【作者】 刘春宇； 潘秀梅； 杨国春；

【Author】 Chunyu Liu;Xiumei Pan;Guochun Yang;Faculty of Chemistry, Northeast Normal University;

【机构】 东北师范大学化学学院；

【摘要】 手性过渡金属Re（Ⅰ）配合物由于其具有奇特的非线性光学性质引起了广大科研工作者的广泛关注^[1]。最近报道了具有[Re₂（L_R）-（CO）₆Cl₂]·4CH₂Cl₂通式的手性双环Re（Ⅰ）配合物的二阶NLO效应比KDP大1.5倍^[2]。然而,它的手性起源没有被指认,在微观层面上的结构与性能的关系也没有被确立。这里我们运用DFT理论计算其电子结构,UV-Vis/CD谱和NLO性质。模拟的CD与实验值符合得很好,因此我们可以指认双环Re（Ⅰ）配合物的绝对构型。基于实验的结构,我们设计了一系列配合物并研究了它们的光物理性质。有趣的是,设计的配合物具有大的二阶非线性光学活性(115.81×10^-30 esu),预期它们是潜在的良好二阶非线性光学材料。更多还原

【Abstract】 Chiral transition metal Re（Ⅰ） complexes have attracted the great interest of the NLO researchers due to their versatile NLO properties.Recently, the second-order NLO response of chiral dinuclear Re（Ⅰ） complex with the formula [Re₂（L_R）-（CO）₆Cl₂]·4CH₂Cl₂ is 1.5 times larger than KDP has been reported.However, its NLO origin has not been determined and structure-property relationship has not been established at the microscopic level.So, it stimulated us to investigate the electronic structures, UV-Vis/CD spectra and second-order NLO properties with the aid of DFT calculations.The simulated CD spectra are in good agreement with the experimental ones, which can be used to assign the absolute configurations（ACs） of chiral dinuclear Re（Ⅰ） complex with high confidence.Based on the experimental complex, we designed a series of complexes and studied their properties.Interestingly, the designed complexes have remarkably large second-order NLO activity.It is expected that our studied complexes have the possibility to be excellent second-order NLO materials.更多还原