Three series of copper-lanthanide/lanthanide coordination polymers (CPs) Ln(III) Cu(II) Cu(I) (bct)3 (H2 O)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), H2 bct=2,5-bis(carboxymethylmercapto)-1,3,4-thiadiazole acid], Ln(III) Cu(I) (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 Ln(III) 2 (bct)3 (H2 O)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 Cu(I) 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 Eu(III) and Tb(III) 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.

A new two-dimensional dysprosium–organic coordination polymer 1-Dy has been synthesized by a hydrothermal method. 1-Dy displays a ferromagnetic interaction between two DyIII ions within the Dy2 dimer and a slow magnetic relaxation with a high effective energy barrier of approximately 160 K under a zero dc field.

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Twenty 3d–4f heterometallic coordination polymers (CPs), namely, [Ln2Co(2,3‐pzdc)4(H2O)6]·2H2O [Ln = La (1), Pr (2), Nd (3), Sm (4), Eu (5), Gd (6), Tb (7)], [Ln2Co(2,3‐pzdc)4(H2O)4]·4H2O [Ln = Dy (8), Er (9)], [Ln2Cu(2,3‐pzdc)4(H2O)6]·2H2O [Ln = La (10), Pr (11), Nd (12), Sm (13), Eu (14), Gd (15), Tb (16)], [Dy2Cu(2,3‐pzdc)4(H2O)4]·4H2O (17), and [Ln2Cu(2,3‐pzdc)4(H2O)4]·2H2O [Ln = Er (18), Yb (19), Lu (20)], are synthesized successfully by the reactions of 2,3‐H2pzdc with LnCl3·nH2O/Ln(NO3)3·nH2O and Co(NO3)2·3H2O/CuCl2·2H2O under hydrothermal conditions. CPs 1–20 are isostructural, and only the coordination and interstitial water molecules, as well as the coordination numbers of LnIII, are different from each other. In 1–20, the 2,3‐pzdc anions link the CoII/CuII and LnIII ions by two coordination modes to form a three‐dimensional (3D) framework with a 3,3,4,4‐connected (4·62)2(42·62·82)(63)2(65·8)2 topology. CPs 6 and 7 manifest the weak ferromagnetic interactions between CoII and LnIII in the low‐temperature range. CP 8 exhibits a field‐induced slow magnetic relaxation behavior. CP 16 shows a magnetic transition between short‐range ferromagnetic ordering at 60 K and long‐range ferromagnetic ordering below 26 K. CP 17 displays field‐induced single‐molecule magnet (SMM) behavior, with a Ueff value of 102.4 K.