Molecular on-surface photochemistry recently emerged as an alternative strategy to thermal reactions to synthesize low-dimensional carbon-based nanomaterials, particularly on nonmetallic surfaces. However, there is still limited knowledge about the crucial aspects influencing photoreactivity in the context of surface chemistry, which contrasts with the fast progress in thermally activated reactions on metal surfaces. By reviewing recent developments in the on-surface photochemistry field, this minireview focuses on some key aspects crucial for the comprehension of photoreactions on surfaces: from the photoexcitation process to basic mechanistic aspects and intermediates characterization, including the molecular preorganization impact on the reaction evolution. To clarify these aspects, we rely upon well-established concepts of traditional photochemistry while highlighting the role of the surface. Finally, it is concluded with considerations on the evolution of the field.

CATRIN RCPTM Palacký University Olomouc Šlechtitelů 27 77146 Olomouc Czech Republic

Department of surfaces and molecular structures Institute of Physics of the Czech Academy of Sciences Cukrovarnická 10 16200 Prague Czech Republic

Organic Chemistry Department Faculty of Chemical Sciences Universidad Complutense Madrid Pl de las Ciencias 2 28040 Madrid Spain

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