Martínez-Abadía Marta, Stoppiello Craig T, Strutynski Karol, Lerma-Berlanga Belén, Martí-Gastaldo Carlos, Saeki Akinori, Melle-Franco Manuel, Khlobystov Andrei N, Mateo-Alonso Aurelio
POLYMAT , University of the Basque Country UPV/EHU , Avenida de Tolosa 72 , Donostia-San Sebastian E-20018 , Spain.
CICECO - Aveiro Institute of Materials, Department of Chemistry , University of Aveiro , Aveiro 3810-193 , Portugal.
J Am Chem Soc. 2019 Sep 11;141(36):14403-14410. doi: 10.1021/jacs.9b07383. Epub 2019 Sep 3.
A high degree of crystallinity is an essential aspect in two-dimensional covalent organic frameworks, as many properties depend strongly on the structural arrangement of the different layers and their constituents. We introduce herein a new design strategy based on core-twisted polycyclic aromatic hydrocarbon as rigid nodes that give rise to a two-dimensional covalent organic framework with a wavy honeycomb (chairlike) lattice. The concave-convex self-complementarity of the wavy two-dimensional lattice guides the stacking of framework layers into a highly stable and ordered covalent organic framework that allows a full 3D analysis by transmission electron microscopy revealing its chairlike honeycomb facets and aligned mesoporous channels. Remarkably, the waviness of the framework does not disrupt the interlayer π-π stacking that shows charge transporting properties similar to those of planar covalent organic frameworks. The implementation of core-twisted aromatics as building blocks for covalent organic frameworks brings new possibilities in the design of highly ordered organic materials.
高结晶度是二维共价有机框架的一个重要方面，因为许多性质强烈依赖于不同层及其组成部分的结构排列。我们在此介绍一种基于核心扭曲多环芳烃作为刚性节点的新设计策略，该策略可产生具有波浪状蜂窝（椅状）晶格的二维共价有机框架。波浪状二维晶格的凹凸自互补性引导框架层堆叠成高度稳定且有序的共价有机框架，这使得通过透射电子显微镜进行完整的三维分析成为可能，揭示其椅状蜂窝面和排列的介孔通道。值得注意的是，框架的波浪状不会破坏层间π-π堆积，这种堆积显示出与平面共价有机框架类似的电荷传输特性。将核心扭曲芳烃用作共价有机框架的构建块为设计高度有序的有机材料带来了新的可能性。
