Research On Tin Compounds Based On Porphyrin And Amino Acid Schiff Base

Both porphyrin and Schiff base are functional nitrogen-containing organic ligands,and are widely used in materials,medicine,catalysis and other fields.It is an important subject of synthetic chemistry to modify the structure and properties of its metal complexes through the structural modification of ligands,and then expand its applications.In this paper,59 corresponding tin compounds were synthesized by using tetra(p-alkoxybenzene)porphyrin,tetra(p-carboxybenzene)porphyrin,L-glutamine Schiff base,L-asparagine Schiff base and m-aminobenzoic acid Schiff base as ligands.The structures of the compounds were characterized by NMR,IR,X-ray single crystal diffraction and other techniques.The crystal structures of 19 compounds were analyzed and the crystalline structures of the compounds were studied.Structural assembly,photophysical properties,electrochemical properties and anticancer activity.1.A series of tetra(p-alkoxybenzene)porphyrin tin compounds[4-(RO)TPP]SnL2(L=Cl,OH,R'COO)with axial ligands(L)of chlorine,hydroxyl and carboxyl groups were synthesized from tetra(p-alkoxybenzene)porphyrin[4-(RO)H2TPP,R=CH2CH3,CH2CH=CH2]prepared by Adler method.The crystal structures of[4-(CH3CH2O)TPP]Sn(OCOC6H4Cl-4)2 and[4-(CH3CH2O)TPP]Sn(OCOC6H4Cl-4)2 indicate that the atoms on the porphyrin ring are in the same plane,and that the tin atoms are N4O2Sn octahedral configurations coordinated by porphyrin nitrogen atoms and carboxyl oxygen with an axial O-Sn-O bond angle of 180°.2.A series of tetrakis[4-(trialkyltin-oxycarbonyl)phenyl]porphyrin 4-(R3SnOCO)4H2TPP(R=Ph,Cy,Bu,Ph(CH3)2CCH2)were prepared by solid-phase grinding method.The crystal structure of 4-(Cy3STiOCO)4H2TPP shows that tin atoms are tri-hydrocarbon and carboxyl coordinated C3OSn tetrahedral configurations,and intermolecular structures are arranged into one-dimensional supramolecular chain structures by Sn…O=C weak interaction.Compared with the ligand 4-carboxyphenylporphyrin,the UV-vis and fluorescence emission spectra of this series of compounds were almost the same,and the fluorescence lifetime changed little;the electrochemical properties showed that the reductivity was enhanced;the anticancer activity was significantly improved,among which the IC50 value of triphenyltin derivatives on MOF-7 cells reached 0.086±0.010 ?M.3.A series of diorganotin derivatives R2Sn[2-O-R'C6H3CH=N-CH(CH2CH2CONH2)COO]? R2Sn[2-O-R'C6H3CH=N-CH(CH2CONH2)COO](R=Me,Bu,Ph;R'=Cl,Br,OH,OMe,NEt2)of a-amino acid(L-glutamine,L-asparagine)salicylaldehyde Schiff base containing amide group were synthesized by by one-pot reaction.Schiff bases of L-glutamine or L-asparagine salicylaldehyde as ONO tridentate chelate ligands form O-C-C-N-Sn and N-C-C-C-O-Sn chelate rings with tin atoms.The tin atoms in the crystal show a five-coordinate triangular bipyramid configuration(C2NO2Sn)and an octahedral configuration(C2NO3Sn)in which amide oxygen or solvent oxygen participates in coordination.The dimers or multimers are formed by Sn…O hydrogen bonds between molecules,and two-dimensional or three-dimensional supramolecular structures are formed by N-H…O?O-H…O hydrogen bonds.The compound exhibits maximum absorption in the range of 275-310 nm and maximum emission in the range of 440-510 nm.Its fluorescence intensity is affected by the group connected to the organotin,and its law is Ph>Me>Bu.Some compounds have obvious anti-proliferative effects on A549,HeLa,HepG2,and GL261 cells.The IC50 value of glutamine salicylaldehyde Schiff base dibutyltin derivative on A549 is 0.33±0.07 ?M.4.A series of triorganotin compounds of 3-aminobenzoic acid Schiff base[3-(2-HO-R'C6H3CH=N)C6H4COO]SnR3?[3-(4-NC5H4CH=N)C6H4COO]SnR3 and[3-(CH3COCH2C(CH3)=N)C6H4COO]SnR3(R=Ph,Cy,Bu;R'is a variety of substituents)were synthesized by one bottle of three-component reaction.In the crystal structure,in addition to the monomer structure,the molecules also self-assemble into 44-membered macrocyclic tetramers and chain polymer structures through the coordination of phenol oxygen,pyridine nitrogen and ketone carbonyl oxygen.Tin atoms have tetrahedral and triangular bipyramidal configurations.there are the centrosymmetric R22(16),R42(22)and R64(34)macrocycle motifs formed by the O-H…O,N-H…O and C-H…O hydrogen-bonds.The maximum absorption occurs at 310 nm and emission occurs at 430 nm in the spectrum,indicating that the compounds have the potential to become fluorescent materials.This kind of compound has good anticancer activity,in which tributyltin 3-(salicylideneamino)benzoate has an IC50 value of 0.130±0.012?M for HeLa cells.In this paper,the synthesis,structure and properties of tin compounds based on porphyrin and amino acid Schiff base ligands were explored,and novel series of tin complexes were obtained,which enriched the contents of porphyrin and organotin compounds and laid an experimental foundation for further study of their applications.