Noncovalent π-stacked robust topological organic framework

Abstract

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.

3D acceptors with multiple A–D–A architectures for highly efficient organic solar cells

“…38,39 Considering the crucial role of morphological stability in the stability of the final device, the excellent stability of multidimensional NFAs based OSCs may partially originate from their potentially robust 3D packing network formed not only by the strong intermolecular p-p stacking but also by the weak noncovalent interactions. 26,27,40…”

“…23 Last but not least, 3D acceptors with a suitably twisted molecular plane can usually form a more robust packing network not only through strong p-p stacking but also through sufficient noncovalent interactions, which should be beneficial for the morphological stability of active layers. 26,27 When taking all the above advantages into consideration, such a 3D NFA is expected to generate highly efficient and stable OSCs, thus making multi-dimensional NFAs very promising for the coming large-scale commercialization of OSCs. Despite the great potential of 3D NFAs, their exploration still confronts huge challenges in terms of both molecular design and chemical construction.…”

Hierarchical Assembly of a Micro‐ and Macroporous Hydrogen‐Bonded Organic Framework with Tailored Single‐Crystal Size

“…These properties, complementary to those exhibited by continuous frameworks, such as metal–organic frameworks (MOFs) [3] and covalent organic frameworks (COFs), [4] make porous molecular materials ideal candidates for advanced applications [2, 5] . Different families of porous molecular materials have been reported thus far, including porous organic salts, [6] porous organic cages, [7] C−H⋅⋅⋅π microporous crystals, [8] π‐organic frameworks, [9] supramolecular organic frameworks (SOFs), [10] halogen‐bonded organic framework (XOF), [11] intrinsically porous molecular materials (IPMs) [12] and hydrogen‐bonded organic frameworks (HOFs) [13] . Despite of the clear progress made, and the great research momentum in the field, outstanding challenges remain, and need to be addressed if the full potential of these materials is to be uncovered.…”

A Noncovalent π‐Stacked Porous Organic Molecular Framework for Selective Separation of Aromatics and Cyclic Aliphatics

“…For example, Yang et al. developed a distinctive noncovalent π⋅⋅⋅π interaction‐stacked organic framework (πOF) with permanent porous and remarkable conductive properties [8] . We employed an organic molecule carrying three identical propeller‐like wedges to construct a durable πOF, which can be used as a new crystalline sponge for rapid molecular structure determination [9] .…”