Study On Syntheses And Structural Characteirzation Of Metal-halide Modiifed By Organic Molecules

For the past few years, the study on the novel coordination polymers is of currenthot topic due to the structural diversity and the potential functional properties inoptics, adsorption and magnetism. In situ ligand synthesis has got considerableattention as an effective approach towards the crystal engineering of coordinationpolymers. Some unusual organic ligands have been synthesized successfully, whichare inaccessible or not easily obtainable via conventional methods. The synthesis ofcoordination polymers have obtained great success in the past several decades. Largenumbers of coordination polymers, which have novel architecture and particularproperties, emerge in endlessly. Especially the detection and study of in situ ligandsynthesis bring more mulriple synthesis methods and more abundant structure aboatcoordination compounds.Based on above mechanism, we synthesized8new coordination polymers by thesimple hydrothermal self-assemblies between metal halide, different kinds of organicamine （just like4,4′-Bipiperidyl dihydrochloride,1,3-Bis（4-piperidyl）propane, and soon） and solvent. By now, we have resolved all the single-crystal structure of them, andcharacterized them by IR, XRD and also fluorescence spectra. According to thedesign and processes of the experiment, the paper includes five chapters.The first chapter is introduction, in this part, we introduced the concepts,histories and sorts of coordination polymers, emphasized to introduce the mechanismand classification. At the end of this part, we explained the research significance,innovation and the results in this paper.In the second chapter, there are only three pages in this part, we introduced theprinciple, methods and the reagent very concisely.In the third chapter, under the hydrothermal conditions, by employing thealkylation reactions between N-heterocyclic ligands with alcohol molecules, four neworganically templated iodo（bromo）cuprates（I） and one iodoplumbate（Ⅱ） coord-ination polymers were synthesized, with the raw material of organic amine are all aliphatic. They are:[H₂bp]₂[Cu₂I₆]（1）,[tmbp][Cu₂I₄]（2）,[tmbp][Cu₂Br₄]（3）,[tmbpp]₂[Cu₄I₈]·2H₂O（4）,[H₂（dmbpp）][Pb₂I₆]（5）. Compound1is a H₂bp²⁺-templatediodocuprate（I）. It crystallizes in space group P21/c, and the asymmetric unit is foundto be composed of one Cu（I） ions （Cu1）, three types of I-ions （I1, I2, I3） and one H₂bp²⁺cation. Compound2is a tmbp²⁺-templated iodocuprate（I）. Compound3is atmbp²⁺-templated bromocuprate（I）. X-ray analysis revealed that both compounds areisostructural to each other, so only the structure of compound2as the representativewill be described here. Compound2crystallizes in space group Pnnm, and theasymmetric unit is found to be composed of one Cu（I） ion （Cu1, occupancy ratio:0.5）,two I-ions （I, I2; occupancy ratio:0.5for each） as well as a quarter molecule oftmbp²⁺cation. Compound4is a tmbpp²⁺-templated discrete iodocuprate（I）. Itcrystallizes in space group P421/c, and the asymmetric unit is found to be composedof one Cu+ion （Cu1）, two types of I-ions （I1, I2）, a half molecule of tmbpp²⁺cationas well as one lattice water molecule （Ow1, occupancy ratio:0.5）. Compound5is admbpp²⁺-templated chained iodoplumbate（II）. It crystallizes in space group P21/n, andthe asymmetric is found to be composed of two types of Pb₂+ions （Pb1, Pb2）, sixtypes of I-ions （I1, I2, I3, I4, I5, I6） and one dmbpp²⁺cation.they have beencharacterized by various ways: Elemental analysis, IR and solid-statephotoluminescence property have been studied on compounds1-5. As a result, theyall have good fluorescence emissions.The fourth chapter is similar to the third, the only different is that, we replacedfatty amine with aromatic amine synthesized coordination polymers6-8, they are：[PbI₂（bpyp）]（6）,[CdI₂（bpyp）]（7）（bpyp=1,3-Di（4-pyridyl）propane）,[Cu₂I₂（qhxo）]（8）（qhxo=5,6,7,8-Tetrahydroquinoxaline）, in both of the third and the forthchapter,we have comparing the syntheses and the structure of all the compounds, thenature of metal ion, the kind of ligands and pH value all effect on the finally products, while the definitive effect factor for different reaction is dissimilar.In the last chapter, we have gave a brief conclusion and some outlook in thisfield.