Self-assembly Of Luminous Organotin(?) Complexes: Synthesis,Structural,Crystal Structure,Preliminary Property And Biological Activities

The self-assembled organotin carboxylate is provided with a brand-new structure,as well as catalytic,anti-cancer,fluorescence and other properties.Therefore,the research on organotin carboxylate has an important theoretical signifiicance and potential application prospect.By choosing the carboxylate ligands with large conjugated ?-bond structure or rigid plane structure,this paper has designed and synthesized a series of organotin carboxylates,determined the crystal structure through IR,1H,13C,119Sn NMR and X-ray single crystal diffraction,studied the luminescence and anti-cancer activity,and found that some of them were provided with stronger fluorescence property,thus laying a foundation for the positioning and tracking function of organotin carboxylate anti-cancer drugs in the body.The main work is as follows:1.Synthesize the one-dimensional polymer chain 1 through the self-assembly of ligand HL1 and triphenyltin hydroxide.In 1,Sn-O bond make the polymer form 2D network structure,which is made up of 30-membered rings.The size of the 30-membered ring channel is 7.669 A x 8.393 A.The fluorescence test results show that,complex 1 is provided fluorescence activity and longer life span?2.23 ns?;the biological activity test results indicate that complex 1 has a strong inhibitory effect on HT1080 tumor cells?IC50 value:1.064 ?g/mL?;2.Synthesize the hexa-coordinate organotin monomer molecules 2 and 3 by the self-assembly of HL² and HL³ with?C6H11?2SnO.In 2,intermolecular hydrogen bond C-H...O and ?…? interaction of aromatic ring made the big ring between the molecules,and further formed 3D supramolecular structure with cavity.The fluorescence test results show that,complexes 2 and 3 have fluorescence activity and longer life span?1.86 ns and 1.98 ns?,so it is expected that complexes 2 and 3 can be used in the research on luminescent materials owing to the higher yield and simple synthesis conditions;3.Synthesize the drum-shaped complex 4 based on the self-assembly of ligand HL⁴ and CH3C6H4SnOOH.Six tin atom has the same chemical environment with a octahedral configuration.In 4,C-H...? interaction betweent molecules made it formed 2D network structure.The fluorescence test results show that,complex 4 is provided with a very good fluorescence activity,and it also has inhibition effect on the three kinds of tumor cells,MCF-7,HepG2 and skov-3 after biological activity test?IC50 value:0.36?g/mL,2.22 ?g/mL and 1.08 ?g/mL,respectively?.It is expected that complex 4 can clinically contribute to the positioning and tracking function of organotin carboxlate anti-cancer drugs in the body owing to its good fluorescence activity and strong inhibition?0.36 ?g/mL?on MCF-7 tumor cells;4.Explore the synthetic route and reaction conditions to synthesize the organotin complexes 5 and the derivatives 6,7,8,9,provide a precursor for the study of anti-cancer and fluorescence activity of organotin complexes;5.Synthesize di-?o-CH₃OC₆O₄?SnO derivatives product 10 and 11,and further obtain complexes 8 and 9 by the reaction though with p-toluenesulfonic acid and adipic acid.The results of X-ray single crystal diffraction show that,complex 13 has a very good large ring structure.The fluorescence test on complex 13 also shows that it is provided with a very good fluorescence activity and long life span?1.43 ns?;6.Synthesize the mixed hydrocarbon organotin complex to get complex 14.Then react with PhMgCl Grignard reagent to obtain complex 15.The results showed that Grignard reagent react with tin atom in preference to ester group,and large ester group of Sn-C fracture rather than relative high polarity Sn-Cl bond.In addition,the complexs formed big ring between adjacent molecules by weak Sn-Cl action,and ring size is 7.669 A × 8.393 A.The fluorescence test results show that complex 15 has the very good fluorescence activity and long life span?2.58 ns?.We hope complex 15 can be clinically conducive to the synthesis of pharmaceuticals owing to its high yield,convenient single crystal output,as well as the relative better lipid solubility for halogen containing.