摘要
采用固相反应方法以[NH4]2[MoS2O2],Cul,Et4NBr和2-(二苯基膦)吡啶(PyPPh2)为原料制备了标题化合物.其结构用单晶分析法测定.测得化合物的分子式为[MoOS3Cu2(PyPPb2)3],该晶体结构属三斜晶系,空间群为P-1,所得晶胞参数为a=1.16736(4)nm,b=1.42254(5)nm,c=1.68034(6)nm,α=100.07°,β=103.2450(10)°,γ=105.0650(10)°,V=2.53991(15)nm3,Z=2,Dc=1.504g@cm-3,F(000)=1166,μ=13.57 cm-1.偏差因子R1=0.0590,wR2=0.1238.簇合物具有高度弯曲的蝴蝶状核,其中MoOS32基团以三齿配体的形式与两个具有不同构型的Cu原子配位,氧原子不参加配位仅以端基形式存在.通过标题化合物在DMF中非线性光学性质的测定,表明其具有较好的非线性吸收和与以往不同的自散焦效应,算得其非线性吸收系数α2=4.4×10-11m@W-1,非线性折射系数n2=-8.225×10-18m2@W-1;从而说明外围配体对非线性光学性质也具有大的影响作用.
Solid state reaction of [NH4](2)[MoS2O2], CuI and Et4NBr with 2 - (diphenylphosphino) pyridine (PyPPh2) results in trinuclear cluster [MoOS3Cu2 (PyPPh2)(3)]. Its crystal structure has been determined on a Simens Smart 1 - K CCD area - detector diffractometer. The crystal is triclinic, space group P (1) over bar with a = 1.16736 (4) nm, b = 1.42254 (5) nm, c = 1. 68034 (6) nm, alpha = 100.07 degrees, beta = 103.2450 (10)degrees, gamma = 105.0650(10)degrees, V = 2.53991(15) nm(3), Z = 2, D-c = 1.504 g . cm(-3), F (000) = 1166, mu = 13.57 cm(-1). The final R-1 = 0.0590, wR(2) = 0.1238. The cluster is highly bent with a butterfly - shaped core in which the MoOS32- unit acts as a tridentate ligand to coordinate with two Cu atoms of different configurations and the O atom serves as a terminal group. Investigation of third - order optical nonlinearity shows that it exhibits considerable nonlinear absorptive and self - defocusing effect with alpha (2) = 4.4 x 10(-11) m . W-1 and n(2) = - 8.225 x 10(-18) m(2) . W-1, respectively. The peripheral ligands also play an important role in the NLO properties of clusters.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
2001年第9期1435-1441,共7页
Acta Chimica Sinica
基金
国家自然科学基金
