Synthesis, Characterization, Crystal Structure And Property Study Of Organotin(?) Carboxylates Based On Amide Carboxylic Acids

Organotin carboxylates own a wide variety of structures, and they are widely usedin catalysis,thermal stability, sterilization, anti-fouling and wood preservation etc. Themolecular and supramolecular structures oforganotincarboxylates, biological activity,especially anticancer activity of them have become the hotspot of research. However, themacrocyclic structure of organotin carboxylates and their potential ability to selectivelyrecognize, to afford model complex that mimic biological systems is rarely explored.In this paper, eleven organotin carboxylates were synthesized by the reactions ofdi-n-butyltin oxide andtriphenyltin hydroxide with aromatic imide carboxylic acidligands.Novel organotin macrocyclic structures are included in the synthesizedcomplexes, and applied to the research of molecular recognition system.All the complexeswere characterized by elemental analysis,1H NMR,13C NMR and FT-IR spectroscopy, andthe structures of the complexes were determined by single crystal X-ray diffractionanalysis.The luminescent property and antitumour activities of complexes owningmacrocyclic structure were preliminary studied. And the UV-Vis spectrum and thermalstability were selectively surveyed for some complexes. The dissertation contains thefollowing works:1. Two amide carboxylate ligands (H2L1/H2L2) were synthesized by the reactions ofpyromellitic dianhydride/1,4,5,8-naphthalenetetracarboxylic dianhydride with glycine.Organotin macrocyclic complexes of rectangular box structure1and2were obtained usingthe ligands to react with di-butyltin oxide respectively. After a series of characterizations, theselective molecular recognition property of them towards aromatic guest molecules werefurther studied. Fluorescence test results showed that complexes1and2have strongfluorescence activity. And a preliminary study of the anti-tumour activity for1to three kindsof tumor cells revealed1has good anticancer activity.2. H2L3was designed and synthesized by the reaction of3,4,9,10-Perylenetetracarboxylic dianhydride and amino-acetic acid. With the complexationwith di-butyltin oxide, a centrosymmetric macrocycle containing nona-nucleareight-fold-ladder-like organo-oxotin cluster (complex3) was obtained. Complex3showshigh luminescent and antitumour activities.3. Di-nuclear centrosymmetric dicarboxylate ring (complex4) was synthesized by thereaction of di-butyltin oxide and H2L4(obtained in the lab). Through the reaction of phthalicanhydride with5-aminophthalic acid, we got H2L5. And a trinuclear tricarboxylate macrocycle (complex5) was synthesized by the reaction of di-butyltin oxide with H2L5. Thermal analysessuggest that complexes4and5have good thermally stability. Besides that,4and5show highanti-tumour activity.4. HL6/HL7was produced by the reaction of benzo[de]isochromene-1,3-dione andglycine/3-aminobenzoic acid. Using them to react with triphenyl stannic hydroxide, we gottwo monomer organotin carboxylates (6and7). After a series of characterizations, themulti-dimensional structures of them are discussed in detail. Ligand HL8was synthesized bythe reaction of phthalic anhydride and p-aminobenzoic acid. Monomers8and9were obtainedby the reactions of di-butyltin oxide with HL6and HL8. Complexes8and9are dibutyltincarboxylates possessing crystallographically imposed two-fold symmetry. After a fullcharacterization, we discussed the multi-dimensional structures of them in detail.5. Complexes10and11were synthesized by the reactions of di-butyltin oxide withligands HL7andHL9. HL9was obtained by the reaction of naphthaleneanhydride and p-aminobenzoic acid. Complexes10and11are dimeric carboxylatetetraorganodistannoxanes and show a “ladder-like” molecular structure. After a series ofcharacterizations, the multi-dimensional structures of them are discussed in detail.