Semiconducting Covalent Organic Frameworks

Semiconductors form the foundational bedrock of modern electronics and numerous cutting-edge technologies. Particularly, semiconductors crafted from organic building blocks hold immense promise as next-generation pioneers, thanks to their vast array of chemical structures, customizable frontier orbital energy levels and bandgap structures, and easily adjustable π electronic properties. Over the past 50 years, advancements in chemistry and materials science have facilitated extensive investigations into small organic π compounds, oligomers, and polymers, resulting in a rich library of organic semiconductors. However, a longstanding challenge persists: how to organize π building units or chains into well-defined π structures, which are crucial for the performance of organic semiconductors. Consequently, the pursuit of methodologies capable of synthesizing and/or fabricating organic semiconductors with ordered structures has emerged as a frontier in organic and polymeric semiconductor research. In this context, covalent organic frameworks (COFs) stand out as unique platforms allowing for the covalent integration of organic π units into periodically ordered π structures, thus facilitating the development of semiconductors with extended yet precisely defined π architectures. Since their initial report in 2008, significant strides have been made in exploring various chemistries to develop semiconducting COFs, resulting in a rich library of structures, properties, functions, and applications. This review provides a comprehensive yet focused exploration of the general structural features of semiconducting COFs, outlining the basic principles of structural design, illustrating the linkage chemistry and synthetic strategies based on typical one-pot polymerization reactions to demonstrate the growth of bulk materials, nanosheets, films, and membranes. By elucidating the interactions between COFs and various entities such as photons, phonons, electrons, holes, ions, molecules, and spins, this review categorizes semiconducting COFs into nine distinct sections: semiconductors, photoconductors, light emitters, sensors, photocatalysts, photothermal conversion materials, electrocatalysts, energy storage electrodes, and radical spin materials, focusing on disclosing structure-originated properties and functions. Furthermore, this review scrutinizes structure-function correlations and highlights the unique features, breakthroughs, and challenges associated with semiconducting COFs. Furnished with foundational knowledges and state-of-the-art insights, this review predicts the fundamental issues to be addressed and outlines future directions for semiconducting COFs, offering a comprehensive overview of this rapidly evolving and remarkable field.