1. Department of Chemistry, Fuzhou University, Fuzhou 350002，China 2. State Key Laboratory of Structural Chemistry, Institute of Material Structure, Chinese Academy of Sciences, Fuzhou 350002，China
Abstract：Five novel organic-molybdenum phosphates with [(PO4)4MoⅤ6O15]12- cluster, Na·(H4TETA)3·(H3O)5·{Zn[(HPO4)2(PO4)2Mo6O15]2} (2)，(H2en)7·(H3O)4·{Cu[(HPO4)2(PO4)2 Mo6O15]2}·H2O (3)，(H3DETA)2·(H3O)3·{Co0.5[(HPO4)2(PO4)2Mo6O15]}·H2O (4)，[Co(H3TETA)]2{Co0.5[(HPO4)(PO4)3Mo6O15]}·3.5H2O (5) and (H3DETA)·(H3O)4·{Co1.5[(HPO4)2(PO4)2Mo6O15]}·0.5H2O (6)，have been synthesized. The relationship between their properties and structures was studied by using FTIR，NIR FT-Raman，UV-Vis DRS and fluorescence etc. In these compounds, every two [(PO4)4Mo6 O15] clusters are coordinated by a metal atom to form a {M[(PO4)4Mo6 O15]2} dimer. In compound 2, 3 and 4, {M[(PO4)4Mo6 O15]2} dimers are hydrogenbonded by the organic molecules and water molecules to form a three-dimensional expended framework, respectively. In compound 5 and 6, {Co[(PO4)4Mo6 O15]2} dimers are coordinated by [Co(H3TETA)] groups and [CoO4] tetrahedra to form a network, respectively. These characteristic vibrational frequencies of the molybdenum phosphates are related to the structure of these compounds. Three characteristic bands in UV-Vis DRS spectra of these compounds have to be attributed to the absorptions of Od→Mo, Oμ→Mo and O→M charge transfer, respectively. These compounds exhibit strong fluorescence emission bands at about 410 nm when excited by 240 nm，which are caused by Oμ→Mo charge transfer.
[1] Pope M T, Muller A. Angew. Chem. Int. Ed. Engl.，1991, 30: 34. [2] Noritaka Mizuno, Toshihiro Yamase, Eugenio Coronado et al. Chem. Rev., 1998, 98： 1. [3] ZHOU Yun-shan et al. International Journal of Inorganic Materials, 2001, 3: 373. [4] Philip Lightfood et al. Acta Cryst., 1996, C52: 1080. [5] XU Lin et al. Journal of Molecular Structure, 2000, 519: 55. [6] Mundi Linda A et al. Inorg. Chem., 1992, 31: 3050. [7] Mayer Linda A et al. Inorg. Chem., 1993, 32: 1579. [8] LIN Zheng-zhong ，ZHANG Han-hui，YANG Rong-sheng et al(林郑忠，张汉辉, 杨融生等). Spectroscopy and Spectral Analysis(光谱学与光谱分析)，2000，20(5)： 593. [9] LIN Zhi-hua, ZHANG Han-hui，GUO Chun-hua et al(林志华，张汉辉, 郭春华等). Spectroscopy and Spectral Analysis(光谱学与光谱分析)，2002, 22(5): 752. [10] SUN Rui-ging，LIN Zheng-zhong，ZHANG Han-hui et al (孙瑞卿，林郑忠，张汉辉等). Spectroscopy and Spectral Analysis(光谱学与光谱分析)，2003，23(3)： 465. [11] LIN Zheng-zhong，ZHANG Han-hui et al (林郑忠，张汉辉等). Chinese Journal of Structural Chemistry(结构化学)，2002，21(1)： 42. [12] LIN Zheng-zhong，ZHANG Han-hui，HUANG Chang-cang et al(林郑忠，张汉辉，黄长沧等). Spectroscopy and Spectral Analysis(光谱学与光谱分析)，2002，22(6)： 1048. [13] 王恩波，胡长文，许 林著. 多酸化学导论. 北京: 化学工业出版社, 1998. 16.
