The Self-Association of Graphane Is Driven by London Dispersion and Enhanced Orbital Interactions

Wang, Changwei; Mo, Yirong; Wagner, J. Philipp; Schreiner, Peter R.; Jemmis, Eluvathingal D.; Danovich, David; Shaik, Sason

doi:10.1021/acs.jctc.5b00075

Cited by 41 publications

(49 citation statements)

References 80 publications

(169 reference statements)

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“…[96] Secondly,t he interactions are accompanied by an intuitively understandable charge-transfer contribution that further shortens H···H contact distances and amounts to about 15 %ofthe total interaction energy. [108] Nature seems to be employing these principles in building membranes from either long-chain fatty acids,o r, when required from more rigid steroid skeletons,e ven all-transfused cyclobutanes ([n]ladderanes [109] )t hat provide exceptionally dense cell walls for some bacteria that have to resist oxidative stress. [60c] Although the assembly of such strained polycycles requires quite some energy,their association leads to dispersion-dominated interaction energies that are significantly higher than even longer straight-chain fatty acids.…”

Section: Methodsmentioning

confidence: 99%

London Dispersion in Molecular Chemistry—Reconsidering Steric Effects

2015

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London dispersion, which constitutes the attractive part of the famous van der Waals potential, has long been underappreciated in molecular chemistry as an important element of structural stability, and thus affects chemical reactivity and catalysis. This negligence is due to the common notion that dispersion is weak, which is only true for one pair of interacting atoms. For increasingly larger structures, the overall dispersion contribution grows rapidly and can amount to tens of kcal mol(-1) . This Review collects and emphasizes the importance of inter- and intramolecular dispersion for molecules consisting mostly of first row atoms. The synergy of experiment and theory has now reached a stage where dispersion effects can be examined in fine detail. This forces us to reconsider our perception of steric hindrance and stereoelectronic effects. The quantitation of dispersion energy donors will improve our ability to design sophisticated molecular structures and much better catalysts.

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Section: Methodsmentioning

confidence: 99%

London Dispersion in Molecular Chemistry—Reconsidering Steric Effects

2015

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“…The distance ( d ) between graphane and graphene sheets is the most important parameter for geometric investigations. It is known that the distance ( d 1 ) between adjacent layers in graphite is 3.35 Å, and the DFT calculated distance ( d 2 ) between two parallel nearest planes of hydrogen atoms of [24]‐GA dimer is 1.83 Å (B3LYP‐D3/6‐31G(d, p)) . Seen from Figure and Supporting Information Figure S1–Figure S5, d in different size of [ n ]‐GA@GE complexes, are all in‐between d 1 and d 2 with a value range 2.60–2.69 Å, and just close to the average value of d 1 and d 2 .…”

Section: Resultsmentioning

confidence: 93%

“…Harmonic frequency analyses were performed at the same level to confirm that these structures were minimum on the potential energy surfaces. Diffuse functions are avoided to use for the sake of computational manageability and comparing with the related noncovalent systems . Conversely, the use of diffuse functions in large systems is not always mandatory .…”

Section: Calculation Details and Methodsmentioning

confidence: 99%

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Van Der Waals heterogeneous layer‐layer carbon nanostructures involving π···H‐C‐C‐H···π···H‐C‐C‐H stacking based on graphene and graphane sheets

et al. 2017

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Noncovalent interactions involving aromatic rings, such as π···π stacking, CH···π are very essential for supramolecular carbon nanostructures. Graphite is a typical homogenous carbon matter based on π···π stacking of graphene sheets. Even in systems not involving aromatic groups, the stability of diamondoid dimer and layer-layer graphane dimer originates from C - H···H - C noncovalent interaction. In this article, the structures and properties of novel heterogeneous layer-layer carbon-nanostructures involving π···H-C-C-H···π···H-C-C-H stacking based on [n]-graphane and [n]-graphene and their derivatives are theoretically investigated for n = 16-54 using dispersion corrected density functional theory B3LYP-D3 method. Energy decomposition analysis shows that dispersion interaction is the most important for the stabilization of both double- and multi-layer-layer [n]-graphane@graphene. Binding energy between graphane and graphene sheets shows that there is a distinct additive nature of CH···π interaction. For comparison and simplicity, the concept of H-H bond energy equivalent number of carbon atoms (noted as NHEQ), is used to describe the strength of these noncovalent interactions. The NHEQ of the graphene dimers, graphane dimers, and double-layered graphane@graphene are 103, 143, and 110, indicating that the strength of C-H···π interaction is close to that of π···π and much stronger than that of C-H···H-C in large size systems. Additionally, frontier molecular orbital, electron density difference and visualized noncovalent interaction regions are discussed for deeply understanding the nature of the C-H···π stacking interaction in construction of heterogeneous layer-layer graphane@graphene structures. We hope that the present study would be helpful for creations of new functional supramolecular materials based on graphane and graphene carbon nano-structures. © 2017 Wiley Periodicals, Inc.

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“…[108] Die Natur scheint diese Prinzipien beim Aufbau von Membranstrukturen aus langkettigen Fettsäuren, rigiden Steroidgerüsten und sogar all-trans-verknüpften Cyclobutaneinheiten ([n]Ladderanen) [109] zu nutzen, denn letztere produzieren außergewçhnlich dichte Membranen, um bestimmte Bakterien vor oxidativem Stress zu schützen.…”

Section: London'sche Dispersionunclassified

London’sche Dispersionswechselwirkungen in der Molekülchemie – eine Neubetrachtung sterischer Effekte

2015

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Die London’sche Dispersion, die den attraktiven Teil des Van‐der‐Waals‐Potentials beschreibt, wurde lange als Element struktureller Stabilität in der molekularen Chemie unterschätzt. Als solches beeinflusst sie auch entscheidend die chemische Reaktivität und Katalyse. Ihre Vernachlässigung ist auf die Annahme zurückzuführen, dass die Dispersionswechselwirkung schwach sei, was nur für eine einzelne paarweise Wechselwirkung zweier Atome stimmt. Für Strukturen zunehmender Größe kann die gesamte Dispersionsstabilisierung mehrere zehn kcal mol−1 betragen. Dieser Aufsatz soll die Wichtigkeit inter‐ und intramolekularer Dispersion anhand von Beispielen für die erste Vollperiode verdeutlichen. Die Synergie aus Experiment und Theorie hat ein Niveau erreicht, auf dem Dispersionseffekte sehr genau verstanden werden können. Als Konsequenz daraus werden wir wohl unser Verständnis bezüglich sterischer Hinderung und stereoelektronischer Effekte überdenken müssen. Die Quantifizierung von Dispersionsenergiedonoren wird unsere Fähigkeiten verbessern, komplexe molekulare Strukturen und Katalysatoren zu entwickeln.

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The Self-Association of Graphane Is Driven by London Dispersion and Enhanced Orbital Interactions

Cited by 41 publications

References 80 publications

London Dispersion in Molecular Chemistry—Reconsidering Steric Effects

London Dispersion in Molecular Chemistry—Reconsidering Steric Effects

Van Der Waals heterogeneous layer‐layer carbon nanostructures involving π···H‐C‐C‐H···π···H‐C‐C‐H stacking based on graphene and graphane sheets

London’sche Dispersionswechselwirkungen in der Molekülchemie – eine Neubetrachtung sterischer Effekte

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