Researchers at the Center for Research in Biological Chemistry and Molecular Materials (CiQUS) at the Universidade de Santiago de Compostela (USC) have created a new method to produce covalent organic frameworks (COFs) that exhibit semiconducting properties without the need for chemical doping. This breakthrough, published in Angewandte Chemie International Edition, introduces a novel approach to enhance the electrical conductivity of COFs, which are materials composed of organic molecules linked by strong covalent bonds. These materials form highly ordered, crystalline structures with tiny pores, making them promising for use in electronics, sensors, and energy storage. However, achieving good electrical conductivity in COFs has typically required the addition of external substances called dopants, which can disrupt the material's structure and reduce its performance. The CiQUS team has developed an alternative strategy by incorporating radical molecules directly into the COF structure. These molecules, known as neutral trioxotriangulene (TOT) radicals, are unique for their highly delocalized spin and exceptional stability. By using these radicals as building blocks, the researchers created a COF with high electrical conductivity at room temperature, among the highest reported for non-doped materials of this type. Importantly, the material maintains a high level of porosity, with a surface area exceeding 1,200 square meters per gram—critical for many applications. Unlike traditional doping methods, the TOT radicals are not added as separate components but are integrated into the molecular framework itself. This integration allows the unpaired electrons in the radicals to generate charge carriers without the need for external chemical species, improving both the material’s conductivity and structural integrity. A significant advantage of this approach is that it combines three key properties—electrical conductivity, crystallinity, and porosity—which are often difficult to achieve simultaneously in COFs. The ordered arrangement of the TOT radicals within the framework also facilitates efficient charge transport, making the material highly functional for various applications. The study shows that the framework can be modified by changing the components and linkages used, offering flexibility to tailor the electronic properties of the material. This versatility could be valuable for future developments in electronics, spintronics, sensors, and energy storage devices. The research was a collaborative effort involving scientists from different groups led by Manuel Souto, Diego Peña, and Francisco Rivadulla, with contributions from the CICECO-Aveiro Institute of Materials at the University of Aveiro, Portugal. The findings open up new possibilities for the design of advanced materials, particularly since the TOT units can reversibly accept electrons, suggesting potential use in battery technologies. Future research will explore these and other potential applications in greater detail.