若干具有[(PO4)2Mo5O15]簇骼的化合物的光谱研究

本文对所合成的具有 (PO4 ) 2 Mo5O1 5]簇骼的 3种新颖的有机 磷钼酸盐簇合物(NH3CH2 CH2 NH3) 2 5(PO4 ) (HPO4 )Mo5O1 5]·7 5H2 O (Ⅰ ) ,(H3NCH2 CH2 NH3) 3·(PO4 ) 2 Mo5O1 5]·3H2 O (Ⅱ )和(H3NCH2 CH2 NH3) 2 ·Cu(en) ](PO4 ) 2 Mo5O1 5]·5H2 O (Ⅲ )用FTIR ,NIR Raman ,紫外 可见漫反射光谱 (UV VisDRS)和荧光光谱等研究手段 ,对其进行光谱研究 ,探讨其结构和性能的关系。在这些化合物中 ,化合物Ⅰ和Ⅱ具有孤立的 (PO4 ) 2 Mo5O1 5]簇骼基元 ,而化合物Ⅲ的 (PO4 ) 2 Mo5O1 5]簇骼基元是由 Cuen]基团桥联成链 ;磷钼酸盐的特征振动频率和这些化合物的结构相关 ;UV VisDRS显示 ,在 2 0 0和 2 6 0nm左右有两个杂多化合物的特征吸收谱带 ;化合物的稳态荧光光谱中 ,观察到以 2 4 0nm激发 ,在大约 4 0 0nm附近出现的由金属氧簇Oμ→Mo跃迁激发所引起的较强的发射峰 ,在化合物 (Ⅲ )中 ,还观察到通过 Cuen]的荷移跃迁的以 5 70nm激发所产生的 6 0 4nm的发射峰。

Spectral Study of the Compounds with [(PO4)2Mo5O15]

Three novel organic-molybdenum phosphates with (PO4)2Mo5O15], namely (NH3CH2CH2NH3)2.5(PO4)(HPO4) Mo5O15].7.5H2O (I), (H3NCH2CH2NH3)3.(PO4)2Mo5O15].3H2O (II) and (H3NCH2CH2NH3)2.Cu(en)] (PO4)2Mo5O15].5H2O (III), were synthesized. The relationship between their properties and structures were studied by using FTIR, NIR-Raman, UV-Vis DRS and fluorescence spectra. Among these compounds, compound I and II possess isolating (PO4)2Mo5O15] cage, while compound III is rather novel whose (PO4)2Mo5O15] cages are bridging into chains by Cuen] groups. The characteristic vibrational frequencies of molybdenum phosphates are related to the structures of these compounds. In the UV-Vis DRS spectra, there are two characteristic peaks of heteropoly compounds at 200 and 260 nm. The fluorescence spectra of these three compounds have been studied, which have emission peaks at about 400 nm excited by 240 nm, which are caused by O mu-Mo, while compound III produces 604 nm emission excited by 570 nm, which is caused by the LMCT of Cuen] group.