【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。更多还原

【Abstract】 Four novel polyoxovanadium borates with [（VO） 12O₆B 18O 42], namely （enH₂）₆H₃[（VO） 12O₆B 18O 42]·13H₂O（1）, [Ni（en）₂]₆H₃[（VO） 12O₆B 18O 42]·8H₂O（2）, [Cu（en）₂]₅H₃[（VO） 12O₆B 18O 42][B（OH）₃]₂·16H₂O（3） and（enH₂）₄Na₄H₃[（VO） 12O₆B 18O 42]·8H₂O（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） 12O₆B 18O 42] cage, there is a ring of B 18O 42 sandwiched between two vanadium-oxygen clusters V₆O 18 by eighteen B—（μ₃—O）—V bonds, while compound （2） is rather six [Ni（en）₂], each connected with the B 18O 42 ring by two Ni—（μ₃—O）—B. In compounds （3） and （4）, the anion clusters [（VO） 12O₆B 18O 42] 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 nm, respectively. The fluorescence spectra of these four compounds have been studied, and they have emission peaks at 415 nm excited by 310 nm which are caused by O_μ→Mo. The fluorescence lifetimes of these compounds have been studied.更多还原