From zero-dimensional complexes to two-dimensional coordination polymers adjusted by metal ions or ligand substituent groups
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Six novel Zn(II), Cd(II) and Co(II) mixed-ligand coordination complexes, namely, Cd(HOBA) 2 (DPE) 2 (H 2 O) 2 ( 1 ), Co(HOBA) 2 (DPE) 2 (H 2 O) 2 ( 2 ), [Zn(DPA) 2 (DPE)] n ( 3 ), [Zn(CPA) 2 (BPP)] n ( 4 ), [Cd 2 (CPA) 4 (BPP) 2 (H 2 O)] n ( 5 ), and [Cd(DPA) 2 (DPE)] n ( 6 ) (H 2 OBA = 4-carboxylphenoxyacetic acid, HDPA = 2,4-dichlorophenoxyacetic acid, HCPA = 2-chlorophenoxyacetic acid, DPE = 1,2-di(pyridin-4-yl)ethylene, BPP = 1,3-bis(4-pyridyl)propane) have been synthesized hydrothermally by the self-assembly of R-phenoxyacetic acid (R = 2,4-dichloro, 2-chloro and 4-carboxyl), N-donor ligands and Zn(II), Cd(II) or Co(II) salts. Single crystal X-ray analyses reveal that in complexes 1 and 2 , the H 2 OBA and DPE act as terminal ligands, generating 0D Cd(II) and Co(II) mononuclear molecules. Complexes 3 and 4 both show 1D chain structures, where the four-coordinated Zn(II) ions are bridged by DPE and BPP, respectively. For complex 5 , the six- and seven-coordinated Cd(II) ions are interconnected through carboxyl groups to form [Cd 2 (CPA) 4 ] building units, which are subsequently extended by BPP ligands into 1D chains. In complex 6 , adjacent Cd(II) ions are bridged by DPA − anions to form a 1D linear chain. Through the bridging of DPE ligands, the 1D chains undergo dimensional expansion and eventually evolve into 2D supramolecular architectures. Furthermore, the thermal stabilities and fluorescence properties of these complexes have also been investigated.
