若干多钒硼酸盐簇合物的光谱研究  

Spectral Study of Some Polyoxovanadium Borates

作　　者：张汉辉[1] 林志华[1] 黄长沧[1] 王永净[1] 孙巧珍[1] 陈义平[1] 吴小园[1] 孙瑞卿[1] 曹彦宁[1] 

机构地区：[1]福州大学化学系

出　　处：《光谱学与光谱分析》2005年第3期369-373,共5页Spectroscopy and Spectral Analysis

基　　金：福建省自然科学基金 (E0 1 1 0 0 1 3);福建省科技三项基金 (K0 2 0 2 8);结构化学国家重点实验室基金资助

摘　　要：合成了具有 [(VO) 12 O6B18O42 ]簇骼的 4种新颖的多钒硼酸盐簇合物 :(enH2 ) 6H3 [(VO) 12 O6B18O42 ]·13H2 O(1) ,[Ni(en) 2 ]6H3 [(VO) 12 O6B18O42 ]·8H2 O(2 ) ,[Cu(en) 2 ]5H3 [(VO) 12 O6B18O42 ][B(OH) 3 ]2 ·16H2 O(3)和 (enH2 ) 4 Na4H3 [(VO) 12 O6B18O42 ]·8H2 O(4)。通过FTIR ,UV VisDRS和荧光光谱等手段对其进行了研究 ,探讨了结构和性能的关系。其中 ,化合物 (1)含有 [(VO) 12 O6B18O42 ]的分立结构 ,环状B18O42 通过 8个B— (μ3 —O)—V键被两个V6O18簇夹在中间 ;而化合物 (2 )是在 (1)的基础上 ,由 6个 [Ni(en) 2 ]各自通过两个Ni— (μ3 —O)—B与B18O42 的桥氧配位形成另一类新的分立型结构 ;化合物 (3)和 (4)的 [(VO) 12 O6B18O42 ]构筑单元间分别通过 [Cu(en) 2 ]2 + 和无机Na+ 离子桥联形成二维层状结构。多钒硼酸盐簇合物的特征振动频率和这些化合物的结构相关 ;UV VisDRS表明 ,在 2 0 5和 2 6 0nm附近出现金属氧簇化合物的荷移跃迁 ;用310nm光激发 ,在约 4 15nm处能引起由Oμ→Mo的荧光发射 ,同时还研究了其荧光寿命。Four novel polyoxovanadium borates with [(VO)(12)O6B18O42], namely (enH(2))(6)H-3 [(VO)(12)O6B18O42] center dot 13H(2)O(1), [Ni (en)(2)](6)H-3[(VO)(12)O6B18O42] center dot 8H(2)O(2), [Cu(en)(2)](5)H-3[(VO)(12)O6B18O42][B(OH)(3)](2) center dot 16H(2)O(3) and(enH(2))(4)Na4H3[(VO)(12) O6B18O42] center dot 8H(2)O(4), were synthesized. The relationship between their properties and structures were studied by using FTIR, UV-Vis DRS and fluorescence etc. Among these compounds, compound (1) possesses isolated [(VO)(12)O6B18O42] cage, there is a ring of B18O42 sandwiched between two vanadium-oxygen clusters V6O18 by eighteen B-(mu(3)-O)-V bonds, while compound (2) is rather six [Ni(en)(2)], each connected with the B18O42 ring by two Ni-(mu(3)-O)-B. In compounds (3) and (4), the anion clusters [(VO)(12)O6B18O42](13-) are connected with [Cu(en)(2)](2+) and Na+, respectively. Thus, the compounds (3) and (4) are extended to an infinite two-dimensional network structure, respectively. These characteristic vibrational frequencies of polyoxovanadium borates are related to the structures of these compounds. In UV/Vis DRS spectra, there are two characteristic peaks of polyoxometalates at 205 and 260 rim, respectively. The fluorescence spectra of these four compounds have been studied, and they have emission peaks at 415 rim excited by 310 nm which are caused by O-mu-> Mo. The fluorescence lifetimes of these compounds have been studied.

关 键 词：簇合物 光谱研究 氧配位 化合物 硼酸盐 OH 结构和性能 NF1 DRS NA^+ 

分 类 号：O641.4[理学—物理化学] O614[理学—化学]