Syntheses, Characterizations, Crystal Structures And Property Of Novel Organotin(Ⅳ) Carboxylate Complexes

With the research and development of anticancer drugs in 1980, Crowe et al. reported that some two organotin(IV) carboxylate compounds have good anticancer activity. Since then, studies on synthesis, structure and antitumour activity of organotin(IV) has become one the organotin(Ⅳ) and anticancer drugs research. In recent years, people have turned to the large ring and chain structure from simple structure synthesis of organotin(Ⅳ) carboxylate, even more people are interested in the large ring structure synthesis of guest molecules.In this thesis, it has been reported the design and synthesis of five (5) new organotin(Ⅳ) carboxylates with two or three-dimensional ring structures, containing three (3) guest molecules; the design and synthesis of a novel supramolecular chain organotin(Ⅳ) carboxylates were also reported. All the complexes were characterized by elemental analyses:IR and NMR spectroscopy, and crystal structure was determined by single X-ray diffraction. The luminescent properties and antitumour activity of some complexes were studied. This thesis consists of the following components:1. The flexible ligand H2L1 (2,2’-(1,3-phenylenebis(oxy) diacetic acid) was synthesized by the reaction of resorcinol and chloroacetic acid. Organotin(Ⅳ) carboxylate (complex 1) is a novel penta-nuclear obtained by using the ligand and dibutyltin(Ⅳ) oxide. Complex 1 is a 16-membered macrocycle. Through hydrogen bonds, complex 1 formed 36 membered rings with two dimensional supramolecular networks, and its anticancer activity was tested. It has been also found that at low and high concentrations, complex 1 provided good anticancer effect than dibutyltin(Ⅳ) oxide.2. The flexible ligand H2L2 (2,2’-(1,4-phenylenebis(oxy) diacetic acid) was also synthesized by the reaction of hydroquinone and chloroacetic acid. By the complexation with dibutyltin(Ⅳ) oxide, a novel tetranuclear organotin(Ⅳ) carboxylate (complex 2) with one dimensional chain structure was obtained. The luminescent properties were tested and compared with those of carboxylic ligand.3. The ligand HL3 was synthesized by the reaction of benzo[de]isochrome-1,3-dione and 3-aminopropanoic acid. By the reaction of triphenyltin(Ⅳ) hydroxide and ligand HL3, a novel mononuclear organotin(Ⅳ) carboxylate (complex 3) was obtained. Through intermolecular C-H…O and C-H…π bonds, complex 3 formed two kind macrocycles. The larger ring contains two toluene guest molecules and the two rings are alternately connected forming a two dimensional supramolecular chain. The luminescent properties were also tested and compared with those of carboxylic ligand.4. A novel dinuclear organotin(Ⅳ) dicarboxylate (complex 4) was synthesized by the reaction of triphenyltin(Ⅳ) hydroxide and ligand HL4. The ligand HL4 was previously obtained by the reaction of pyromellitic dianhydride and 3-aminopropanoic acid. Through Sn-O bonds, complex 4 forms a macrocyclic coordination structure. Intermolecular C-H…O bonds connect the macrocycles and form a 3D supramolecular network. With the help of the two kinds of intermolecular interactions in complex 4, two rings are alternately connected forming a two dimensional supramolecular network. Free toluene molecules are located on both sides in it.5. The ligand HL5 was synthesized by the reaction of 1,4,5,8-naphtalenetetracarboxylic dianhydride with 3-aminopropanoic acid. By the reaction of triphenyltin(IV) hydroxide and ligand HL5, a novel dinuclear organotin(IV) carboxylate (complex 5) was obtained. Through Sn-O and intermolecular C-H…O bonds in complex 5, two rings are alternately connected to form a two dimensional supramolecular network. Free toluene molecules are located on both sides in it.6. The ligand HL6 was obtained by the same method as HL4 with pyromellitic dianhydride and 3-aminobenzoic acid. By the reaction of triphenyltin(IV) hydroxide and ligand HL6, a novel dinuclear organotin(IV) carboxylate (complex 6) was also obtained. Through intermolecular C-H…O bonds in complex 6, two rings are alternately connected and form a two dimensional supramolecular network. Free ethanol molecules are bound to tin atoms.