Synthesis And Study The Optical And Electrical Properties Of The N-containing Heterocyclic, Carboxylic(Sulfonic) Ligands And Their Metal Compounds

In recent years, coordination compounds have attracted considerable attention due totheir intriguing structural topologies and potentials to be employed as functional materials influorescence, catalysis, adsorption, nonlinear optics and magnetism. The design andconstruction of multi-dimensional, multi-nuclear coordination compounds via assemblyreactions of metal ions with functional ligands is one of the hottest research topics. Organicligands are important elements when constructing the coordination compounds. Functionalligands not only affect the synthesis of coordination compounds, but also their structures,stability and performances. In this dissertation, we chose the4-（8-hydroxyquinoline-5-azo）-benzensulfonic acid （H₂QBS）,2-（1H-imidazol-1-yl） aceticacid （Hima）, o-methacrylamidobenzoic acid （o-MAABA） to react with4,4’-bpy,1,10-Phen and metal ions. Finally, a series of coordination compounds and coordinationpolymers were obtained. Based on the structural characterizations of the correspondingcompounds, their chemical and physical properties, such as photoluminescence and UV-visspectra were investigated. Moreover, compounds with good solubility were selected andmemory devices based on these compounds were fabricated to study their memory effects.These results were briefly described as follows:1. The reaction between metal salts and H₂QBS gave rise to five coordinationpolymers:[Na₂（QBS）（H₂O）2]_n（1,3D framework）,{[Pb（QBS）（DMSO）]·2（ⁱPrOH）}_n（2·2i^PrOH,2D layer）,{[Zn（QBS）（DMSO）]·2DMSO}_n（3·2DMSO,1D chain）,[Mn（QBS）（ⁱPrOH）（DMSO）]_n（4,1D ladder） and [Cd₂（QBS）₂（DMSO）₂（H₂O）₄]_n（5,1Dchain）. These coordination polymers were characterized by elemental analysis and IRspectroscopy and X-ray diffraction. Their photo-stability was also studied by irradiation ofdifferent light sources （450nm,365nm and254nm）. Under blue light （450nm） and365 nm light, the colors of all compounds were well preserved and absorption spectra showedslightly changes. However, after being irradiated under higher energy UV light （254nm）,the coordination between metal ions and ligands was disassociated and therefore the colorfaded. Furthermore, the electronic memory performance of H₂QBS and compound3wasstudied, and both of them exhibited stable binary WORM behavior.2. The reaction between metal salts, o-MAABA and1,10-Phen gave rise to sixcoordination compounds: Zn（o-MAABA）₂（Phen）（6, mononuclear structure）,[Cd（o-MAABA）₂2H₂O]₂（7, binuclear structure）,{[Pb₂Cl（o-MAABA）₂（Phen）₄] Cl}2H₂O（8·2H₂O, binuclear structure）,[Pb（NO₃）（o-MAABA）（Phen）]_n（9,1D chain）,Mn₂Cl₃（Phen）3（o-MAABA）（H₂O）0.5（10, binuclear structure） and[Cu₂（Phen）₂（OH）₂]₂（o-MAABA）（11, binuclear structure）. These compounds werecharacterized by elemental analysis, IR spectroscopy, X-ray diffraction and theirphotoluminescent properties were studied. Solid-state room temperature luminescencespectra showed emission bands of compound6located at524nm （λex=352nm）;compound7at452nm （λex=330nm）; compound9at479nm and584nm （λex=390nm）and compound10at494nm （λex=423nm）, which are mainly assigned to theLigand-Metal Charge Transfer （LMCT）. Furthermore, electronic memory ofP（o-MAABA）-Cu（Phen）Cl₂was studied, showing stable binary WORM behavior.3. The reaction between metal salts, Hima and4,4’-bpy gave rise to sevencoordination polymers:[Pb₃（imaH）₂Cl₆]_n（12,2D layer）,[Pb（ima）₂（NO₃）₂]_n（13,1D chain）,[Li₂H（ima）₂（H₂O）₂Cl]_n（14,1D chain）,[Zn（imaH）（ima）Cl]_n（15,1D chain）,[Cd（imaH）Cl₂]_n（16,1D chain）,[M（ima）₂]_n（（17, M=Fe;18, M=Co）,2D layer）,[Pb₂（4,4’-bipy）（ima）（NO₃）₃]_n（19,3D framework） and [Ag₄（4,4’-bipy）₃（ima）₂（NO₃）₂（H₂O）₂]_n（20,3D framework）. These coordination polymers were characterized by elemental analysis, IRspectroscopy and X-ray diffraction. Among them,12,15,16,19and20exhibit goodphotoluminescence properties. Solid-state room temperature luminescence spectra showedemission bands of compound12located at455nm （λex=390nm）, compound15at425nm （λex=390nm）, compound16at550nm （λex=390nm）, compound19at552nm （λex=346nm） and compound20at444nm （λex=369nm）, which are mainly assigned to theLigand-Metal Charge Transfer （LMCT）.4. A functional polymer, PAzo-py, was designed and synthesized, which wasassembled with Cu（Phen）Cl₂and Mn（Phen）₂Cl₂before spincoating into films and then its memory performance was studied. The memory characteristics of ITO/PAzo-py/Al,ITO/PAzo-py-Cu（Phen）Cl₂/Al and ITO/PAzo-py-Mn（Phen）₂Cl₂/Al were tested, and theirmemory behaviors were found be different. The storage performance of ITO/PAzo-py/Alshowed the binary electronic memory behavior, while ITO/PAzo-py-Cu（Phen）Cl₂/Al andITO/PAzo-py-Mn（Phen）₂Cl₂/Al showed ternary behaviors and thus our “2+1” design ideahas been realized, namely, ensuring the performance of original material not affected andwhen a new memory element was introduced, ternary storage could be obtained andhigh-density storage could be realized.