Synthesis, Characterization, and Photochromic Properties of Hybrid Organic-Inorganic Materials Based on Molybdate, DABCO, and Piperazine
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- 作者：Violaine Coué ; Ré ; mi Dessapt ; Martine Bujoli-Doeuff ; Michel Evain ; Sté ; phane Jobic
- 刊名：Inorganic Chemistry
- 出版年：2007
- 出版时间：April 2, 2007
- 年：2007
- 卷：46
- 期：7
- 页码：2824 - 2835
- 全文大小：668K
- 年卷期：v.46,no.7(April 2, 2007)
- ISSN：1520-510X
文摘
Prompted by our interest in new photochromic organic-inorganic hybrid materials, the reactivity of [Mo7O24]6-toward a structure-directing reagent diamine such as 1,4-diazabicyclo[2.2.2]octane (DABCO) and piperazine (pipz)has been investigated, and three new molybdenum(VI)-containing compounds, namely, (H2DABCO)3[Mo7O24]·4H2O(1), (H2DABCO)[Mo3O10]·H2O (2), and (H2DABCO)2(NH4)2[Mo8O27]·4H2O (3), have been synthesized andcharacterized. New synthetic routes to achieve the known compounds (H2DABCO)2(H2pipz)[Mo8O27] (4), (H2pipz)3[Mo8O27] (5), and (H2DABCO)2[Mo8O26]·4H2O (6) are also reported. All of these compounds contain different poly(oxomolybdate) clusters, i.e., discrete [Mo7O24]6- blocks in 1, infinite polymeric chains 1/
[Mo3O10]2- in 2, 1/[Mo8O27]6-in 3-5, and 1/[Mo8O26]4- in 6, associated in a tridimensional assembly by hydrogen bonds with H2DABCO2+and/or H2pipz2+ cations. Interconversion pathways and chemical factors affecting the stabilization of the differentspecies are highlighted and discussed. At the opposite of 6, compounds 1-5 show photochromic behavior underUV excitation. Namely, compounds 1-5 shift from white or pale yellow to pale pink, reddish brown, or purple underUV illumination depending on the chemical nature of the mineral framework, with the kinetics of the color changebeing dictated by the nature of the organic component and by the organic-inorganic interface.
[Mo3O10]2- in 2, 1/[Mo8O27]6-in 3-5, and 1/[Mo8O26]4- in 6, associated in a tridimensional assembly by hydrogen bonds with H2DABCO2+and/or H2pipz2+ cations. Interconversion pathways and chemical factors affecting the stabilization of the differentspecies are highlighted and discussed. At the opposite of 6, compounds 1-5 show photochromic behavior underUV excitation. Namely, compounds 1-5 shift from white or pale yellow to pale pink, reddish brown, or purple underUV illumination depending on the chemical nature of the mineral framework, with the kinetics of the color changebeing dictated by the nature of the organic component and by the organic-inorganic interface.