Coordinate Self-assembly,Crystal Structure,Property Study Of Organic Ligands With N And Organotin Complexes And The Preliminary Study Of Electrochemistry

Organotin complexes have a wide variety of structures,and are widely used as catalysts,heat stabilizers,fungicides,antifouling coatings and wood preservatives.The molecular and supramolecular structures and bioactivity of organotin complexes,especially anticancer activity have become one of the hottest research point.However,there are few reports focused on the molecular recognition ability,the luminescent and electrochemical properties of the organotin complexes.In this paper,we synthesized twelve novel organotin complexes by the reactions of mono-alkyl stannate,di-alkyltin oxide,tri-alkyltin hydroxide,tetra-alkyltin with carbazole carboxylic acid,aromatic imide carboxylic acid,ferrocene dicarboxylic acid based on the former research.All the organotin complexes were characterized by elemental analysis,IR and NMR,and their crystal structures were determined by X-ray single crystal diffractometor.Some organotin carboxylates owning potential molecular recognition ability were found,and the bond lengths of tin atoms and carboxyl oxygen atoms were compared.The luminescent property,anticancer activities and electrochemical properties of the representative organotin complexes were investigated.This paper contains the following work:1: Two carbazole carboxylate ligands(HL~1 and HL~2)were synthesized by the reactions of carbazole with bromoacetic acid and 3-bromopropionic acid.The drum-like organotin complexes 1,2 and 3 were obtained using ligands HL~1 and HL~2 to react with mono-(p-tolyl)stannate,mono-phenyl stannate and mono-n-butyl stannate.They contain a central six-core Sn6O6 stannoxane held together by six substituted carboxylate peripheries,and they are all supramolecules,in which complex 2 has potential molecular recognition ability.In contrast to the average bond lengths of Sn-O,the effect of the hydrocarbyl group on the Sn-O coordination in the Sn6O6 core is n-butyl>phenyl?p-tolyl.Luminescent results show that complexes 2 and 3 exhibit strong fluorescence properties.The anti-tumour activity for 1 to three kinds of tumor cells was studied preliminarily.2: The carboxylate ligand HL3 was synthesized by the reactions of 1,8-naphthalene anhydride with aminoacetic acid.The ladder-like organotin complexes 4,5 and 6 were obtained using ligands HL~1 and HL3 to react with dicyclohexyltin oxide and dibenzyltin oxide.They contain a central dimeric tetraalkyldistannoxane Sn2O2,and they are all supramolecules,and complexes 4 and 5 have potential molecular recognition ability.In contrast to the average bond lengths of Sn-O in 4-6,the inhibition of the hydrocarbyl group of dihydrocarbyltin oxide on Sn and O coordination in the short ladder Sn4O4 is phenyl>benzyl>cyclohexyl.Luminescent results show that complex 4 exhibits strong fluorescence property.The anti-tumour activity for 5 to three kinds of tumor cells was studied preliminarily.3: The carboxylate ligand HL4 was synthesized by the reactions of 1,8-naphthalene anhydride with m-aminobenzoic acid.The “U-shaped” organotin complexes 7 and 8 were obtained using ligands HL3 and HL4 to react with diphenyltin oxide and di-n-butyltin oxide.They contain a six-coordinated tin atom center bridging by two hydroxyl groups and two ligands.In contrast to the average bond lengths of Sn-O in 7 and 8,the blocking effect of the hydrocarbyl groups in the dialkyltin oxide on the tin-oxygen coordination is phenyl>n-butyl.Luminescent results of 4 and 5 show that the fluorescence of 1,8-naphthalene anhydride was quenched by diphenyltin oxide and di-n-butyltin oxide.4: The composite 9 was first obtained using ligand HL4 and 1,8-naphthalene anhydride to react with tri-phenyltin hydroxide.It is a composite formed by ?…? stacking of naphthalene ring in the triphenyltin carboxylate and 1,8-naphthalene anhydride,and this is the first case of organotin carboxylate complex composited with ligand.A monomer complex 10 in which tri-phenyltin hydroxide connects with coordinated water also obtained during the experiment.Luminescent result shows that 9 has stronger fluorescence property in comparison with ligand.5: The carboxylate ligand H2L5 was synthesized by the reactions of ferrocene and acetic anhydride.Crystals 11 and 12 were obtained using ligand HL5 to react with tetra(p-tolyl)tin,.The crystal structures show that 11 is tetra(p-tolyl)tin,and 12 is a polymer in which Fe atom connects the two toluene ring of 11.The crystal structure of complex 12 was preliminary solved.6: The electrochemical properties of the representative organotin complexes 1 and 5 were characterized by cyclic voltammetry,and their electrocatalytic reduction ability to H2O2 was studied preliminarily.A composite of Co/N/GR(GR=graphene)was synthesized and its electrochemical properties were tested.It is found that Co/N/GR composite had good ORR(oxygen reduction reaction)activity and may be used as an efficient and inexpensive electrocatalyst for ORR.