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

Bibulić, Petar; Rončević, Igor; Bermanec, Vladimir; Vančik, Hrvoj

doi:10.5562/cca3220

Cited by 10 publications

(9 citation statements)

References 14 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%

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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%

“…In addition, morphology of the p-dinitrosobenzene polymer as examined by scanning electron microscopy (SEM), shows interesting features (Figure 10b) [50]. Figure 9.…”

Section: One-dimensional Polymerization Reactionsmentioning

confidence: 99%

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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“…Electrochemically, the disclosed oximates (1-5) undergo 1-electron redox per oximate group to form nitroso derivatives followed by significant reversible structural modifications, which is strongly dependent on the conjugation as well as molecular structures (Figure 2). On one hand, para-dioximate compounds (e.g., Li2-BQDO) are oxidized to the intermediate phase (e.g., para-dinitrosobenzene) which undergoes intermolecular polymerization through azodioxy (-ONNO-) linkage 25 to poly(1,4phenyleneazine-N,N-dioxide) (PNND) (Mechanism 1) 26 . The in-situ formation of PNND upon oxidation of Li2-BQDO is confirmed by Rietveld refinement of the experimental PXRD pattern (Fig.…”

Section: Redox (Oxoammonium Cation ↔ Aminoxy Anion) Molecular Design ...mentioning

confidence: 99%

Revealing the Solid-State Electrochemistry of Conjugated Oximates: Towards a New Functionality for Organic Batteries

Wang

Apostol

Rambabu

et al. 2022

Preprint

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In the rising advent of organic Li-ion cathodes with practical characteristic of being air-stable while in the reduced lithium-reservoir form, we report herein a new class of organic Li-ion positive electrode materials - the conjugated oximate lithium salts. The solid-phase electrochemistry of first five examples of the oximate class, including cyclic (aromatic), acyclic (non-aromatic), aliphatic and tetra-functional stereotypes, uncovers the complex interplay between the molecular structure and the electroactivity in the solid phase, as well as the potential of this rich family as cathode materials for lithium-ion batteries. The conjugation of oximate functions within the molecular core is found to endow excellent air stability of lithiated reduced phases, an important prerequisite for practical use as Li-ion positive electrode materials. Amongst the exotic features characterizing the solid-state electrochemistry of this class of materials, the most appealing one belongs to the reversible solid-state polymerization through intermolecular azodioxy coupling (-ONNO-) and the intramolecular furoxan cyclization of their oxidized forms. In the disclosed series of materials, the best performing candidate delivers high reversible capacity of 357 at an average potential of 3.0 vs. Li+/Li0, attaining over 1 KWh kg-1 specific energy content.

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“…Isothermal solid-state kinetics can be described by both bulk-based and mechanistic models. , Bulk-based models (Table ) originated from the investigation of phase transformations and diffusion-controlled reactions. − They have a single rate parameter, analogous to a rate constant in mechanistic models, which limits their flexibility and robustness but provides a straightforward determination of activation parameters. The majority of solid-state processes can be adequately described either by a simple exponential model or the Avrami-Erofeev equation …”

Section: Introductionmentioning

confidence: 99%

“…The majority of solid-state processes can be adequately described either by a simple exponential model or the Avrami-Erofeev equation. 34 Unlike in mechanistic models, the activation parameters obtained by bulk-based models (and isoconversional models, described below) only empirically describe the transformation, that is, give the temperature dependence of the rate parameter. Thus, we shall use the modifier "observed" when referring to activation parameters obtained by nonmechanistic models.…”

Section: Introductionmentioning

confidence: 99%

Isothermal and Isoconversional Modeling of Solid-State Nitroso Polymerization

et al. 2020

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The solid-state formation of azodioxide polymers from aromatic dinitroso compounds with different spacer groups was used as a model reaction for a comprehensive analysis that included bulk-based, mechanistic, and isoconversional kinetic methods. Dinitroso species were prepared in situ from azodioxides by UV cleavage under cryogenic conditions, after which their thermally induced conversion to azodioxides was followed by Fourier transform IR spectroscopy. The obtained data were used to calculate activation parameters and determine the influence of the spacer on the kinetics. Isoconversional models suggest a distribution of activation energies, pointing to an important (topochemical) effect of the local environment on the reactivity. In general, bulk-based and isoconversional kinetic models gave poorer fits but produced mutually consistent rate parameters. Similar energies and entropies of activation were obtained with all three approaches, suggesting that they all describe the same underlying physical phenomena; that is, the polymerization by bond-making is the dominant process.

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

Cited by 10 publications

References 14 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

Revealing the Solid-State Electrochemistry of Conjugated Oximates: Towards a New Functionality for Organic Batteries

Isothermal and Isoconversional Modeling of Solid-State Nitroso Polymerization

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