Abstract
This review is focused on the dimerization and dissociation of aromatic C-nitroso compounds and their dimers, the reactions that could be used as a convenient model for studying the thermal organic solid-state reaction mechanisms. This molecular model is simple because it includes formation or breaking of only one covalent bond between two nitrogen atoms. The crystalline molecular solids of nitroso dimers (azodioxides) dissociate by photolysis under the cryogenic conditions, and re-dimerize by slow warming. The thermal re-dimerization reaction is examined under the different topotactic conditions in crystals: disordering, surface defects, and phase transformations. Depending on the conditions, and on the molecular structure, aromatic C-nitroso compounds can associate to form one-dimensional polymeric structures and are able to self-assemble on gold surfaces.
Highlights
Over the last decades, solid-state chemistry has emerged as a rapidly growing area of science
It is of crucial importance to gain deeper insights into the mechanistic basis of reactions occurring in the solid state
While the studies of photochemically-induced processes and their basic mechanistic studies initiated by Cohen, Schmidt, Buergi, and Dunitz et al are available from the vast literature [3,4,5,6,7,8,9,10,11], the mechanisms of the thermal organic solid-state reactions are still an open issue
Summary
Solid-state chemistry has emerged as a rapidly growing area of science. I.e., the breaking and/or formation of chemical bonds are, in crystalline molecular solids, more or less accompanied by and coupled with phase changes of the crystal lattice [7]. From the shapes of the kinetic curves it is possible to estimate which of the processes (chemical reaction or the phase change) is dominant. Avrami-Erofeev [15,16,17,18] These the solid-state kinetics of phase the transformations have mathematical representations describedrecently by the representations described by the (AE). Dimensionality of the reaction (parameter m).solid-state kinetics of the thermally-induced reactions is. The main difficulty in the experimental solid-state kinetics of theorthermally-induced reactions is in in satisfying thethe reproducibility of measurements [23,24].
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