A computational study on multiple formaldehyde complexes and their possible chemical reactions as well as the catalytic effect in the gas phase

Mirdoraghi, Somayeh; Piri, Farideh; Vahedpour, Morteza

doi:10.1007/s42452-020-2443-7

Cited by 2 publications

(3 citation statements)

References 28 publications

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“…The 1,3-dioxetane motif is reported earlier in GO by modeling studies and the particle swarm optimization search . Though referred to as epoxide pairs, the optimized geometry clearly shows the rhombic 1,3-dioxetane motif, with the short 1,3 C–C nonbonding distance slightly larger than the computed equilibrium geometry of the molecule (∼1.95 Å) . Since the C–C σ-bond is broken during its formation, it is augmented by a CC bond in the C 2 O stoichiometry.…”

Section: Resultsmentioning

confidence: 99%

“…25 Though referred to as epoxide pairs, the optimized geometry clearly shows the rhombic 1,3-dioxetane motif, with the short 1,3 C−C nonbonding distance slightly larger than the computed equilibrium geometry of the molecule (∼1.95 Å). 48 Since the C−C σ-bond is broken during its formation, it is augmented by a C�C bond in the C 2 O stoichiometry. Among the different ways of distributing this double bonddioxetane combo, we explored the isomeric possibilities based on the nature of π-conjugation.…”

Section: 3-dioxetane Sheets Withmentioning

confidence: 99%

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Alternatives for Epoxides in Graphene Oxide

Jhaa,

Pancharatna,

Balakrishnarajan

2023

J. Chem. Inf. Model.

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The structural mystery of the long-known graphene oxide (GO) unfolds as one of the most abstract conceptual problems among nanomaterials. Generally construed as the oxidized form of graphene, it is proposed to host a variety of functional groups with oxygen and hydrogen. Theoretical studies are abundant on the highly strained epoxides, while larger cyclic ethers having one or more oxygen atoms and vinylogous carbonyls are paid scant attention even though they are predicted by several structural models. The nature of the geometric and electronic structures of these alternative functional groups, the preferred distribution on the graphene lattice, comparative stability, etc., remain unexplored. Our systematic inquiry into the impact of hexagonal and periodic constraints on these mystic functional groups unveils several surprises. Among those that retain the hexagonal carbon backbone, epoxides are surprisingly more stable than larger ethers despite the excessive strain associated with their acute triangular geometry. Epoxidation conserves the planarity of the carbon backbone, which allows their optimal distribution on the lattice by reducing the repulsive interactions from oxygen lone pairs and π-electrons. These findings categorically rule out the possibility of 1,3-ethers in GO and settle the longstanding debate on its existence. They face severe steric repulsion even in low-dimensional systems that tear the σ-skeleton of graphene completely apart, reducing its dimensionality. We show that selective breaking of the σ-bonds is preferred over that of epoxides if backed by cyclic delocalization of electrons. Particularly, 1,6-diones in trans orientation are thermodynamically favored and justify the large holes experimentally observed through microscopic imaging.

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Section: Resultsmentioning

confidence: 99%

Section: 3-dioxetane Sheets Withmentioning

confidence: 99%

Alternatives for Epoxides in Graphene Oxide

Jhaa,

Pancharatna,

Balakrishnarajan

2023

J. Chem. Inf. Model.

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show abstract

“…The 1,3 dioxetane motif is reported earlier in GO by modeling studies 26 and the particle swarm optimization search 25 . Though referred to as epoxide pairs, the optimized geometry clearly shows the rhombic 1,3 dioxetane motif, with the short 1,3 C-C nonbonding distance slightly larger than the molecule (~1.95Å) 46 . Since the C-C σ-bond is broken during its formation, it is augmented by a C=C bond in the C2O stoichiometry.…”

Section: 3-dioxetane Sheets With Residual π-Frameworkmentioning

confidence: 99%

Enigmatic Alternatives for Epoxides in Graphene Oxide

Jhaa

Pancharatna²,

Balakrishnarajan

2023

Preprint

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The structural mystery of the long-known graphene oxide (GO) unfolds as one of the formidably abstract conceptual problems among nanomaterials. Generally construed as the oxidized form of graphene, it is variously proposed to host a variety of functional groups with oxygen and hydrogen. Theoretical studies are abundant on the highly-strained epoxides, while larger cyclic ethers having one or more oxygen atoms and vinylogous carbonyls are paid scant attention even though they are predicted by several structural models. The nature of the geometric and electronic structure of these alternative functional groups, the preferred distribution on the graphene lattice, comparative stability, etc., remains unexplored. Our systematic inquiry into the impact of hexagonal and periodic constraints on these mystic functional groups unveils several surprises. Among those that retain the hexagonal carbon backbone, epoxides are surprisingly more stable than larger ethers despite the excessive strain associated with their acute triangular geometry. Epoxidation conserves the planarity of the carbon backbone that allows their optimal distribution on the lattice by reducing the repulsive interactions from oxygen lone pairs and π-electrons. These findings categorically rule out the possibility of 1,3 ethers in GO and settle the long-standing debate on its existence. They face severe steric repulsion even in low dimensional systems that tear down the σ-skeleton of graphene completely apart, reducing its dimensionality. We show that selective breaking of the σ-bonds is preferred over epoxides if backed by cyclic delocalization of electrons. Particularly, 1,6-diones in trans orientation are thermodynamically favored and justify the large holes experimentally observed through microscopic imaging.

show abstract

A computational study on multiple formaldehyde complexes and their possible chemical reactions as well as the catalytic effect in the gas phase

Cited by 2 publications

References 28 publications

Alternatives for Epoxides in Graphene Oxide

Alternatives for Epoxides in Graphene Oxide

Enigmatic Alternatives for Epoxides in Graphene Oxide

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