Study on the Relationship between Structure and Spectroscopy of Two Compounds Containing 2,2′-Bipy and [MoO3] Cluster Skeletons
ZHANG Zi-ming1, CHEN Yi-ping1, 2*, YOU Zhu-chai1, SU Liu-qin1, WANG Hao1, SUN Yan-qiong1
1. Department of Chemistry, Fuzhou University, Fuzhou 350108, China 2. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
Abstract：Two compounds of molybdate with 2,2′-bipy and [MoO3]: [(2,2′-bipy)2(MoO3)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 spectra(FTIR), thermal perturbation 2D-IR correlation spectrum (2D-IR COS), thermogravimetric analysis(TGA), scanning electron microscopy(SEM), High temperature infrared 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 Ⅱ 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 the compound Ⅰ and Ⅱ structure analysis. The synchronous and asynchronous correlation 2D-IR spectra of compounds also identified the compounds Ⅰ and Ⅱ molybdenum-oxygen cluster skeletons sequencing of vibration intensity change with temperature consistent with the high temperature 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. According 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 Ⅰand Ⅱsteady-state fluorescence spectrum under the excitation of 277 and 295 nm respectively revealed compound Ⅰ and Ⅱ have the strongest emission peak at 460 and 480 nm respectively. This paper illustrates the coordination situation of these two compounds, and reveals the inherent law of valence electrons in molecule energy level transition. In the meantime it was verified that the weak interaction not only plays a role of stability in the frame of the structure of the complexes, but also plays an important role in heat resistance.
张子明1, 陈义平1, 2*，尤珠钗1, 苏柳钦1，王 昊1，孙燕琼1 . 两种含有2,2′-bipy及[MoO3]簇骼化合物的结构与谱学关系研究 [J]. 光谱学与光谱分析, 2013, 33(11): 2953-2958.
ZHANG Zi-ming1, CHEN Yi-ping1, 2*, YOU Zhu-chai1, SU Liu-qin1, WANG Hao1, SUN Yan-qiong1 . Study on the Relationship between Structure and Spectroscopy of Two Compounds Containing 2,2′-Bipy and [MoO3] Cluster Skeletons. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2013, 33(11): 2953-2958.
[1] Chen Xiangyi, Chen Yiping, Chai Feng, et al. Journal of Molecular Structure, 2013, 1035 (3): 462. [2] Chen Xiangyi, Chen Yiping, Xia Zemin, et al. Dalton Transaction, 2012, 41 (5): 10035. [3] Chen Yiping, Wang Yeqin, Zhang Hanhui, et al. Journal of Molecular Structure, 2008, 883-884(7): 103. [4] WANG En-bo, LI Yang-guang, LU Ying, et al(王恩波，李阳光, 廘 颖，等). DUOSUAN HUAXUE GAILUN(多酸化学概论). Changchun: Northeast Normal University Press(长春：东北师范大学出版社), 2009. 262. [5] Ben-Daniel R, Neumann R. Angewandte Chemie International Edition, 2003, 42(1): 92. [6] Gregory A, Rik V D, Tatjana N P V. Inorganic Chemistry, 2011, 50(22): 11552. [7] Wu Qing, Wang Ju, Zhang Ling, et al. Angewandte Chemie International Edition, 2005, 44(5): 4048. [8] Liu T B, Diemann E, Li H L, et al. Nature, 2003, 426(11): 59. [9] Jean-Daniel C, Pierre M, Anne D. Inorganic Chemistry, 2009, 48(13): 6222. [10] Pamela J Z, Robert C H, Jon Z. Chem. Mater., 1997, 9(9): 2019. [11] Dai Limei, You Wansheng, Li Yangguang, et al. Inorganic Chemistry Communications, 2010, 13(3): 421. [12] Marta A, Tatiana R A, Margarida M A, et al. Inorganic Chemistry, 2010, 49(15): 6865. [13] Noda I. Applied Spectroscopy, 1993, 47(9): 1329. [14] Noda I. Journal of Molecular Structure, 2010, 974(9): 3. [15] Fang Lei, Yan Bing, Chen Haohong. Journal of Solid State Chemistry, 2008, 181(7): 2845. [16] CAO Xi-zhang, SONG Tian-you, WANG Xing-qiao(曹锡章，宋天佑，王杏乔). Inorganic Chemistry Ⅲ(无机化学，第3版). Beijing: Higher Education Press(北京：高等教育出版社), 1994. 968.
