Institut des Matériaux Jean Rouxel, Université de Nantes, CNRS, 2 rue de la Houssinière, BP 32229, 44322 Nantes, France.
Inorg Chem. 2010 Dec 20;49(24):11309-16. doi: 10.1021/ic1007796. Epub 2010 Nov 16.
We investigate the reactivity of MoO(4)(2-) toward six organoammonium cations (+)(Me(3-x)H(x)N)(CH(2))(2)(NH(y)Me(3-y))(+) (x, y = 1-3) at different synthesis temperatures ranging from 70 to 180 °C. A total of 16 hybrid organic-inorganic materials have been synthesized at an initial pH of 2, via ambient pressure and hydrothermal routes, namely, (H(2)en)[Mo(3)O(10)]·H(2)O (1), (H(2)en)[Mo(3)O(10)] (2), (H(2)en)[Mo(5)O(16)] (3), (H(2)MED)(2)[Mo(8)O(26)]·2H(2)O (4), (H(2)MED)[Mo(5)O(16)] (5), (N,N-H(2)DMED)(2)[Mo(8)O(26)]·2H(2)O (6), (N,N-H(2)DMED)(2)[Mo(8)O(26)]·2H(2)O (7), (N,N'-H(2)DMED)(2)[Mo(8)O(26)] (8), (N,N'-H(2)DMED)[Mo(5)O(16)] (9), (H(2)TriMED)(2)[Mo(8)O(26)]·4H(2)O (10), (H(2)TriMED)(2)[Mo(8)O(26)]·2H(2)O (11), (H(2)TriMED)[Mo(7)O(22)] (12), (H(2)TMED)(2)[Mo(8)O(26)]·2H(2)O (13), (H(2)TMED)(2)[Mo(8)O(26)] (14), (H(2)TMED)(2)[Mo(8)O(26)] (15), and (H(2)TMED)[Mo(7)O(22)] (16). All of these compounds contain different polyoxomolybdate (Mo-POM) blocks, i.e., discrete β-Mo(8)O(26) blocks in 6, 10, 13, 14, (1)/(∞)Mo(3)O(10), and (1)/(∞)Mo(8)O(26) polymeric chains in 1, 2, 4, 7, 8, and 15, respectively, and (2)/(∞)Mo(5)O(16) and (2)/(∞)Mo(7)O(22) layers in 3, 5, 9, 12, and 16, respectively. The structures of 5, 9, and 14 have been resolved by single-crystal X-ray analyses. The characterization of the different Mo-POM blocks in 1-16 by Fourier transform Raman spectroscopy is reported. The impact of the synthesis temperature on both the composition and topology of the Mo-POM blocks is highlighted.
我们研究了 MoO(4)(2-) 与六种有机铵阳离子 (+)(Me(3-x)H(x)N)(CH(2))(2)(NH(y)Me(3-y))(+) (x, y = 1-3) 在不同合成温度下的反应性，温度范围从 70 到 180°C。通过常压和水热途径，在初始 pH 值为 2 的条件下，共合成了 16 种杂化有机-无机材料，分别为 (H(2)en)[Mo(3)O(10)]·H(2)O (1)、(H(2)en)[Mo(3)O(10)] (2)、(H(2)en)[Mo(5)O(16)] (3)、(H(2)MED)(2)[Mo(8)O(26)]·2H(2)O (4)、(H(2)MED)[Mo(5)O(16)] (5)、(N,N-H(2)DMED)(2)[Mo(8)O(26)]·2H(2)O (6)、(N,N-H(2)DMED)(2)[Mo(8)O(26)]·2H(2)O (7)、(N,N'-H(2)DMED)(2)[Mo(8)O(26)] (8)、(N,N'-H(2)DMED)[Mo(5)O(16)] (9)、(H(2)TriMED)(2)[Mo(8)O(26)]·4H(2)O (10)、(H(2)TriMED)(2)[Mo(8)O(26)]·2H(2)O (11)、(H(2)TriMED)[Mo(7)O(22)] (12)、(H(2)TMED)(2)[Mo(8)O(26)]·2H(2)O (13)、(H(2)TMED)(2)[Mo(8)O(26)] (14)、(H(2)TMED)(2)[Mo(8)O(26)] (15) 和 (H(2)TMED)[Mo(7)O(22)] (16)。所有这些化合物都包含不同的多钼酸盐 (Mo-POM) 块，即离散的β-Mo(8)O(26) 块在 6、10、13、14 中，(1)/(∞)Mo(3)O(10) 和(1)/(∞)Mo(8)O(26) 聚合链在 1、2、4、7、8 和 15 中，分别，以及(2)/(∞)Mo(5)O(16)和(2)/(∞)Mo(7)O(22)层在 3、5、9、12 和 16 中。通过单晶 X 射线分析解析了 5、9 和 14 的结构。通过傅里叶变换拉曼光谱对 1-16 中不同的 Mo-POM 块进行了表征。强调了合成温度对 Mo-POM 块的组成和拓扑结构的影响。
