Synthesis, Structure And Performance Of The Complexes With Alkylenedithiomethylene Malonic Acid As Coordination Agent

As the carboxyl complexes have special properties and diversiform structure, thesecomplexes have extensive potential application in many fields such as magnetics, catalyst,molecule carriers, gas storage and ergonomics. So the study of the complexes andcoordination polymers enriched the study of the theories. These compounds have the potentialapplication in many fields. In this research, two novel compounds in which alkylenedithiomethylene Malonic acidact as the main coordination agents and the compounds containing N atom (such as pyridine,Phenanthroline Ethanediamine and 4,4'-Bipyridinyl) act as the associating coordination agentshave been synthesized by the means of solution and solid-liquid diffusing reactions. 9coordination complexes and polymers have been designed and synthesized in which thetransition metals Cu(II) and Zn(II) acted as the centre ions. These compounds have beencharacterized by X-ray single crystal diffraction analysis, and some properties of them havebeen tested and analyzed.Four complexes were constructed with copper ion and 2-[1,3-Dithiolan-2-ylidene-malonic acid (dyma): Cu(Hdyma)₂(en)₂ (2-1), [Cu₂(dyma)₂(phen)₂]·4H₂O-·2DMF(2-2), [Cu(dyma)(py)₂]n (2-3) and [Cu(dyma)(H₂O)·H₂O]n (2-4). These complexes have beencharacterized by FT-IR spectroscopy and temperature-changing magnetic susceptibility. Allstudies proved that the novel coordination agent (dyma) was a tetra-dentate molecule when itcoordinated with the copper ions, and the binuclear part Cu₂O₂ acted as the sub-unit (SBU).As a result, the 1D polymer(2-1) was obtained. Three complexes (2-1, 2-2 and 2-3) with thedifferent structures were constructed when the N atom containing agents participate in thereactions.Four complexes were constructed with Zinc ions and dyma: [Zn(phen)₂(H₂O)₂]-(dyma)(H₂dyma) (3-1), Zn(phen)₂(dyma) ·DMF·1/6H₂O (3-2), [Zn(py)₂(dyma)-(H₂O)]n·nH₂O (3-3) and [Zn₂(bipy)₂(dyma)₂H₂O]·3.5H₂O (3-4). Their T-IR spectroscopy andthe fluorescence were studied. It proved that the novel coordination agent dyma was veryimportant in constructing the polymers, which constructed different complexes (3-2, 3-3 and3-4) with different N-containing associate coordination agents. Dyma not only exhibiteddifferent coordination means, but also formed hydrogen bond each other to construct highdimensional complexes. A 3D coordination polymer,[Cu(en)2]?2[Cu(en)2(H2O)]?[Cu6(H2O)6(ddba)5Cu2(en)4]?Cl2?14H2O (4-1), which contained2D nano-holes was synthesized with (1,3-dithiotan-2,4-diylidene)bismalonic acid)(ddba) andEthanediamine. The rresult proved that there were three coordination ions: [Cu(en)2]2+,[Cu(en)2(H2O)]2+ and [Cu6(H2O)6-(ddba)5Cu2(en)4]4+. The copper ions showed four differentcoordination numbers and geometrical structures. 4 coordination, planar quadrangle;5coordination, tetragonal pyramid;6 coordination, octahedron;7 coordination, triagonalbipyramid. The coordination anion [Cu6(H2O)6(ddba)5Cu2(en)4]4-formed the 3D coordinationpolymer which contained the 2D nano-holes linked by covalence bonds, the sizes of thesehole were 11.306×12.134 ? in ab side and 9.213×12.134? in bc side. The hole unit containedone [Cu(en)2]2+ ion , two [Cu(en)2(H2O)]2+ ions, and fourteen H2O molecules. Thecoordination polymer was a super-molecular structure containing the host molecules and ionsand guest ones.The structure features and the rules of assembly of the complexes containing dyma werestudied and some disciplinary conclusions were concluded.