以2,4-二氯苯氧乙酸(HL)和2,2’-联吡啶(2,2’-bipy)为配体合成了一个三核锌(Ⅱ)配合物[Zn3L6(2,2’-bipy)2].该配合物晶体属三斜晶系,空间群P(1-),晶胞参数:a=1.073 85(6) nm,b=1.329 58(7) nm,c=1.515 80(10) nm,α=66.961 0(10)°,β=69.387 0(10)°,γ=72.992 0(10)°,V=1.833 77(19) nm3,Dc=1.656 g·cm-3,Z=1,μ(Mo Kα)=1.483 mm-1,F(000)=920,最终偏离因子R1=0.030 6,wR2=0.075 7.由于2,4-二氯苯氧乙酸根的桥联配位作用,配合物形成了三核结构.在该配合物的分子中,位于中间位置的锌(Ⅱ)离子的配位数是6,处于八面体配位环境中,而位于端位的2个锌(Ⅱ)离子的配位数都是5,处于三角双锥配位环境中.本工作还测定了标题配合物的磁性、荧光和电化学性能,结果表明:在28～300 K范围内,配合物有抗磁性;当激发波长为664 nm时,配合物在660 nm附近有1个强的荧光发射峰;在循环伏安过程中配合物的电子转移是准可逆的,对应的电极反应是Zn(Ⅱ)/Zn(O).%A new complex [Zn3L6(2,2'-bipy)2] with 2,4-dichlorophenoxy acetic acid (HL) and 2,2'-bipyridine as the ligands has been synthesized.The crystal data for this complex are as follows:triclinic,space group P(1-),a=1.073 85(6) nm,b=1.329 58(7) nm,c=1.515 80(10) nm,α=66.961 0(10)°,β=69.387 0(10)°,γ=72.992 0(10)°,V=1.833 77(19) nm3,Dc=1.656 g·cm-3,Z=1,μ(Mo Kα)=1.483 mm-1,F(000)=920,final discrepancy factors R1=0.030 6,wR2=0.075 7.The crystal structure shows that the title complex forms trinuclear structure by bridging 2,4-dichlorophenoxy acetic acid anions.Zn(Ⅱ) ion in middle position is coordinated with six oxygen atoms,giving a six-coordinated distorted octahedral geometry.Compared with Zn(Ⅱ) ion in middle position,Zn(Ⅱ) ion in end position is located in a five-coordinated distorted trigonal bipyramid environment.The magnetic,luminescence and electrochemical properties of the title complex are also studied.The results show that the title complex is a diamagnetism system in temperatures range of 28～300 K,and when the exciting radiation set at 664 nm,the title complex can give off one broad emission band at around 660 nm.The electron transfer is quasi reversible in the electrode reaction,corresponding to Zn(Ⅱ)/Zn(O).CCDC:874918.
展开▼
