Synthesis, Characterization, Crystal Structure And Property Study Of Organotin(IV) Carboxylates Based On Aromatic Carboxylic Acids

The chemistry of organotin has been studied since 1849 and developed considerably during last 30 years, highlighting the syntheses of a number of complexes with interesting properties. Organotin complexes have been used extensively as catalysts, stabilizers, biocides, anti-fouling agents and wood preservatives. In recent years, the investigations on the structure mode and biological activities, especially anti-tumor activity of organotin complexes have become the focus on organotin chemistry.In this paper, eight organotin carboxylates were synthesized by the reactions of di-n-butyltin oxide, triphenyltin hydroxide, trihexamethylenetin hydroxide with rigid aromatic carboxylic acid ligands including naphthalene-1,4-dicarboxylic acid, 5-amino-isophthalic acid, imide acid. The ligands and their metal complexes were characterized by elemental analysis, FT-IR and 1H NMR spectroscopy, and the structures of the complexes were determined by single crystal X-ray diffraction analysis. The luminescent property and antitumour activities of complexe 1 were preliminary studied. The dissertation contains the following works:1. Three complexes (n-Bu₂SnL¹)₄·2C₆H₆ (1),(Ph₃Sn)₂L¹(ONC₃H₇)₂ (2),(Cy₃Sn)₂L¹ (3) have been synthesized by the reaction of naphthalene-1,4-dicarboxylic acid (H₂L¹)and di-n-butyltin oxide, triphenyltin hydroxide, trihexamethylenetin hydroxide. Interestingly, complex (1) has a centrosymmetric tetranuclear diorganotin dicarboxylate with 36-membered macrocycle, which is formed by n-Bu2Sn and ligand alternately linking. Luminescent property study of complex (1) has shown that the fluorescent intensity strengthened markedly compared with ligand. Pilot studies indicated that complex (1) has shown good antitumour activities.2. The complex (Ph₃Sn)₂L²(OC₂H₅)₂ (4) has been synthesized by the refluxing reaction of 5-amino-isophthalic acid (H₂L²)and triphenyltin hydroxide in anhydrous toluene, then forms two-dimensional layered polymer containing tetranuclear 28-membered (â… ) and tetranuclear 48-membered (â…¡) two types of macrocycles. In the molecular structure of complex (4), Sn atoms are five-coordinated and present the distorted trigonal bipyramidal geometry structures. Through three different types of intermolecular O-H···O hydrogen bonding interactions, complex (4) forms 2D structures containing two types of macrocycles.3. First, four kinds of imide acids (H2L3,HL4,H2L5,HL6) have been prepared by using 1,8-naphthalene dicarboxylic anhydride, phthalic anhydride with p-aminobenzoic acid, 5-amino-isophthalic acid, then four complexes Ph₃SnL³ (5),(Ph₃Sn)₂L⁴·C₇H₈ (6),Ph₃SnL⁵ (7),(Ph₃Sn)₂L⁶ (8) have been synthesized by the reaction of corresponding imide acids and triphenyltin hydroxide. There exist intermolecular O-H···O hydrogen-bonding interactions in these complexes. Through hydrogen bonding interactions, one-dimensional chains are formed in complex (5), complex (7) and complex (8); 2D structure is formed in complex (6).