorganization of the further coordination spheres, including the anion network.
Słowa kluczowe
Anions, Coordination Compounds, Crystals, Ligands, Molecules
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Pełny tekst licencji: https://creativecommons.org/licenses/by/3.0/pl/legalcode
Adres publiczny
http://dx.doi.org/10.1021/acs.inorgchem.4c02671
Strona internetowa wydawcy
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