二茂铁基-双酮锌配合物的合成、电化学活性及多光子吸收

Design,Synthesis,Electrochemical Activity and Multiphoton Absorption of Ferrocenyl Diketone Zn(Ⅱ)􀃭Complex

合成了具有推-拉电子(D-A)构型的二茂铁基双酮配体(L)及配合物(NHEt_(3))[Zn(L)_(3)]。晶体结构分析表明,二茂铁双酮脱去一个质子,以烯醇式与Zn^(2+)配位,得到-1价的二茂铁双酮基锌配合物。循环伏安和原位红外电化学方法研究发现,(NHEt_(3))[Zn(L)_(3)]发生了两步氧化和一步还原过程:随着氧化过程中电位的增加,其中1个二茂铁(Fc)配体被氧化成Fc^(+),形成D-A不对称结构模式;随着氧化的继续,2个Fc配体也被氧化,3个Fc^(+)与锌中心仍成D-A结构模式,最后将Fc^(+)一步还原成Fc。理论计算结果表明,配合物的电子离域程度高,有利于电荷流动。非线性光学实验结果显示,该配合物在近红外区具有大的双/三光子吸收效应和三阶非线性光学极化率。

A functional ferrocenyl ligand(L)with D-A configuration and its complex(NHEt_(3))[ZnL3]were synthesized.Single crystal analysis shows that the ferrocene diketone loses a proton to coordinate with Zn^(2+),which finally gives the negative monovalent ferrocene diketo Zn(Ⅱ)complex.The results from electrochemical cyclic voltammetry and IR in situ revealed that(NHEt_(3))[Zn(L)_(3)]went through two-step oxidation and one-step reduction process.As the potential increased during the oxidation process,one ferrocene(Fc)unit was oxidized to Fc^(+),forming a D-A asymmetric structure mode.Along with the oxidation continued,the other Fc units were also oxidized.The three Fc^(+)with Zn^(2+)still formed the D-A structure mode,and finally the Fc^(+)was reduced to Fc in one step.Theoretical calculation result shows that the complex is prone to exist high degree of electron delocalization.The experiment results from nonlinear optical property determinations show that the complex has a larger two/three-photon absorption cross sections and third-order nonlinear optical susceptibility in near IR region.CCDC:2070926,L;2070927,(NHEt_(3))[Zn(L)_(3)].