Chemical functionalization is one of the most powerful and widely used strategies to control the properties of nanomaterials, particularly in the field of graphene. However, the ill-defined structure of the present functionalized graphene inhibits atomically precise structural characterization and structure-correlated property modulation. Here we present a general edge chlorination protocol for atomically precise functionalization of nanographenes at different scales from 1.2 to 3.4 nm and its application in graphene nanoribbons. The well-defined edge chlorination is unambiguously confirmed by X-ray single-crystal analysis, which also discloses the characteristic non-planar molecular shape and detailed bond lengths of chlorinated nanographenes. Chlorinated nanographenes and graphene nanoribbons manifest enhanced solution processability associated with decreases in the optical band gap and frontier molecular orbital energy levels, exemplifying the structure-correlated property modulation by precise edge chlorination.

The structural and electronic properties of four isomers of didodecyl[1]‐benzothieno[3,2‐b][1]benzothiophene (C12‐BTBT) have been investigated. Results show the strong impact of the molecular packing on charge carrier transport and electronic polarization properties. Field‐induced time‐resolved microwave conductivity measurements unravel an unprecedented high average interfacial mobility of 170 cm² V⁻¹ s⁻¹ for the 2,7‐isomer, holding great promise for the field of organic electronics.

Multifunctional materials can be engineered by combining multiple chemical components, each conferring a well-defined function to the ensemble. Graphene is at the centre of an ever-growing research effort due to its combination of unique properties. Here we show that the large conformational change associated with the trans–cis photochemical isomerization of alkyl-substituted azobenzenes can be used to improve the efficiency of liquid-phase exfoliation of graphite, with the photochromic molecules acting as dispersion-stabilizing agents. We also demonstrate reversible photo-modulated current in two-terminal devices based on graphene–azobenzene composites. We assign this tuneable electrical characteristics to the intercalation of the azobenzene between adjacent graphene layers and the resulting increase in the interlayer distance on (photo)switching from the linear trans-form to the bulky cis-form of the photochromes. These findings pave the way to the development of new optically controlled memories for light-assisted programming and high-sensitive photosensors.