两种含有2,2′-bipy及[MoO_3]簇骼化合物的结构与谱学关系研究  

Study on the Relationship between Structure and Spectroscopy of Two Compounds Containing 2,2′-Bipy and[MoO_3 ]Cluster Skeletons

作　　者：张子明[1] 陈义平[1,2] 尤珠钗 苏柳钦 王昊[1] 孙燕琼[1] 

机构地区：[1]福州大学化学系,福建福州350108 [2]中国科学院物质结构研究所结构化学国家重点实验室,福建福州350002

出　　处：《光谱学与光谱分析》2013年第11期2953-2958,共6页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(21003020);国家人才培养基金项目(J1103303);结构化学国家重点实验室项目(20130015);福州大学科技发展基金项目(2010-XQ-09)资助

摘　　要：利用程序控温的水热合成法得到了两种含有2，2＇-bipy及[M003]簇骼的化合物：[（2，2＇-bipy）2（Mo03）3]。（工）和[（2，2＇-bipy）（M003）]n（11）。为了阐明这两个化合物结构与谱学的关系，通过XRD、FT-IR、热微扰2D-IR相关光谱、TG分析、SEM、高温红外分析、uV_visDRS光谱和固体荧光光谱研究手段进行研究，进而探讨结构与性能的关系。其XRD说明了化合物I和Ⅱ是纯物相；FTIR的特征振动频率和热微扰2D-IR相关光谱的响应峰与化合物I和Ⅱ的结构解析相一致，2D-IR的同步和异步相关光谱图还确定了化合物I和Ⅱ的钼氧簇骼振动强度随升温变化的先后顺序与高温红外解析相一致；通过TG分析和高温红外分析研究化合物I和Ⅱ的热稳定性；化合物I和Ⅱ的UV Vis DRS光谱显示在225～350 nm有宽的紫外吸收谱带；化合物I和Ⅱ的固体荧光光谱分别在277和295nm的激发下得到的最强发射峰值分别为460和480nm。本文阐明了化合物I和Ⅱ的配位情况，揭示了价电子在分子中相应能级间跃迁的内在规律；还验证了弱相互作用力在配合物的结构框架中不但起稳定作用，而且在耐热性扮演重要的角色。Two compounds of molybdate with 2, 2＇-bipy and [ MoO3 ] ： [ （ 2, 2＇-bipy）2 （ MoCh ）3 ]n （ I ） and [（ 2, 2＇-bipy） （MOO3）]n （ II ） were successfully synthesized by hydrothermal synthesis method with programmable temperature control. In order to clarify the relationship between the structure and spectroscopy of these two compounds, both of them were characterized by means of X-ray powder diffraction （XRD）, Fourier transform infrared speetra（FTIR）, thermal perturbation 2D-IR correla tion spectrum （2D-IR COS）, thermogravimetrie analysis（TGA）, scanning electron microscopy（SEM）, High temperature infra red analysis, UV-Vis DRS adsorption spectra and solid fluorescence spectrum to investigate the relationship between structure and properties of the title compounds. The powder XRD patterns of the complexes are well matched with the simulation based on single-crystal analysis, which indicate that compound I and [I are in a pure phase. The characteristics of vibration frequency of FTIR and thermal perturbation relative spectral response of 2D-IR peak is consistent with thecompound I and I] structure a nalysis. The synchronous and asynchronous correlation 2D-IR spectra of compounds also identified the compounds I and ]1 mo lybdenum-oxygen cluster skeletons sequencing of vibration intensity change with temperature consistent with the high tempera ture infrared analysis. Through the TGA and high temperature infrared analysis it was found that the decomposition temperature was more than 300 ℃ and maximum weight losses rates above 800 ℃, which suggest that they have good thermal stability. Ac cording to the UV-Vis DRS spectrum of the compound I and Ⅱ there exists a wide ultraviolet absorption band in a range of 225 to 350 nm. The compound I and Ⅱ steady-state fluorescence spectrum under the excitation of 277 and 295 nm respectively re vealed compound I and Ⅱ have the strongest emission peak at 460 and 480 nm respectively. This paper illustrates the coordina tion situat

关 键 词：钼酸盐 光谱分析 晶体结构 二维相关光谱 

分 类 号：O657.3[理学—分析化学] O614[理学—化学]