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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P1,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(0)。
A trinuclear zinc (Ⅱ) complex [Zn3L6 (2,2 ’- bipy) was synthesized from 2,4-dichlorophenoxyacetic acid (HL) and 2,2’- bipyridyl -bipy) 2]. The complex crystal belongs to the triclinic system with the space group P1, with unit cell parameters of a = 1.073 85 (6) nm, b = 1.329 58 (7) nm, c = 1.515 80 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 deviation factor R1 = 0.0306, wR2 = 0.0757. Due to the bridging coordination of 2,4-dichlorophenoxyacetate, the complex formed a trinuclear structure. In the molecule of the complex, the coordination number of zinc (Ⅱ) ion located in the middle position is 6, which is in octahedral coordination environment, and the coordination numbers of the two zinc (Ⅱ) ions located at the end position are both 5, in the triangle double cone coordination environment. The work also determined the magnetic, fluorescent and electrochemical properties of the title complex. The results show that the complex has diamagnetism within the range of 28 ~ 300 K; when the excitation wavelength is 664 nm, the complex has 1 A strong fluorescence emission peak; during the cyclic voltammetry of the complex electron transfer is quasi-reversible, the corresponding electrode reaction is Zn (Ⅱ) / Zn (0).