Crystalline covalent-organic frameworks (COFs) are a powerful platform for advancing a myriad of applications extending from gas storage and separation to catalysis and optoelectronics. The tunability, modularity, and crystalline nature of COFs portend the ability to prepare a novel class of multidimensional and multifunctional crystalline porous materials. Of particular interest is the integration of two- and three-dimensional electron acceptors (tetracyanoquinodimethane and fullerene-based derivatives) into a two-dimensional crystalline motif. The precise donor-acceptor (D-A) alignment achieved in these materials is imposed by the rigid COF scaffold, which can promote directional charge and energy transfer, and as a result, enhance device performance.<br/><br/>In this work, we investigate the possibility of tailoring the electronic properties of D-A COFs through postsynthetic modification of the scaffold, resulting in a covalent bond between D and A moieties. Furthermore, we reveal tunable electronic properties that led to significant conductivity enhancements. Comprehensive characterization techniques and studies of the novel D-A motifs, for example, powder X-ray diffraction, cyclic voltammetry, and theoretical calculations reveal the effect of D-A alignment on the materials electronic structure. The presented D-A strategic design could be used as a blueprint for the development of electroactive and conductive multidimensional and multifunctional crystalline porous materials.

Well-defined donor-acceptor covalent-organic frameworks

ACS Spring Meeting 2021

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