Synthesis, Structure And Property Study Of Organotin (IV) Complexes Based On Aromatic Acids

Organotin compounds are atracting more and more attention on account of their wide industrial, agricultural and pharmacal applications, as well as their various molecular and supramolecular structures. Among the organotin compounds, the study of organotin carboxylates goes deep most. Recent research indicates that the structures of organotin carboxylates mainly depend on the carboxylic ligands and organotin, especially on the numbers of organic substituent group of organotin compounds and the numbers of carboxyl and its relative location.In addition, the cordinating heteroatoms along with its relative location will also influene the structures of organotin carboxylates, making them more complicated. In all, through self-assembled reactions, organotin compounds and carboxylic acid derivative ligands will generate organotin carboxylates with complicated structures, which demonstrate entirely different molecular and supramolecular structures. With large amount of thorough research, we found that the studies on carboxylic derivative ligands combined by organic acid anhydride are fairly few, thus we selected this discuss to carry out a series of research. The main contributions of the thesis are as follows:1.4,6-H2L1, 2,5- H2L1, 4,6- H2L2, 2,5- H2L2, 4,6- H2L3, 2,5- H2L3 and 2,5- H2L4 were prepared by the Diels-Alder reaction of pyromellitic dianhydride with benzene, toluene, ethylbenzene, and isopropylbenzene, respectively. The self-assembly reaction of rigid aryl dicarboxylate （H2L ligands） with di-n-butyltin oxide, triphenyltin hydroxide and tricyclohexyltin hydroxide formed eleven organotin carboxylates. As follow: [（n-Bu₂Sn）₄（4,6-L1）O₂（OH）（OC₂H₅）]₂·2（C₂H₅OH） （1）, [（n-Bu₂Sn）₄（4,6-L1）O₂（OH） （OC₄H₉）]₂·2（C₄H₉OH） （2）, [（n-Bu₂Sn）₄（4,6-L2）O₂（OH）（OC₂H₅）]₂·2（C₂H₅OH） （3）, [（n-Bu₂Sn）₄（4,6-L3）O₂（OH）（OC₂H₅）]₂·2（C₂H₅OH） （4）, （Ph₃Sn）₂（2,5-L1）（C₂H₅OH）₂ （5）, （Ph₃Sn）₂（4,6-L1）（DMF）₂ （6）, （Ph₃Sn）₂（2,5-L2）（C₂H₅OH）₂ （7）, （Ph₃Sn）₂（4,6-L2） （H₂O）₂·（C₂H₅OH）·4H₂O （8）, （Cy3Sn）₂（4,6-L2）（DMF）₂ （9）, （Ph₃Sn）₂（2,5-L3）（C₂H₅OH）₂ （10） and （Ph₃Sn）₂（2,5-L4）（DMF）₂ （11）. Where 4,6- H2L1=4,6-dibenzoylisophthalic acid, 2,5-H2L1=2,5-dibenzoylterephthalic acid, 4,6-H2L2=4,6-bis（4-methylbenzoyl）isophthalic acid, 2,5-H2L2=2,5-bis（4-methylbenzoyl）terephthalic acid, 4,6-H2L3=4,6-bis（4-ethylbenzoyl） isoph- thalic acid, 2,5-H2L3=2,5-bis（4-ethylbenzoyl）terephthalic acid, and 2,5-H2L4=2,5-bis （4-iso- propylbenzoyl）terephthalic acid.2.H2L5 was prepared by the a lcoholys is reaction of pyromellitic dianhydride with ethanol. The self-assembly reaction of rigid aryl dicarboxylic acid （H2L5 ligands） with triphenyltin hydroxide and tricyclohexyltin hydroxide formed three organotin carboxylates. [（Ph₃Sn）₂（L5）]n （12）, [（Ph₃Sn）₂（L5） （H₂O）₂]·2（DMF） （13） and [（Cy3Sn）₂（L5）]·3（H₂O）（14）. Where H2L5=benzene-1,2,4,5-tetracarboxylic acid diethyl ester.3.2,5- H2L6 was prepared by the ammonolysis reaction of pyromellitic dianhydride with 4-nitro-phenylamine. The self-assembly of rigid aryl dicarboxylic acid （H2L6 ligands） with tricyclohexyltin hydroxide formed one organotin carboxylate. [（Cy3Sn）₂（2,5-L6） （DMF）₂]·2DMF·1.5C6H6（15）. Where 2,5-L6=2,5-bis（4-nitro-phenylcarbamoyl）terephthalic acid.4.H4L7 was prepared by the hydrolysis reaction of pyromellitic dianhydride. The self-assembly of rigid aryl tetracarboxylic acid （H4L4 ligands） with triphenyltin hydroxide and tricyclohexyltin hydroxide formed three organotin carboxylates. [（Ph3Sn）8（L7）₂ （HOCH2CH3）₂]n·2n（CH3CH₂OH） （16） [（Ph3Sn）4（L7）（DMF）4] （17） [（Cy3Sn）4（L7）（DMF）4] （18）. Where H4L7= benzene-1,2,4,5-tetracarboxylic acid.5.The self-assembly of semi-rigid aryl dicarboxylic acid （H2L8 ligands） with triphenyltin hydroxide and tricyclohexyltin hydroxide formed three organotin carboxylates. （Ph₃Sn）₂L8（C₂H₅OH）₂ （19）, （Ph₃Sn）₂L8（DMF）₂ （20） and [（Cy3Sn）₂L8]·2（C₂H₅OH）（21） Where H2L8=4,4’-（propane-1,3-diyl）dibenzoic acid.6.The self-assembly recatin of rigid aryl carboxylate （HL9 ligands） with triphenyltin hydroxide resulted （Ph2Sn）（L9）₂（DMF）（22）. Where L9=4-amino-benzoic acid; The self-assembly of rigid aryl sulfoacid（HL9 ligands） with di-n-butyltin oxide and triphenyltin hydroxid formed two organotin sulphonate. [（n-Bu₂Sn）₄（L10）₂O₂（OH）₂]（23）, [（Ph3Sn）3（CO3）L10（H₂O）₂]·（DMF）（24）. Where L10=4-amino-benzenesulfonic acid.