Synthesis,Structures And Biological Activity Studies Of Organotin Complexes Derived From Polycarboxylic Acids

Organometallic compounds,which are involved in the fields of Inorg.Chem.and organic chemistry,have shown important application values in the fields of industry,agriculture,national defense as well as medicine,and are one of the research hotspots in modern chemistry.Organotin compounds,as an important part of organometallic compounds,have attracted more and more attention of chemists due to their diverse structures and wide applications in functional materials,organic synthesis and exhibit good antibacterial and inhibiting cancer cell proliferation properties in areas such as biological activity.In the past several years,many studies have showed that some organotin(IV)complounds have shown potential in the prevention and antitumor activity in a variety of tumor cells via activate apoptosis pathway.Therefore,it is of great significance to study the structure-activity relationship between organotin compounds and their anticancer activities.From the perspective of coordination chemistry,the oxygen electron-donating atoms from dicarboxylic acids allow them to serve as either a multidentate or a bridging building block,which can make organotin compounds present more exquisite and interesting structures.Therefore,we selected four dicarboxylic acids ligands to react with organotin precursors,and the structures and properties of organotin carboxylates are also detailed in this research.The main part works as follows:1.Eight organotin(IV)complexes 1-8,have been designed and synthesized by the reactions of 4,4?-oxybisbenzoic acid and triorganotin(IV)c hloride or oxide.The single crystal diffraction reveals that:(1)a 1:2 ratio reaction of 4,4?-oxybisbenzoic acid ligand with trimethyltin chloride obtained monomers,1D infinite helical chain,1D infinite polymeric chain containing 28-membered macrocyclic ring and 2D network structure.(2)a1:2 ratio reaction of 4,4?-oxybisbenzoic acid ligand with bis(tri-n-butyltin)oxide obtained2D network structure.(3)a 1:2 ratio reaction of 4,4?-oxybisbenzoic acid ligand with triphenyltin chloride obtained monomer.The cell viability of organotin complexes 1-4 on human cervical cancer cell lines(He La)and human hepatocellular carcinoma cell lines(Hep G-2)were assessed by MTT colorimetric assays.The results show that complexes 3and 4 exhibit high cytostatic activity against two cell lines even higher than cisplatin.In addition,the interactions between complexes 1-4 and bovine serum albumin(BSA)were also investigated.The complexes could quench the intrinsic fluoresce nce of BSA in a static quenching process and there existence of just one binding site in BSA.2.Organotin(IV)complexes 9-16,have been synthesized by the reactions of1,4-naphthalenedicarboxylic acid and organotin(IV)precursors.The results show that:(1)the products of the reaction of the ligand with Me₃Sn Cl and(n-Bu₃Sn)₂O are 2D network structures.(2)reaction with Ph₃Sn Cl to obtain the monomer structure.(3)the central tin atoms of the products of the ligand with dialkyltin and 1,10-phenanthroline display seven-coordinated distorted pentagonal bipyramidal geometry.(4)the half inhibitory concentration values of organotin complexes 9-11 on He La and Hep G-2 cells were assessed,and the complexes exhibit higher anticancer activity.Meanwhile,complex 11showed higher anticancer activity by inducing mitochondrial membrane permeability(MMP)collapse and further excessive reactive oxygen species(ROS)production in Hep G-2 cells.3.We selected 2,6-naphthaienedicarboxylic acid as ligand and studied the reactions of ligand with trialkyltin and dialkyltin.Six novel organotin complexes 17-22 were obtained and characterized.The single crystal diffraction reveals that:(1)the central tin atoms of the products obtained by the reaction between the ligand and t he trialkyltin display five-coordinated trigonal bipyramid geometry.(2)the central tin atoms of the products of the ligand with dialkyltin and 1,10-phenanthroline display seven-coordinated distorted pentagonal bipyramidal geometry.(3)in vitro anticancer activity experiments show that organotin carboxylate have good biological activity.4.We selected 4,4'-stilbenedicarboxylic acid as ligand and studied the reactions of ligand with organotin(IV)precursors.Four organotin(IV)complexes 23-26 were obtained and characterized.The results showed that:(1)the products obtained by the reactions of ligand with Me₃Sn OH and(n-Bu₃Sn)₂O displayed 2D network structures.(2)reaction with Ph₃Sn OH to obtain the monomer structure.(3)the cell viability of organotin complexes23-26 on He La and Hep G-2 cells were assessed,and the complexes exhibit higher anticancer activity.Meanwhile,complex 24 induced apoptosis by inducing mitochondrial membrane permeability(MMP)collapse and excessive reactive oxygen species(ROS)production in Hep G-2 cells.