Organic frameworks (OFs) offer a novel strategy for assembling organic semiconductors into robust networks that facilitate transport, especially the covalent organic frameworks (COFs). However, poor electrical conductivity through covalent bonds and insolubility of COFs limit their practical applications in organic electronics. It is known that the two-dimensional intralayer π∙∙∙π transfer dominates transport in organic semiconductors. However, because of extremely labile inherent features of noncovalent π∙∙∙π interaction, direct construction of robust frameworks via noncovalent π∙∙∙π interaction is a difficult task. Toward this goal, we report a robust noncovalent π∙∙∙π interaction-stacked organic framework, namely πOF, consisting of a permanent three-dimensional porous structure that is held together by pure intralayer noncovalent π∙∙∙π interactions. The elaborate porous structure, with a 1.69-nm supramaximal micropore, is composed of fully conjugated rigid aromatic tetragonal-disphenoid-shaped molecules with four identical platforms. πOF shows excellent thermostability and high recyclability and exhibits self-healing properties by which the parent porosity is recovered upon solvent annealing at room temperature. Taking advantage of the long-range π∙∙∙π interaction, we demonstrate remarkable transport properties of πOF in an organic-field-effect transistor, and the mobility displays relative superiority over the traditional COFs. These promising results position πOF in a direction toward porous and yet conductive materials for high-performance organic electronics.

有机框架（OFs）提供了一种新颖的策略，可将有机半导体组装到有助于运输的坚固网络中，尤其是共价有机框架（COF）。但是，由于共价键的导电性差以及COF的不溶性，限制了它们在有机电子产品中的实际应用。众所周知，二维层内π∙∙∙∙π转移控制着有机半导体的传输。但是，由于非共价π∙∙∙π相互作用的固有不稳定特性，通过非共价π∙∙∙ππ相互作用直接构建鲁棒的框架是一项艰巨的任务。为了实现这一目标，我们报告了一个健壮的非共价π∙∙∙π相互作用堆叠有机框架，即πOF，由永久的三维多孔结构组成，该结构通过纯层内非共价π∙∙∙π相互作用保持在一起。精细的多孔结构具有1.69 nm的超大微孔，由具有四个相同平台的完全共轭的刚性芳族四方双蝶形形状的分子组成。πOF显示出优异的热稳定性和高可回收性，并显示出自修复特性，通过该特性，通过在室温下进行溶剂退火，可以恢复母体孔隙率。利用长距离π∙∙∙π相互作用，我们证明了πOF在有机场效应晶体管中的出色传输特性，并且迁移率显示出优于传统COF的优势。