Design and Synthesis of Two-Dimensional Covalent Organic Frameworks with Four-Arm Cores: Prediction of Remarkable Ambipolar Charge-Transport Properties
Design and Synthesis of Two-Dimensional Covalent Organic Frameworks with Four-Arm Cores: Prediction of Remarkable Ambipolar Charge-Transport Properties
复制标题
DOI：
10.1039/c9mh00035f
复制
发表时间：
2019-02
影响因子：
13.3
通讯作者：
Simil Thomas;Hong Li;Raghunath R. Dasari;Austin M. Evans;William R. Dichtel;S. Marder;V. Coropceanu
中科院分区：
文献类型：
--
作者：
Simil Thomas;Hong Li;Raghunath R. Dasari;Austin M. Evans;William R. Dichtel;S. Marder;V. Coropceanu
我们考虑了三种二维 (2D) π 共轭聚合物网络（即共价有机框架，COF）材料，这些材料基于通过二乙炔连接体连接的芘、卟啉和锌卟啉核心。它们的电子结构在密度泛函理论全局混合水平上进行了研究，表明价带和导带的宽度很大，范围在 1 到 2 eV 之间。使用分子方法推导相邻核心单元之间的电子耦合和电子振动耦合，预计三个 π 共轭 2D COF 具有双极电荷传输特性，电子和空穴迁移率在 65-95 cm2V-1s-1 范围内。这些预测值将这些 2D COF 列为迁移率最高的有机半导体之一。此外，我们还合成了基于锌卟啉的二维COF，并通过粉末X射线衍射和表面积分析进行了结构表征，证明了这些电活性网络的可行性。
We have considered three two-dimensional (2D) π-conjugated polymer networks (i.e., covalent organic frameworks, COFs) materials based on pyrene, porphyrin, and zinc-porphyrin cores connected via diacetylenic linkers. Their electronic structures, investigated at the density functional theory global-hybrid level, are indicative of valence and conduction bands that have large widths, ranging between 1 and 2 eV. Using a molecular approach to derive the electronic couplings between adjacent core units and the electron-vibration couplings, the three π-conjugated 2D COFs are predicted to have ambipolar charge-transport characteristics with electron and hole mobilities in the range of 65-95 cm2V-1s-1. Such predicted values rank these 2D COFs among the highest-mobility organic semiconductors. In addition, we have synthesized the zinc-porphyrin based 2D COF and carried out structural characterization via powder X-ray diffraction and surface area analysis, which demonstrates the feasability of these electroactive networks.