【作者】 张良；

【导师】 谢闯； 朱振兴；

【作者基本信息】 天津大学 ， 化学工程， 2018， 硕士

【摘要】 本文以氯化铋和硫脲为反应物,应用反应溶剂筛选的方法,在以甲酸-水体系为反应溶剂中发现了一种新型的配位化合物。用缓慢蒸发法得到该新型配位化合物的单晶,结合红外分析和拉曼分析,应用单晶衍射分析得到DCBPB的单晶结构,其化学式为μ-二氯-[三氯(硫脲)二铋]-五氯(硫脲)铋盐(中文简称:七硫脲三氯化铋,英文简称:DCBPB),该晶体属于三斜晶系,P1空间群,晶胞参数为:a=7.0606(2)?,b=8.8106(4)?,c=16.3247(8)?,α=99.242(4)°,β=95.309(3)°,γ=105.856(3)°,Z=1。本文对DCBPB原料的合成及其单晶的生长条件进行了讨论,研究了反应溶剂甲酸水体系中甲酸与水的体积比,反应温度,反应物中氯化铋和硫脲的摩尔比对DCBPB纯度的影响,最终得到适宜合成DCBPB的反应条件。测定了DCBPB在甲酸水溶液(V/V=3:2)中的溶解度,并考查了在20°C,30°C,40°C甲酸水溶液(V/V=3:2)中恒温蒸发培养DCBPB单晶的情况。在对DCBPB晶体的性能检测方面,利用Kurtz-Perry粉末法测定其倍频系数,应用紫外可见近红外分光光度计、荧光光谱仪、热重分析仪分别研究了该晶体的光透过率、荧光性能、热稳定性。并定性分析了已知四种氯化铋与硫脲的配合物的分子结构与其晶体性能的关系。研究了DCBPB与β-三硫脲氯化铋(简称β-BTC)在溶液中悬浮相互转化过程,发现β-BTC在40°C甲酸水溶液(V/V=3:2)中转化成DCBPB的速率是DCBPB在40°C盐酸(pH=0.50)中转化成β-BTC的速率的5.33倍。本文上述研究内容尚未见文献报道。更多还原

【Abstract】 Crystals of a new organometallic nonlinear optical(NLO)compound have been successfully grown from formic acid aqueous solutions of thiourea and bismuth chloride by slow evaporation technique by means of reaction solvent screening.The molecule structure of the coordination is confirmed by SCXRD,FTIR,FT-Raman and elemental analyzer,and its molecular formula is di-μ-chloro-bis-[chlorotri(thiourea)bismuth(III)]-pentachloro(thiourea)bismuthate(III)(DCBPB).The SCXRD of DCBPB testimony proves it crystallizes in triclinic space group P1 with unit cell dimensions of a= 7.0606(2)?,b= 8.8106(4)?,c= 16.3247(8)?,α= 99.242(4)°,β= 95.309(3)°,γ= 105.856(3)°,Z=1.Firstly,in order to find out the suitable condition for DCBPB synthesis,we study the effect of reaction conditions,including reaction temperature,molar ratio of bismuth chloride and thiourea in reaction,volume ratio of formic acid and water in reactive solvents,on the purity of DCBPB.Solubility of DCBPB range 20°C to 40°C was determined by dynamic method,and DCBPB single crystals growth conditions were studied by constant temperature slow evaporation technique at 20°C,30°C,40°C.As to performance test for DCBPB,second harmonic generation(SHG)test was carried out by Kurtz-Perry powder method.UV-Visible spectrometer,fluorescence spectrophotometer,thermal gravimetric analyzer were used to determine its optical transmittance spectrum,fluorescence and thermal stability respectively.We discovered mutual transformation process between DCBPB and β-bismuth thiourea chloride(β-BTC)suspended in solution,the ratio of β-BTC converting into DCBPB in formic acid aqueous solution(V/V = 3:2)is 5.33 times as well as the ratio of DCBPB converting into β-BTC in hydrochloric acid(pH=0.50)at same 40°CNo similar reports to above research have been published in literatures up to date.更多还原