Study On The Structure And Properties Of Metal Complexes Based On The Tartaric Acid Derivatives

Metal organic complexes are an important class of new materials in the vast field of metal organic materials.Metal organic complexes are some of the most promptly rising fields in chemical and material sciences,not only due to the fascinating structural topologies but also because of their potential in various applications.Metal organic complexes are currently eliciting noteworthy attention for their prospective applications in gas storage,purification,molecular sensing,drug delivery,biomedicine,hotoluminescence,molecular based magnetisms and photo catalysis.So the study of metal organic complexes has an important theoretical and practical significance.In this paper,three kinds of metal organic complexes were synthesized by using three kinds of tartaric acid derivatives as ligands:32-membered copper（II）complex based on[Cu₄O₃X]cube,2,3-diacetyl pheny tartaric acid derivatives transition metal complexes and 2,3-diacetyl-p-toluene tartaric acid rare earth complexes.The 10 novel complexes have been obtained,characterized by X-Ray single crystal diffraction,infrared spectroscopy,elemental analysis,powder diffraction and their properties have been studied like as the fluorescence,magnetic properties,photocatalytic,electrocatalytic.The main conclusions are as following:1.The first 32-membered Cu（II）cluster（Cu₄Cl（OH）₃）₈（BI）₂₄（HBI）₆（H₂O）_3.5（DMF）_4.5]⁸⁺·8OH^-·4H₂O·3.5DMF（1）（HBI = benzimidazole）with a big cubic structure consisting of eight small cubical cores exhibited a higher photocatalytic activity for the degradation of rhodamine B（～99%）dye within 15 min under UV light irradiation,effective electrocatalytic activity for nitrite reduction and strong antiferromagnetic interactions among the Cu（II）centers.2.2,3-diacetyl pheny tartaric acid and 2,3-diacetyl-p-toluene tartaric acid as ligands reacted with transition metal salt to obtain three 2,3-diacetyl pheny tartaric acid derivatives transition metal complexes:[M（DBTA）（DMF）（H₂O）4][M=Ni（2）,Co（3）]（H2DBTA=2,3-diacetyl pheny tartaric acid）and[Cu（HDTTA）₂（DMF）（H₂O）]-DMF-H₂O（4）（H₂DTTA=2,3-diacetyl-p-toluene tartaric acid）.X-Ray crystal diffraction analysis showed that all the complexes were zero dimensional structures of polar space group P21 and could form one-dimensional and two-dimensional planar structure through intermolecular hydrogen bonds.The solid fluorescence determination showed that the complex 2,3 had strong fluorescence.It may be attributed to the intermolecular hydrogen bond which made the structure more stable,thus reducing the overall non-radiative decay rates.But,the fluorescence of complex 4 was quenched because of the introduction of the Cu²⁺ at room temperature.The study of magnetic property showed that the complex 2 and complex 4 had ferromagnetism while complex 3 had antiferromagnetism.The different magnetism of isostructuralism phenomenon was due to the Co²⁺ions in six coordination octahedron with larger spin-orbit coupling,which had high magnetic anisotropy.The study of photocatalytic property showed that complex 4 had a good adsorption effect on methylene blue dye.3.2,3-diacetyl-p-toluene tartaric acid reacted with Rare earth metal salt to abtain six complexes[Ln（DTTA）3（CH₃O）₃]n[Ln= Pr（5）,Ce（6）,Nd（7）,Sm（8）,Eu（9）,Gd（10）]（H₂DTTA=2,3-diacetyl-p-toluene tartaric acid）.X-Ray diffraction analysis showed that they were isomorphic with infinite one-dimensional chain structure of polar space group R3.Each ligand bridges two Ln³⁺ through terminal carboxyl group and each Ln³⁺ ion showed a 9-coordinated tri-capped trigonal prism.The solid fluorescence spectra showed that the complex 9 emitted strong red light at room temperature,which originated from the rare earth Eu³⁺ ion.Complex 5,7,8 also had strong fluorescence originated from the ligand,while complex 6 and 10 were quenched.The study of magnetic property measurement showed that complex 5 and complex 9 were antiferromagnetic interaction among metal ions while complex 10 displayed ferromagnetic interaction among metal ions at room temperature.The study of AC susceptibility at low temperature showed that there was no obvious magnetic relaxation process in the complexes.