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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 vanadium borate clusters with [(VO) 12 O6B18O42] clusters were synthesized: (enH2) 6H3 [(VO) 12 O6B18O42] · 13H2O (1), [Ni ] 6H3 [(VO) 12 O6B18O42] · 8H2 O (2), [Cu (en) 2] 5H3 [(VO) 12 O6B18O42] [B (OH) 3] 2 .16H20 (3) and Na4H3 [(VO) 12 O6B18O42] .8H20 (4). FTIR, UV VisDRS and fluorescence spectroscopy were used to study the relationship between structure and properties. Among them, the compound (1) contains a discrete structure of [(VO) 12 O6B18O42], and the ring B18O42 is sandwiched by two V6O18 clusters through eight B- (μ3 -O) -V bonds; (1), another kind of new discrete structure was formed by coordination of 6 [Ni (en) 2] through bridging oxygen of two Ni- (μ3-O) -B and B18O42. (VO) 12 O6B18O42] building blocks of (4) are bridged by [Cu (en) 2] 2 + and inorganic Na + ions, respectively, to form a two-dimensional layered structure. The characteristic vibrational frequencies of multi-vanadium borate clusters correlate with the structures of these compounds; UV VisDRS shows that the charge-transfer transitions of metal oxygen cluster compounds occur near 205 and 260 nm; with 310 nm light excitation at about 4 15nm can cause the fluorescence emission from Oμ → Mo, also studied its fluorescence lifetime.