Aromatic C‐Nitroso Compounds: From Solid‐State Reactivity to New Materials

This review represents the investigations of the aromatic C‐nitroso compounds and their dimerizations to corresponding azodioxides in specific environments, in polycrystalline phase and on the organized surfaces. The behavior of these compounds is discussed within the frame of basic principles of physical organic chemistry extended to the reaction mechanisms in the solid state where chemical reactions are coupled with the phase transitions. Particularly, the property of formation of mixed dimers (by combining structurally different nitroso compounds) shows that the nitroso monomers differ in selectivity. The fundamental knowledge thus acquired was crucial for the investigations of these compounds and their dimerization/polymerization reactions in the design of new materials for applications in the field of molecular electronics and as porous substances for gas adsorption. Nitroso compounds equipped with two or more nitroso groups form interesting polymers which could behave as, e.g., semiconductors. Dimerization and polymerization of aromatic C‐nitroso compounds were studied experimentally on the organized surfaces by a range of methods such as atomic force microscopy (AFM), scanning tunneling microscopy (STM), ellipsometry, nano‐FTIR and Raman spectroscopy providing valuable findings that may be used in future design of organic electronic devices.