Syntheses, Structures And Properties Of Coordination Polymers Based On Resoricn[4]arene

A series of novel capsule-based coordination polymers（CPs）, namely, [Cd（TTR4A）（L1）]·2.5H₂O（1）, [Cd（TTR4A）（L2）]·2DMF·2H₂O（2）, [Cd（TTR4A）（L3）]·2DMF·1.5H₂O（3）, [Cd（TTR4A）（L4）]·1.5H₂O（4） and [Zn（TTR4A）（L1）]·DMF·H₂O（5）, have been hydrothermally synthesized through the reaction of a bowl-like tetrakis（1,2,4-triazol-ylmethy1）resorcin[4]arene（TTR4A） ligand with d10 metal salts in the presence of varied dicarboxylates（H₂L1 = fumaric acid, H₂L2 = 1,3-benzenedicarboxylic acid, H₂L3 = 5-hydroxy-1,3-benzenedicarboxylic acid, H₂L4 = biphenylethene-4,4’-dicarboxylic acid and DMF = N,N-dimethylformamide）. CPs 1-3 show the rare 2D capsule-based network structures. In 1-3, two TTR4 A bowls share two Cd（II） cations to give a capsule, which are further extended by the dicarboxylates into the 2D networks. CP 4 features a fascinating 3D 3-connected framework structure constructed from the bowl-like [Cd₂TTR4A] units and L4 anions. In 5, each TTR4 A coordinates with two Zn（II） cations by using two 1,2,4-triazole groups to generate a capsule, which are further linked by L1 anions into a 2D network structure. Significantly, the solid-state emissions and temperature variable luminescence were studied for 1-4. In particular, the remarkable metal-ion exchange property of CP 1 was investigated in single-crystal to single-crystal（SCSC） manner.