Syntheses And Prope Rties Of Coordination Polymers Constructed By A Resorcin[4]-based Tetracarboxylate

By using a new resorcin[4]arene-based tetracarboxylate, three coordination polymers(CPs), namely [(CH3)2NH2][Cd2NaL(HCOO)2(HCOOH)(H2O)]·H2O(1), [(CH3)2NH2]2[CdL]·CH3OH·4H2O(2) and [(CH3)2NH2][Zn2Na3L2(H2O)2]·H2O(3), have been synthesized under solvothermal conditions(H4L = 2,8,14,20-tetra-pentyl-4,10,16,22-tetrakis((4-carboxybenzyl)oxy)-6,12,18,24-tetra- methoxy-r esorcin[4]arene). The structures of 1-3 have been confirmed by single-crystal X-ray diffraction analyses. Among them, carboxyl groups of L anions present four different coordination modes. In 1, L and HCOO- link Cd(II) and Na(I) ions to yield an unusual 3D 4-connected heterometallic framework with(42·64)(4·83·10·12) topology. In 2, L anions link Cd(II) ions to give a 3D binodal 4-connected framework with(42.63.8)2 topology. In 3, four Zn(II) and eight Na(I) atoms are joined together through carboxylate groups from ten L ligands to give a rare centrosymmetric dodecanuclear heterometallic cluster, and adjacent dodecanuclear heterometallic clusters are joined together by L anions, yielding a 2D(3,8)-connected(3·42)(34·46·56·68·73·8) network. Properties of the three coordination polymers have been investigated. Most strikingly, CPs 1 and 2 display unusual metal- ion exchange characters. CP 2 shows remarkable reversible adsoption of I2 molecules. In addition, CPs 1-3 can selectively adsorb organic dyes and behave highly luminescent sensing properties for small molecules.