Structure and topochemistry of azodioxide oligomers in solid state

Bibulić, Petar; Rončević, Igor; Varga, Katarina; Mihalić, Zlatko; Vančik, Hrvoj

doi:10.1016/j.molstruc.2015.10.009

Cited by 14 publications

(17 citation statements)

References 20 publications

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“…The very fast dimerization reaction of p-bromonitrosobenzene after cryogenic photolysis could be attributed to the strong topochemical effect where the reaction starts from the "intimate monomer pair" of the molecules at the nitrogen-nitrogen distance of 2.3 Å (the term strong topochemical effect is used as a terminus technicus describing the influence of the vicinity of the reactive centers on the reactivity in formation of covalent bond). Similar kinetic behaviour was also observed in solid-state photothermal reactions of polymeric p-dinitrosobenzene [49,50]. The kinetics of this polymerization reaction will be discussed later in more detail.…”

Section: Dimerization Starting From the "Intimate Monomer Pair"supporting

confidence: 71%

Aromatic C-Nitroso Compounds and Their Dimers: A Model for Probing the Reaction Mechanisms in Crystalline Molecular Solids

Biljan

Vančik

2017

Crystals

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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.

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Section: Dimerization Starting From the "Intimate Monomer Pair"supporting

confidence: 71%

Aromatic C-Nitroso Compounds and Their Dimers: A Model for Probing the Reaction Mechanisms in Crystalline Molecular Solids

Biljan

Vančik

2017

Crystals

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“…[6] The AE model has been successfully used to describe many solidstate processes-phase transitions, nanocluster formation, crystallization and chemical reactions. [13][14][15][16] DOI: 10.5562/cca3220…”

Section: Avrami-erofeev Modelmentioning

confidence: 99%

“…The observable folding which appears in larger crystalline particles is expected from the extent of molecular folding found in PNND by calculation. [6] Such a robust structure is a consequence of regular molecular arrangement and as such could be a suitable starting material for the study of the photochemical and thermochemical reaction mechanisms in the solid state.…”

Section: Morphology Of the Submicrometer Particles Of Pnndmentioning

confidence: 99%

“…[6] The azodioxy bonds reform upon warming the samples. This is indicated by the decrease of the monomeric -N=O signal (1521 cm -1 ) and the simultaneous increase of the E-ONNO signal (1264 cm -1 ).…”

Section: Photodissociation and Re-dimerizationmentioning

confidence: 99%

“…It has been found that by deposition of 1,4-dinitrosobenzene vapor onto the surface cooled to 12 K produces a solid layer consisting only of the nitroso monomer. [6,7] Warming the sample to around 150 K causes fast polymerization. Recently, it has been found that the formation of polymers under cryogenic condition is not a simple process.…”

Section: Introductionmentioning

confidence: 99%

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Polymerization of 1,4-dinitrosobenzene: Kinetics and Submicrocrystal Structure

et al. 2017

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In this study, the structure of the polycrystalline poly(l,4-phenyleneazine N,N-dioxide) was investigated by Scanning Electron Microscopy and related with the previously calculated molecular structure. Kinetics of polymerization of 1,4-dinitrosobenzene, prepared by both cryogenic UV photolysis and in vacuo deposition were measured by time-resolved FT-IR spectroscopy. Acquired data was analyzed by curve fitting with the standard Avrami-Erofeev and two-step consecutive reactions models. Activation parameters were calculated from Arrhenius and Eyring-Polanyi equations, for both models. The results obtained by using the two models, along with the goodness-of-fit parameters, were compared. It was shown that both bulk-based and reaction-based models can be used to adequately describe solid-state chemical reaction kinetics. Furthermore, a two-step consecutive reactions model is a suitable alternative to the most commonly used AvramiErofeev model.

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Thermally‐Induced Reactions of Aromatic Crystalline Nitroso Compounds

et al. 2019

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Three types of organic solid‐state reactions, dimerizations, dissociations, and Z‐E isomerizations were investigated by using the transformations of aromatic C‐nitroso compounds in crystalline solids as a convenient molecular model. Here we propose a conceptual frame for solid‐state organic reaction mechanisms by examining activation parameters obtained from kinetic measurements under specific experimental conditions. The possibility of the appearance of a sort of short‐lived intermediate liquid phase that constitutes a critical condition for initiating chemical reaction in crystalline solids, similarly to the mechanism for the thermal solid‐state reactions proposed by Paul and Curtin is discussed. The analogy of the proposed concept with the recent hypothesis about the variable rigidity/softness of the reaction cavity in the enzyme reactions, and with the newest molecular dynamic simulation studies of solid phase transformations was considered.

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Structure and topochemistry of azodioxide oligomers in solid state

Cited by 14 publications

References 20 publications

Aromatic C-Nitroso Compounds and Their Dimers: A Model for Probing the Reaction Mechanisms in Crystalline Molecular Solids

Aromatic C-Nitroso Compounds and Their Dimers: A Model for Probing the Reaction Mechanisms in Crystalline Molecular Solids

Polymerization of 1,4-dinitrosobenzene: Kinetics and Submicrocrystal Structure

Thermally‐Induced Reactions of Aromatic Crystalline Nitroso Compounds

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