Synthesis, Structures And Properties Of Aromatic Carboxylic Silver Coordination Polymers Containing Nitrogen-, Phosphorus- Heterocyclic Ligands

As newly-identified functional molecule-based materials, metal-organic coordination polymers have been a focus of coordination and material chemistry due to their flexible tailoring structures as well as their facile functionalizing properties. Nowadays, new metallic crystalline materials with predetermined structures and properities of optics, electric and magnetism and so on can be obtained by selecting functional metal ions and special organic ligands with functional groups. In this work, aromatic-carboxyl acids such as benzonic acid(ba) and its derivates, terephthalic acid (bdc) and its derivates, sulfobenzonic acids (sb) and sulfosalicylic acid(ssal) were chosen as organic ligands to have synthesized 34 novel carboxylate-based silver(Ⅰ) complexes with N-and P-donor neutral ligands. These complexes all have been characterized by X-ray single crystal structure analysis, IR, UV, element analysis, thermal stability behavior, and fluorescent emission. Also, the catalysis and electro-catalysis behaviors of some complexes were analyzed and researched, covering the following aspects:1.17 Ag-complexes were synthesized based on bdc,2-abdc and 2-nbdc with N-bridging ligands. In them,8 complexes were obtained bridged by 4,4’-bipy (1-7, 30); 4 complexes bridged by bpe (8-11), and one binary complex and 3 geometric isomers bridged by bpmb ligand (13-15). Another is a 2D cluster complex without neutral bridging ligand (29). Since the electro-catalysis behavior of these complexes to H2O2 is similar, the bridging structures of these Ag(I) complexes are important. And moreover, interactions of Ag-Ag, π-π and Ag…π can not be neglected for the electro-catalysis behavior.2.4 new Ag-complexes were synthesized based on bdc and its derivates with PPh3 (25-28). Here, complex [Ag2(PPh3)2(2-abdc)]·2CH3OH] (25), shows excellent fluorescence property not only in solid state but also in liquid state, indicating that substituent group on phenyl has great influence on the properties of complexes. Moreover, considering a tetranuclear Ag-complex, [Ag4(PPh3)4(3-nbdc)2] (28), was obtained when 2-nitroterephthalic acid (2-nbdc) was changed into 3-nitrophthalic acid (3-nbdc), the position of two carboxyl groups on phenyl are important to the structures. Besides, compared with those bridging ligands, the difference of those neutral ligands is another factor leading to different structures of these complexes.3.9 novel Ag-complexes were synthesized based on sb and ssal ligands with N-donor bridging ligands. Here,5 Ag-complexes were obtained with sb and bpmb ligands (16-20), and another 4 complexes were obtained with ssal and 4,4’-bipy, bpe and bpmb ligands (21-24). The behavior of catalysis to oxidation of MPS by H2O2 indicates that sulfonic group is indispensable to the catalytic property of these complexes. In addition, complex 17 shows great catalytic and recyclable behavior in oxidation of MPS and has actual application value.4. To compare with the structures and properities of those polycarboxylate-silver(I) complexes, we also got 4 Ag-complexes based on benzoic acid (ba) derivatives with N-donor bridging ligands. And we drew the conclusion that in the process of coordination with Ag ion, monocarboxylic acids have shown their special characters, and the difference of substituent groups has great influence on the structures of these complexes.We have summarized and analyzed systematically the influence of synthetic methods and conditions, solvent choice, reaction temperature and substituent groups on phenyl and so on to the structures, stability, spectrum properties and catalytic behavior of these 34 complexes, which are important to choose organic ligands to design and synthesize functional coordination complexes. Besides, these information offers important reference value to design novel Ag complexes as H2O2 detectors and catalysts.