Study On Self-assembled Reactions Of Tri- And Diorganotin Moieties With Mercapto-carboxylate Ligands And Supramolecular Structures Of These Derivatives

Organotin compounds are attracting more and more interests due to their wide industrial,agricultural and pharmacal applications, as well as their diversely molecular andsupramolecular structures. In this field, a large number of articles about this motif are issuedevery year. Its research range is expanding constantly, including organometallic chemistry,coordination chemistry, structure chemistry, biochemistry and pharmacology, etc., thus itbecomes the front field that has the development prospect.Among the organotin compounds, the most ubiquitous are the organotin carboxylates. Inmore recent years, it has also been found that it demonstrated other structural types are formeddue to the presence of additional coordinating sites along with the carboxylate group. Due tothis reason, we select two types of substituted-carboxylate ligands—one is the rigidmercaptobenzoic acid and the other is the flexible mercaptoacetic acid and 2,3-mercaptosuccinicacid—and carried out a series of research on the self-assembled reactions and supramolecularstructures of organotin derivatives from these ligands. The main contributions of the thesis areas follows:1. Investigations on the reactions of di-and triorganotin with o-mercaptobenzoic acid. Eightnew organotin compounds were obtained and their structures are studied. In the triorganotinderivatives of o-mercaptobenzoic acid, the products are dinuclear monomers or coordinationpolymers depending on the different substitutes attached on tin atoms. When the R = Ph,PhCH2, the products are monomers;while the R = Me, nBu, the products are coordinationpolymers. In the diorganotin derivatives of o-mercaptobenzoic acid, the products aresix-nuclear macrocycles and their structures don't display apparent difference. Interestingly,these macrocyclic molecules are further linked to 2D supramolecular structures throughintermolecular C-H···S and C-H···π weak hydrogen bonding interactions.2. Investigations on the reactions of di-and triorganotin with m-mercaptobenzoic acid. Eightnew organotin compounds were obtained and their structures are studied. In the triorganotinderivatives of m-mercaptobenzoic acid, the products are also dinuclear monomers orcoordination polymers depending on the different substitutes attached on tin atoms. When theR = Ph, PhCH2, the products are monomers;while the R = Me, nBu, the products arecoordination polymers. In the diorganotin derivatives of m-mercaptobenzoic acid, the productsare six-nuclear macrocycles with double-cavity structure and their structures don't displayapparent difference. Interestingly, these macrocyclic molecules are further linked to 1D or 2Dsupramolecular structures through intermolecular C-H···S and π-π interactions.3. Investigations on the reactions of di-and triorganotin with p-mercaptobenzoic acid.Thirteen new organotin compounds were obtained and their structures are studied. In thetriorganotin derivatives of p-mercaptobenzoic acid, the products are mononuclear monomersor coordination polymers depending on the different substitutes attached on tin atoms. WhenR3SnCl: (p-mercaptobenzoic acid) = 1:1, the products are monomer formed with S atom, andthese complexes are further linked to dimers through intermolecular O-H···O hydrogen bonds;.while R3SnCl: (p-mercaptobenzoic acid) = 1:2, the products are dinuclear monomers orcoordination polymers, and these complexes are further linked to1D or 2D supramolecularstructures through intermolecular C-H···O or C-H···S weak hydrogen bonds. In the diorganotinderivatives of p-mercaptobenzoic acid, when R3SnCl: (p-mercaptobenzoic acid) = 2:1,theproducts are mononuclear formed with S atom, and these molecules are further linked to form1D or 2D supramolecular structures through intermolecular O-H···O and C-H···O interactions.4. Investigation on the reaction of trimethyltin with mercaptoacetic acid under solvothermalcondition. A mixture of mercaptoacetic acid, KOH, trimethyltin chloride, CH3OH and H2Owas heated in a Teflon-lined autoclave at 150°C for 3 days. After cooling down to roomtemperature, colorless crystals of mixed tri-and dimethyltin coordination polymer,{[(Me3Sn)(μ2-OH)][Me2Sn(μ3-SCH2CO2)]}n were obtanied. To our knowledge, it is the firstmixed organotin coordination polymer. The structure analysis shows that it is a helical chian,and these helical chains are linked together through inter-helix O-H···S H-bonding interactionsto form a 2D corrugated sheet.5. Investigations on the reactions of di-and triorganotin with 2,3-dimercaptosuccinic acid.Nine new organotin compounds were obtained and their structures are studied. In thetriorganotin derivatives of 2,3-dimercaptosuccinic acid, the products are tetranuclearmonomers, and these tetranuclear molecules are further linked to 2D network throughintermolecular C-H···π and Sn···S interactions. In the diorganotin derivatives of2,3-dimercaptosuccinic acid, the products are dinuclear monomers, and these dinuclearmolecules are further linked to 1D helical chain through intermolecular C-H···π interactions.macrocycles and their structures don't display apparent difference. Interestingly, thesemacrocyclic molecules are further linked to 2D supramolecular structures throughintermolecular C-H···S and C-H···π weak hydrogen bonding interactions. Reaction oftributyltin with 2,3-dimercaptosuccinic acid under solvothermal condition and obtained adibutyltin coordination polymer, {[(nBu2Sn)2(dmsa)]2?MeOH}n. In this coordination polymer,the coordinated methanol molecules are found, thus the corresponding host-guest chemistryand molecular reorganization in this complex are considered.In conclusion, through selecting different organotin compounds and differentmercapto-carboxylate ligands, through self-assembled reactions, we can obtain aimedorganotin compounds. It is not only make the environment of tin atom in theses complex tobecome complicated and variable, such as from four-coordinated tetrahedron tosix-coordination octahedron, but also affect the supramolecular structures in these complex,such as 1D linear structures, 2D networks and 3D frameworks. To lucubrate and probe themolecular and supramolecular structures of these complexes, we can not only understand thesecompounds' structures adequately, but also inspire us to explore their potential values in thefuture.