Functionalization of Diamond(100) by Diels−Alder Chemistry

and, George T. Wang; Bent, Stacey F.; Russell, Jr. and John N.; Butler, James E.; D'Evelyn, Mark P.

doi:10.1021/ja993024i

Cited by 91 publications

(93 citation statements)

References 29 publications

(19 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The authors outline several possibilities based on mechanisms proposed for thermal reactions of similar species at diamond [68,69,70] and silicon [71,72] surfaces, and the earlier work of Mazur and Murray, who proposed that surface carbon radicals form when carbon substrates are heated under vacuum or are abraded in the absence of air [29,30]. Figures 7-9 depict possible reaction pathways.…”

Section: Grafting Using Alkenes and Alkynesmentioning

confidence: 99%

Covalent modification of graphitic carbon substrates by non-electrochemical methods

Barrière

Downard

2008

J Solid State Electrochem

156

119

View full text Add to dashboard Cite

Abstract:New methods for modifying graphitic carbon surfaces without electrochemical assistance, and without the deliberate formation of carbon surface oxygen functionalities, have emerged in the past decade. The approaches rely on spontaneous reactions of aryldiazonium salts, primary amines, ammonia and iodine azide at room temperature, chemical reduction of aryldiazonium salts, reactions of alkenes and alkynes at elevated temperatures, and photochemical reactions of alkenes, alkynes, azides and diazirines. This review describes the methodology and scope of these reactions at graphitic carbon materials (excluding carbon nanotubes), examines mechanistic possibilities and future prospects.

show abstract

Section: Grafting Using Alkenes and Alkynesmentioning

confidence: 99%

Covalent modification of graphitic carbon substrates by non-electrochemical methods

Barrière

Downard

2008

J Solid State Electrochem

156

119

View full text Add to dashboard Cite

show abstract

“…We start our discussion of the slab model used in this calculation by first considering the relaxed (100) surface of diamond, which contains unsaturated dimers with significant carboncarbon double bond character that has been successfully functionalized with a Diels-Adler reaction [24]. The C(100) surface is one of the high surface energy facets and is one of the growth faces of DLC surface films.…”

Section: C(100)2x1-h Model and Computational Methodsmentioning

confidence: 99%

Atomistic Frictional Properties of the C(100)2x1-H Surface

Jones

Tang

Hsia

et al. 2013

Advances in Tribology

View full text Add to dashboard Cite

Density functional theory-(DFT-) based ab initio calculations were used to investigate the surface-to-surface interaction and frictional behavior of two hydrogenated C(100) dimer surfaces. A monolayer of hydrogen atoms was applied to the fully relaxed C(100)2x1 surface having rows of C=C dimers with a bond length of 1.39Å. The obtained C(100)2x1-H surfaces (C-H bond length 1.15Å) were placed in a large vacuum space and translated toward each other. A cohesive state at a surface separation of 4.32Å that is stabilized by approximately 0.42 eV was observed. An increase in the charge separation in the surface dimer was calculated at this separation having a 0.04 e transfer from the hydrogen atom to the carbon atom. The Mayer bond orders were calculated for the C-C and C-H bonds and were found to be 0.962 and 0.947, respectively. C-H bonds did not change substantially from the fully separated state. A significant decrease in the electron density difference between the hydrogen atoms on opposite surfaces was seen and assigned to the effects of Pauli repulsion. The surfaces were translated relative to each other in the (100) plane, and the friction force was obtained as a function of slab spacing, which yielded a 0.157 coefficient of friction.

show abstract

“…In fact, [4+2] cycloaddition reaction occurs on the clean diamond (100)-2 × 1 surface, where the surface dimer acts as a dienophile. The surface product was found to be stable up to approximately 1,000 K [59,60]. 1,3-Butadiene attains high coverage as well as forms a thermally stable adlayer on reconstructed diamond (100)-2 × 1 surface due to its ability to undergo [4+2] cycloaddition [61].…”

Section: [4+2] Cycloadditions On Surfacementioning

confidence: 99%

A Mechanistic Spectrum of Chemical Reactions

Inagaki

2009

Orbitals in Chemistry

View full text Add to dashboard Cite

The mechanism of chemical reactions between electron donors and acceptors continuously changes with the power of the donors and the acceptors. The interaction between the HOMO (d) of the donors and the LUMO (a*) of the acceptors or delocalization of electrons is important for the reactions. The electron d-to-a* transferred configuration mixes to a significant extent. As the donors and/or the acceptors are strong, their excited configurations appreciably mixes together with the transferred configuration. The d-a and d*-a* orbital interactions are important in addition to the d-a* interaction. Reactions have features characteristic of the excited-state reactions although the donor-acceptor system is not really excited, but in the ground state. This process is termed pseudoexcitation. The a-d-a*-d* interaction is important. For much stronger donors and acceptors, the electron transferred configuration is stable and predominant. Covalent bonds do not form but instead ionic pairs, and electron transfer results. A mechanistic spectrum of chemical reactions is composed of the delocalization, pseudoexcitation, and electron transfer bands.

show abstract

Functionalization of Diamond(100) by Diels−Alder Chemistry

Cited by 91 publications

References 29 publications

Covalent modification of graphitic carbon substrates by non-electrochemical methods

Covalent modification of graphitic carbon substrates by non-electrochemical methods

Atomistic Frictional Properties of the C(100)2x1-H Surface

A Mechanistic Spectrum of Chemical Reactions

Contact Info

Product

Resources

About