Design, Synthesis And Property Studies Of Azolylbenzoic Acid Organotin Complexse

Organotin has been receiving considerable attention in recent years, for some of them are biologically active or have been used as reagents or catalysts in organic reactions. Furthermore, a surprisingly large structural diversity can be achieved by relatively simple synthetic variations from organotin compounds. Admittedly this field is quite nascent, but the recent results in this area are quite exciting.In this work, we synthesised a series of multifunctional ligands HL1-HL4, introducing azoles group into the carboxylic acid, which contained both N donor atoms and O donor atoms in order to bridge metal ions to give rise to a wide variety of complexes ranging from discrete entities to three-dimensional supramolecular structure. Main research results obtained were concluded as follows:1. The recent developments in the research for organotin complexes were reviewed and the idea of designing of this dissertation was put forward based on related literatures.2. Four new ligands,4- imidazolylbenzoic acid (HL1),4- pyrazolylbenzoic acid (HL2),4-triazolylbenzoic acid (HL3) and 4-tetrazolylbenzoic acid (HL4) were synthesized. The structures were characterized by 1HNMR, IR, MS and elemental analyses. Single X-ray diffraction analysis showed that HL1 have two different crystal structures in two different growth condition. The hydrogen bond play the key role in forming the 3-D framework.3. Reactions of Ph3Sn(OH) or n-Bu2SnO with various heterocyclic substituted benzoic acids afford the polymer (C6H5)3Sn(L)∞[HL=4-imidazolylbenzoic acid (1)], the mononuclear (C6H5)3Sn(L) [HL=4-pyrazolylbenzoic acid (2), 4-triazolylbenzoic acid (3) and 4-tetrazolylbenzoic acid (4)] and the tetranuclear [(n-Bu2Sn)4(L)2O2(OCH3)2] [HL=4-pyrazolylbenzoic acid (5),4-triazolylbenzoic acid (6)]. X-ray diffraction analyse show 1-D infinite chain of polymer 1, single molecular structures of complexes 2 and 4, single molecule structures of complex 3 containing solvent CH3OH molecule and similar ladder-type structures of complexes 5 and 6. All the complexes show an extensive supramolecular organization in the solid state. The cumulative effects of various intermolecular interactions, such as C-H…O, C-H…N, O-H…N, C-H…πandπ…πinteractions result in different mimic-3D supramolecular structures of 1-6. In some extent, ligands consisting of both imidazole and carboxylate as building block may have a tendency to form polymer.4. The photoluminescence of ligands and 1-6 were also measured in the solid state at room temperature. The emission range varied extensively, which was considered to mainly originate from the influence of the coordination molds of metal atom and diverse intermolecular interactions in the solid state.5. The effect of the new compounds on antibacterial as well as antiproliferative activities were examined. The activity both on antibacterial and on antitumour of complexes are excellent than that of relevant ligands, which indicate the obviously synergistic effects and the structure-activity relationship are also discussed.