Functionalization of UiO-66 Metal-Organic Framework and Highly Cross-Linked Polystyrene with Cr(CO)3: In Situ Formation, Stability, and Photoreactivity
Functionalization of UiO-66 Metal-Organic Framework and Highly Cross-Linked Polystyrene with Cr(CO)3: In Situ Formation, Stability, and Photoreactivity
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DOI：
10.1021/cm1005899
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发表时间：
2010-08-24
影响因子：
8.6
通讯作者：
Bordiga, Silvia
中科院分区：
文献类型：
--
作者：
Chavan, Sachin;Vitillo, Jenny G.;Bordiga, Silvia
本文采用互补光谱技术和理论计算，详细研究了两种高孔材料--新近合成的金属有机骨架材料UiO-66和交联聚（苯乙烯-co-二乙烯基苯）树脂中（芳烃）Cr（CO）（3）物种的形成和稳定性。特别是，傅里叶变换红外（FT-IR），紫外-可见（UV-vis），和X射线吸收近边结构（XANES）光谱，加上理论计算，允许形成（芳烃）Cr（CO）（3）物种被跟踪原位，从Cr（CO）（6）前体开始，监测材料的振动和电子性质的变化。EXAFS光谱给出了功能化的单位的结构证据。最后，通过用N-2分子取代一个CO配体，还探索了Cr（CO）（3）在UiO-66中的光诱导反应性。整体呈现的数据将成为一个系统的程序，用于调查功能化的多孔基质的发展的起点。
The formation and stability of (arene)Cr(CO)(3) species inside two highly porous materials-UiO-66, which is a recently synthesized metal-organic framework, and a cross-linked poly(styrene-co-divinylbenzene) resin-are investigated in detail by means of complementary spectroscopic techniques and theoretical calculations. In particular, Fourier transform infrared (FT-IR), ultraviolet-visible (UV-vis), and X-ray absorption near-edge structure (XANES) spectroscopies, coupled with theoretical calculations, allow the formation of the (arene)Cr(CO)(3) species to be followed in situ, starting from the Cr(CO)(6) precursor, monitoring the changes in the vibrational and electronic properties of the materials. EXAFS spectroscopy gives the structural evidence of the functionalized unities. Finally, the photoinduced reactivity of Cr(CO)(3) in UiO-66 is also explored, by following the substitution of one CO ligand with a N-2 molecule. The overall presented data would become the starting point for the development of a systematic procedure for investigating functionalized porous matrices.