Metal ions Directed Self-assembly based on Mixed Ligands: From 2D hcb Net to 3D cds Framework

Two coordination polymers (CPs), namely, [Zn(BPDC)(3-bpdb)(0.5)(H2O)(2)](n) (1), and [Ni(BPDC)(3-bpdb)(H2O)(2)](n) (2) (where H2BPDC = 4,4'-biphenyldicarboxylic acid, 3-bpdb = 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene) have been solvothermally synthesized and characterized by single-crystal X-ray diffraction, IR, elemental analyses, PXRD, and SEM. CP 1 possesses a 2D 3-connected hcb net, and weak hydrogen bonding and pi center dot center dot center dot pi stacking contacts further link the 2D networks to form 3D supramolecular structure. The structure of 2 presents a 4-connected threefold interpenetrated cds framework. Through structural analysis, it is found that the coordination geometry of metal ions significantly affects the binding behaviors of the ligands and the resultant extended networks of the CPs. Besides, the Hirshfeld surface analyses detailed the surface characteristics of the two CPs. In addition, the thermal stabilities and photoluminescent properties were also investigated.