The physical and electronic properties of Metal-Organic Frameworks containing dipyridylthiazolo[5,4-d]thiazole
CRYSTENGCOMM(2023)
摘要
Five Metal-Organic Frameworks ({[M-2(tdc)(2)(L )(2)]2DMF}, tdc = 2,5-thiophenedicarboxylate, M = Zn-II (1 -Zn ), Cu-II (1 -Cu ), Mn-II (1 -Mn ), {[Zn(oba)(L )]DMFH2O} (2 -Zn ), oba = 4,4 '-oxybisbenzoate, and {[Zn-2(bpdc)(2)(L )(2)]L }, (3 -Zn ) bpdc = 4,4 '-biphenyldicarboxylate) that incorporate the redox-active 2,5-dipyridylthiazolo[5,4-d]thiazole (DPTzTz) ligand (L ) have been synthesised and their electronic properties elucidated. The ligand-based organic radicals were generated using in situ techniques and monitored using a suite of solid-state spectroelectrochemistry techniques. The absence of a near infra-red band (NIR), indicating through-space intervalence charge transfer (IVCT), in all analysed materials suggests that both the inter-ligand distance between cofacial TzTz moieties and the flexibility of the TzTz moiety affect the through-space IVCT.
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