Theoretical investigation on switchable second-order nonlinear optical (NLO) properties of novel cyclopentadienylcobalt linear [4]phenylene complexes.
Theoretical investigation on switchable second-order nonlinear optical (NLO) properties of novel cyclopentadienylcobalt linear [4]phenylene complexes.
复制标题
新型环戊二烯基钴线性[4]亚苯基配合物可切换二阶非线性光学（NLO）特性的理论研究
DOI：
10.1007/s00894-012-1681-z
复制
发表时间：
2013-04
影响因子：
2.2
通讯作者：
Qiu, Yong-Qing
中科院分区：
文献类型：
--
作者：
Wang, Wen-Yong;Du, Xiao-Feng;Ma, Na-Na;Sun, Shi-Ling;Qiu, Yong-Qing
环戊二烯基钴（CpCo）线性[4]亚苯基配合物（4 =苯环数）是一类新型的有机金属配合物，当CpCo在热或光的触发下沿线性[4]亚苯基沿着迁移时，表现出高效的可切换非线性光学响应.本文采用密度泛函理论（DFT）方法计算了CpCo线性[4]亚苯基配合物的二阶非线性光学性质.所有的泛函都产生相同的β tot值顺序：1<2<4<3。采用极化连续模型（PCM）研究了四氢呋喃（THF）溶液中溶剂对二阶非线性光学性质的影响。溶剂导致轻微增强的非线性光学响应的研究有关的配合物在真空中的非线性光学响应。用TDDFT方法研究了配合物的电子吸收光谱。TDDFT计算结果表明，配合物2-4在近红外光谱区的最大吸收峰与配合物1相比发生了红移，吸收强度降低。我们还发现，钴（Co）原子在所有配合物中都起着施主的作用，d → π* 和π → π* 电荷转移（CT）跃迁对二阶非线性光学响应的增强有贡献。此外，发现实验上存在的两个配合物1和3在β tot值上有很大的差异。我们期望这种差异可以刺激基于CpCo线性[4]亚苯基络合物的新型可切换NLO材料的研究。
As a kind of novel organometallic complexes, the cyclopentadienylcobalt (CpCo) linear [4]phenylene complexes (4 = number of benzene rings) display efficient switchable nonlinear optical (NLO) response when CpCo reversibly migrates along the linear [4]phenylene triggered by heating or lighting. In this paper, the second-order NLO properties for CpCo linear [4]phenylene complexes were calculated by using the density functional theory (DFT) methods with four functionals. All of the functionals yield the same order of β tot values: 1<2<4<3. The effect of solvent on second-order NLO properties has been studied using polarized continuum model (PCM) in the tetrahydrofuran (THF) solution. The solvent leads to a slight enhancement of the NLO responses for the studied complexes relevant to their NLO responses in vacuo. The electronic absorption spectra were investigated by the TDDFT methods. The TDDFT calculations indicate that the maximum absorption peaks of complexes 2-4 in the near-infrared spectrum area show the bathochromic shift together with a decreasing intensity compared to complex 1. We have also found that the cobalt (Co) atom acts as a donor in all the organometallic complexes and the d → π* and π → π* charge transfer (CT) transitions contribute to the enhancement of second-order NLO response. Furthermore, two experimentally existing complexes 1 and 3 are found to have a large difference in β tot values. It is our expectation that this difference may stimulate the search for a new type of switchable NLO material based on CpCo linear [4]phenylene complexes.
登录
查看更多内容
影响因子：
4.4
作者：
OUDAR, JL
通讯作者：
OUDAR, JL
影响因子：
--
作者：
CHOPRA, P;CARLACCI, L;PRASAD, PN
通讯作者：
PRASAD, PN
影响因子：
56.9
作者：
MARDER, SR;BERATAN, DN;CHENG, LT
通讯作者：
CHENG, LT
影响因子：
4.4
作者：
BECKE, AD
通讯作者：
BECKE, AD
影响因子：
4.9
作者：
Marder, SR
通讯作者：
Marder, SR