Efficient modification of pyrene-derivative featuring third-order nonlinear optics via the click post-functionalization
Efficient modification of pyrene-derivative featuring third-order nonlinear optics via the click post-functionalization
复制标题
通过点击后功能化对具有三阶非线性光学的芘衍生物进行有效修饰
DOI：
10.1016/j.tetlet.2013.06.121
复制
发表时间：
2013-09-04
影响因子：
1.8
通讯作者：
Yang, Huai
中科院分区：
文献类型：
--
作者：
Jin, Zhaokui;Wang, Dong;Yang, Huai
通过[2+2]环加成反应合成了一系列具有非平面结构的N，N-双十二烷基苯胺基取代的给体和TCNE/TCNQ加合受体的芘衍生物。由于TCNE和TCNQ的有效点击，产物在可见光（近红外区）显示出强的电荷转移（CT）带，强的氧化还原活性和相关的物理化学性质。紫外/维斯光谱和电化学研究表明，这些系统的CT性能很容易通过强氰基受体亲核试剂，这有一个较大的影响最低未占分子轨道（LUMO）的引入可调。特别是与TCNE的加成物相比，TCNQ点击的产物具有更强的D-A共轭和更大的π间隔。Z扫描实验表明，TCNQ产物具有较大的三阶非线性光学性质。这可能指向潜在的有趣的应用，新的芘衍生物在光电子器件和开发新的改性过程的设计不同的芘为基础的分子电子器件。(C)2013作者由爱思唯尔有限公司出版。保留所有权利。
A series of pyrene derivatives featuring nonplanar structures of N,N-didodecylanilino-substituted donor and TCNE/TCNQ adduct acceptors have been efficiently synthesized via formal [2+2] cycloaddition. As the efficient click by TCNE and TCNQ, the products show strong charge-transfer (CT) bands in the visible (near-IR region), potent redox activities, and related photophysical properties. UV/vis spectra and electrochemical studies show that the CT properties of these systems are readily tunable by strong cyano acceptor introduction on the nucleophile, which have a larger effect on the lowest unoccupied molecular orbital (LUMO). In particular, compared with the adduct of TCNE, the product clicked with TCNQ possessed a stronger D-A conjugation and bulkier pi spacers. The TCNQ product also has a larger third-order nonlinear optical property which was characterized by Z-scan experiments. This could point to potentially interesting applications of the new pyrene derivatives in optoelectronic devices and develop the new modification process for the design of different pyrene-based molecular electronic devices. (C) 2013 The Authors. Published by Elsevier Ltd. All rights reserved.