A Study On Novel Construction Of Metal-assembled And Metal-Cluster Architectures Based On Hydroxypolycarboxylic Acids

The exquisite designed construction of metal-assembled and metal-cluster frameworks by use of the principles of self-assembly, especially for coordination polymers and supramolecular architectures, represents a topical and current research interest in chemistry, materials, medicals and biology areas today. This reason is not only in their fascinating structural diversity, but in their unusual physical, chemical behavior and potential applications in the fields of optical, electronic, magnetic, catalytic, molecular recognition, absorbent, ion exchange, gas storage and biology activity. Lately, it is demonstrated that considerate selectively controlling inorganic building units and creating strategies of assembly is the key in constructing target polymers and which is a most challenging issue facing scientists either. In this theses, we choose α-hydroxybutanedioic acid (H₃hbd), 2,3-dihydroxybutanedioic acid (H₄dhbd) and 2-hydroxy-l,2,3-tricarballylic acid (H₄htb), a group of ligands with biological activity of hydroxypolycarboxylic acids, as building units and copper which is the necessary element of human being to be the metal center, meanwhile, accompany aromatic ligands including N donors. As results, 15 novel organo-matel supramolecular polymers namely [Cu(Hhbd)(bpy)].3H₂O}_n(1), [Cu(Hhbd)-(phen)₂].1.5H₂O.2MeOH (2), {[Cu(Hhbd)(phen)].H₂O-MeOH}_n(3), [Cu₂(Hhbd)₂-(terp)₂].2MeOH (4), [Cu₂(H₂dhbd)₂(pyOH)₂(H₂O)₂].pyOH.2H₂O(5), {[Cu₂(dhbd)-(bipy)₂].10H₂O}_n(6), [Cu₂(H₂dhbd)(bipy)₄][H₂dhbd].10H₂O (7), [Cu₂(dhbd)-(dpa)2H2O] -6H2O (8), [QuoCHdhM^^dhMW^yNHrl^O-MeOH (9), {[Cu12-(Hdhbd)4(H2dhbd)6]-8pyNH2-18H2O}n (10), [Cu2(Hdhbd)2(terp)2]-2MeOH-6H2O (11), [Ni(H2dhbd)-(phen)2]-5H2O (12), {Cu2(htb)(phen)2-3.5H2O}n (13), [Cu(phen)2-CO3]- 7H2O(14) and {[Cu2(CN)2(dppt)2]-2H2O}n (15) have been synthesized. The structures of 15 complexes have been determined by the X-ray single crystal diffraction analysis, and IR spectra, electronic reflectance spectra, thermal analyses, cyclic voltammograms and temperature dependence of magnetic susceptibility measurement were used to investigate their spectroscopy characters and properties. The results show that the 3 kinds of hydroxypolycarboxylic acids mentioned above play an important role in the construction of novel organo-metal supramolecular polymers, which not only present 8 kinds of new modes of coordinating to transition metals, but also could be as donor-acceptor of hydrogen bonds formulating multi-dimensional expanded networks, furthermore, they cooperate with assistant ligands providing potential supramolecular recognition sits for tz-k aromatic stacking and hydrogen bonds interactions to build up 1-D open channeled 3-D multi-porous supramolecular polymers [(1), (3),(7), (8), (9),(10) ,(11)], 3-D supramolecular polymers[(6), (12), (13) and (14)], 2-D honeycomb-like supramolecular polymers(5), 2-D supramolecular networks (2) and 2-D ladder-shaped supramolecular polymers [(4), (15)] based on lower dimensional building blocks, on the other hand, we also discover 4 kinds of new small water clusters. Meanwhile, some regular conclusion have been summarized through the comparison studies on structures, assembled rules, spectroscopy characters, electrochemistry and magnetic properties of the supramolecular polymers constructed from 3 kinds of hydroxypolycarboxylic acids.