Synthesis, Structures And Properties Of Functional Supramolecular Compounds From Bipyridine And 1,3,5-benzenetricarboxylic Or 1,2,4,5-benzenetetracarboxylic Acid

Functional supramolecular compounds have been widely researched because of their novel topological structures and various properties. Now, the design and synthesis of functional supramolecular compounds have been applied in catalysis, magnetism,materials, host-guest, luminescence, and so on. As we know, some factors, such as the suitable ligands, metal ions and counterions, are important in the synthesis of expected supramolecular architectures.In this dissertation, 1,3,5-benzenetricarboxylic acid(H3BTC) and 1,2,4,5-benze netetracarboxylic acid(H4BTA) are served as O-ligands, because of their various c oordination modes, while a rigid 1,4-bis[2-(4-pyridyl)ethenyl]benzene(simplified as bpeb) is used as the N-ligand. At the same time, Pb2+, Zn2+and Mn2+ions are u sed as node. Under solvothermal conditions, seven supramolecular compounds ha ve been synthesized, namely, {[Co2(bpeb)(Hbpeb)2(H2O)2(BTA)]I2(H2O)4}n(1),{[Ni2(bpeb)(Hbpeb)2(H2O)2(BTA)]I2(H2O)4}n(2),[Co3(BTC)2(bpeb)6]n(3), [Ni3(BTC)2(bpeb)6]n(4),{[Mn3(Hbpeb)(HBTC)2(BTC)](DMF)3]}n(5), [Pb2(H2bpeb)(BTC)2(H2O)4]n(6), a nd {[Zn6(HBTC)2(BTC)5(Hbpeb)(bpeb)(H2O)2](Hbpeb)2(H2bpeb)2(H2O)14}n(7)(H3BT C = 1,3,5-benzenetricarboxylic acid,H4BTA=1,2,4,5-benzenetetracarboxylic acid). I n this work, temperature, solvents, counterions, p H and concentration can influen ce the size and quality of crystals. Above new complexes are characterized by th e single-crystal X-ray diffraction, TG analysis, XRPD, FT-IR and luminescent spe ctra.1. The isostructural 1 and 2 are synthesized under the solvothermal reaction of Co2+/Ni2+, H4 BTA, KI and bpeb. The complex 1 is a porous three-dimensional(3D)metal-organic framework with void occupied by two different components, theprotonated Hbpeb and the rare [I2(H2O)4]2-anion cluster. The characteristic solid-state luminescent emissions of 1 and 2 are around 531 and 497 nm at room temperature,respectively.2. Other five supramolecular polymers were synthesized from the salts of Co2+/Ni2+/Mn2+/Pb2+/Zn2+, H3 BTC and bpeb under the solvothermal conditions.Complexes 3 and 4 are isostructural by X-ray powder diffraction(PXRD). 3 displays an interesting porous 3D three-fold interpenetrated metal-organic framework and strong fluorescent emission around 487 nm. Complex 5 has trinuclear manganese clusters, and the three-dimensional(3D) 3,5-connected {42?6}{42?65?83} topology. Complexes 6 and 7illustrate 2D layered structures sandwiched with bpep ligands. Luminescent emission band of 6 is at 597 nm.