混配杂多化合物[C_(10)H_(10)N]_4PMo_9W_3O_(40)·2DMF的合成、表征、晶体结构及非线性光学性质  

Synthesis,Characterization,Crystal Structure and Nonlinear Optical Property of a Mixed-Valence Heteropolyoxometallate [C_(10)H_(10)N]_4PMo_9W_3O_(40)·2DMF

作　　者：王敬平[1] 牛景扬[1] 党东宾[1] 柏艳[1] 

机构地区：[1]河南大学化学化工学院,开封475001

出　　处：《应用化学》2002年第2期144-148,共5页Chinese Journal of Applied Chemistry

基　　金：河南省杰出青年基金;河南省自然科学基金资助项目 ( 0 0 40 3180 0和 0 0 40 40 30 0 )

摘　　要：合成了混合价钨钼混配杂多化合物 [C1 0 H1 0 N]4 PMo9W3O4 0 · 2 DMF,晶体属单斜晶系 ,空间群 P2 1 /n,a=1 .490 6(4 ) nm,b=1 .2 496(1 ) nm,c=1 .765 2 (5 ) nm,β=98.1 6(1 )°,V=3 .2 5 47(1 3 ) nm3,Z=2 ,Dc=2 .791 Mg/m3,Mr=2 73 5 .84,最终偏离因子 R=0 .0 5 3 1 ,Rw=0 .1 3 62 .晶体结构研究表明 ,钨原子取代钼以后阴离子中所有键长均有不同程度的改变 ,PO4 四面体畸变增大 .ESR研究表明 ,还原电子在钼原子间离域且其离域程度随温度降低而减弱 ;非线性光学性质测定显示化合物具有三阶非线性光学性质 ,χ( 3) =1 .48×1 0 - 1The crystal structure of a mixed valence compound, [C 10 H 10 N] 4PMo 9W 3O 40 ·2DMF is reported. The crystal is monoclinic with space group P2 1/n, a =1 490 6(4) nm, b =1 249 6(1) nm, c = 1 765 2(5) nm, β =98 16(1)°, V = 3 254 7(13) nm 3 , Z =2, D c=2 791 g/nm 3, M r=2 735 84, R = 0 053 1 and R w=0 136 2. A certain change in bond distance is found for all of anions and the PO 4 tetrahedron is markedly distorted after displacement of molybdenum atom by tungsten. The reduced electrons are delocalized among the molybdenum atoms and the degree of delocalization decreases with the decrease in temperature. The compound exhibits the third order nonlinear optical properties,with the third order susceptibility being χ (3) =1 48×10 -13 esu.

关 键 词：混合价 杂多金属氧酸盐 晶体结构 混合价 钨钼混配杂多化合物 合成 表征 非线性光学性质 

分 类 号：O641.4[理学—物理化学] O482[理学—化学]