Systematic Investigation of Reaction-Time Dependence of Three Series of Copper-Lanthanide/Lanthanide Coordination Polymers: Syntheses, Structures, Photoluminescence, and Magnetism

Three series of copper–lanthanide/lanthanide coordination polymers (CPs) LnIIICuIICuI(bct)3(H2O)2 [Ln=La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Er (10), Yb (11), and Lu (12), H2bct=2,5‐bis(carboxymethylmercapto)‐1,3,4‐thiadiazole acid], LnIIICuI(bct)2 [Ln=Ce (2 a), Pr (3 a), Nd (4 a), Sm (5 a), Eu (6 a), Gd (7 a), Tb (8 a), Dy (9 a), Er (10 a), Yb (11 a), and Lu (12 a)], and LnIII2(bct)3(H2O)5 [Ln=La (1 b), Ce (2 b), Pr (3 b), Nd (4 b), Sm (5 b), Eu (6 b), Gd (7 b), Tb (8 b), and Dy (9 b)] have been successfully constructed under hydrothermal conditions by modulating the reaction time. Structural characterization has revealed that CPs 1–12 possess a unique one‐dimensional (1D) strip‐shaped structure containing two types of double‐helical chains and a double‐helical channel. CPs 2 a–12 a show a three‐dimensional (3D) framework formed by CuI linking two types of homochiral layers with double‐helical channels. CPs 1 b–9 b exhibit a 3D framework with single‐helical channels. CPs 6 b and 8 b display visible red and green luminescence of the EuIII and TbIII ions, respectively, sensitized by the bct ligand, and microsecond‐level lifetimes. CP 8 b shows a rare magnetic transition between short‐range ferromagnetic ordering at 110 K and long‐range ferromagnetic ordering below 10 K. CPs 9 a and 9 b display field‐induced single‐chain magnet (SCM) and/or single‐molecule magnet (SMM) behaviors, with Ueff values of 51.7 and 36.5 K, respectively. Time‐dependent assembly: Three series of copper–lanthanide/lanthanide coordination polymers have been successfully prepared under hydrothermal conditions by modulating the reaction time and structurally characterized (see figure). Their syntheses, structures, photoluminescence, and magnetism have been systematically investigated.