多酸-查耳酮杂化分子的制备及其光交联性能  

Preparation of polyoxometalate-chalcone hybrid and its photo-polymerization property

作　　者：张洁[1,2] 龙泳[1] 宣为民[1] 林长亘[1,2] 宋宇飞[1] 

机构地区：[1]北京化工大学化工资源有效利用国家重点实验室,北京100029 [2]北京化工大学国际软物质研究中心,北京100029

出　　处：《科学通报》2017年第7期685-692,共8页Chinese Science Bulletin

基　　金：国家重点基础研究发展计划(2014CB932104);国家自然科学基金(U1407127;U1507102);中央高校基金(YS1406);中国博士后基金(2016M591048)资助

摘　　要：光敏型多酸杂化分子及其光响应特性是目前多酸功能材料的研究重点.本文采用共价修饰的方法将光敏型查耳酮基团嫁接至Anderson型多酸骨架上,制备了一类新型的光敏杂化分子.利用核磁共振、傅里叶转换红外、高分辨质谱、单晶X射线衍射等技术确认了多酸-查耳酮分子的结构;并利用紫外光谱、核磁共振和凝胶渗透色谱技术详细研究了多酸-查耳酮分子的光交联特性.该工作为新型光敏多酸杂化分子的制备及功能应用提供了良好借鉴.Photo-sensitive polyoxometalate-based hybrid materials have attracted much attention in recent years due to their unique photo-responsive properties. Here we represent a new type of photo-sensitive polyoxometalate-based hybrid by covalently tethering chalcone moieties onto Anderson cluster. Various techniques including nuclear magnetic resonance（NMR）, Fourier transform infrared spectoscopy（FT-IR）, electrospray ionization-mass spectrometry（ESI-MS） and single-crystal X-ray diffraction have been utilized to characterize the structure and composition of the resultant hybrid. The 1H and 13C NMR spectra show well resolved peaks that can be unambiguously assigned and are in good accordance with the molecular structure. Characteristic stretching vibrations of MO and Mo–O–Mo bonds can be found at 940 and 668 cm-1 in the FT-IR spectrum respectively, whilst the chalcone moieties give stretching bands at 1665/1593 cm-1（C=O–C=C） and 1568/1511 cm-1（C=C）. The ESI-MS spectrum of the hybrid provides us more convincing structural informations. For instance, the isotopic peaks observed at m/z=2167.81 can be clearly ascribed to the anionic fragment of {[（n-C4H9）4N]2[（Mn Mo6O24）{（CH2）3CNHCOCH2OC6H4C2H2COC6H5}2]}-, suggesting the successful modification of Anderson cluster with chalcone molecules. Single-crystal X-ray diffraction analysis reveals that the hybrid crystallizes in a mono-clinic system with a C2/c space group, where organic chalcone moieties are covalently bonded to the Anderson cluster via μ3-oxo bridging ligands. The photo-polymerization properties of the hybrid have been investigated in detail using UV-Vis spectroscopy, 1H NMR, and gel permeation chromatography. For example, when irradiated at UV light of 365 nm the hybrid undergoes a [2π＋2π] cycloaddition reaction, leading to an absorbance decrease at wavelength of 332 nm in the UV-Vis spectrum. Meanwhile, a new absorbance peak attributed to the generated cyclobutane structure is observed at 245 nm. This process gives a total

关 键 词：多金属氧酸盐 查耳酮 光交联 共价修饰 杂化分子 

分 类 号：TB34[一般工业技术—材料科学与工程]