Adsorption of iodoalkanes on graphite

Sun, Chengguo; Brewer, Adam Y.; Clarke, Stuart M.; Bhinde, Tej; Parker, Julia

doi:10.1080/00268976.2012.762127

Cited by 4 publications

(5 citation statements)

References 32 publications

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“…This implies that any interaction between iodine atoms is rather weak, in contrast with the strong iodine–iodine interactions that have been observed for iodoalkanes, where iodine atoms on neighboring molecules are positioned closer than the sum of their van der Waals radii. 35 The lack of strong interactions is supported by the DFT calculations, which indicate that the vast majority of the binding energy of the layer is due to dispersion interactions. However, the molecules are oriented so that the σ-hole of one iodine atom would point at the belt of electron density surrounding the circumference of the neighboring iodine atom.…”

Section: Discussion and Conclusionmentioning

confidence: 87%

“…34 The zigzag arrangement of iodine atoms closely resembles the placement of iodine atoms in iodoalkane overlayers. 35,36 In the flat arrangement, where the iodine atoms approach each other most closely, the I−I separation is 4.36 Å, somewhat larger than the sum of the van der Waals radii, 3.96 Å. This implies that any interaction between iodine atoms is rather weak, in contrast with the strong iodine−iodine interactions that have been observed for iodoalkanes, where iodine atoms on neighboring molecules are positioned closer than the sum of their van der Waals radii.…”

Section: ■ Discussion and Conclusionmentioning

confidence: 99%

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Combined Diffraction and Density Functional Theory Calculations of Halogen-Bonded Cocrystal Monolayers

Sacchi¹,

Brewer²,

Jenkins³

et al. 2013

Langmuir

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This work describes the combined use of synchrotron X-ray diffraction and density functional theory (DFT) calculations to understand the cocrystal formation or phase separation in 2D monolayers capable of halogen bonding. The solid monolayer structure of 1,4-diiodobenzene (DIB) has been determined by X-ray synchrotron diffraction. The mixing behavior of DIB with 4,4′-bipyridyl (BPY) has also been studied and interestingly is found to phase-separate rather than form a cocrystal, as observed in the bulk. DFT calculations are used to establish the underlying origin of this interesting behavior. The DFT calculations are demonstrated to agree well with the recently proposed monolayer structure for the cocrystal of BPY and 1,4-diiodotetrafluorobenzene (DITFB) (the perfluorinated analogue of DIB), where halogen bonding has also been identified by diffraction. Here we have calculated an estimate of the halogen bond strength by DFT calculations for the DITFB/BPY cocrystal monolayer, which is found to be ∼20 kJ/mol. Computationally, we find that the nonfluorinated DIB and BPY are not expected to form a halogen-bonded cocrystal in a 2D layer; for this pair of species, phase separation of the components is calculated to be lower energy, in good agreement with the diffraction results.

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Section: Discussion and Conclusionmentioning

confidence: 87%

Section: ■ Discussion and Conclusionmentioning

confidence: 99%

Combined Diffraction and Density Functional Theory Calculations of Halogen-Bonded Cocrystal Monolayers

Sacchi¹,

Brewer²,

Jenkins³

et al. 2013

Langmuir

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“…The compressibility ratio of acetic acid in the bulk and surface is significantly different with the 2D layer being approximately 2 orders of magnitude bigger than the bulk. There is evidence that these 2D layers are more susceptible to expanding/contracting relative to 3D crystals partly due to a change in the coordination number. , This is also supported by data reported in the literature, where the pure stearic acid bulk isothermal compressibility coefficient is approximately 7.9 × 10 –5 bar –1 and the 2D compressibility coefficient of stearic acid Langmuir layer at the air–water interface in the condensed phase is 3.0 × 10 5 bar –1 ; the 2D layer is 10 orders of magnitude more compressible. (Details of the compressibility calculation are provided in the Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

A Novel Study on the Role of Pressure on Surface Adsorption from Solutions

2023

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In this work, we present experimental data on the behavior of model additives adsorbed at the solid/liquid interface as a function of pressure. We report that some additives adsorbed from non-aqueous solvents exhibit rather little variation with pressure, while others exhibit more significant changes. We also display the important pressure dependence of added water. This pressure dependence is relevant, indeed central to many commercially important situations where the adsorption of molecular species to the solid/liquid interface under high pressure is key, such as wind turbines, and this work should help in understanding how protective, anti-wear, or friction-reducing agents can persist (or not) under these extreme conditions. With a very significant gap in the fundamental understanding of the role of pressure on adsorption from solution phases, this important fundamental study provides a methodology to investigate the pressure dependence of these academically and commercially important systems. In the best case, one may even be able to predict which additives will lead to more adsorption under pressure and avoid those that may desorb.

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“…It has been well documented that haloperfluorocarbons (X–PFCs) act as good XB donors and are capable of establishing strong XBs with electron-rich molecules, especially pyridine derivatives. ,− Therefore, the specific N···X–PFC synthons have been commonly utilized in 3D crystal engineering and supramolecular architecture. The formation of 2D XB-based monolayers of X-PFCs and pyridyl species was first reported by Clarke et al, and in their pioneering works, the self-assembled cocrystal physisorbed monolayers involving 4,4′-bipyridine and 1,4-diiodotetrafluorobenzene ( 4F2I ), 1,4-dibromotetrafluorobenzene ( 4F2I ), 1,4-diiodobenzene ( 4H2I ) on graphite were identified via synchrotron X-ray diffraction and DFT calculations. − Moreover, they also studied the adsorbed monolayers of several halogenated alkanes and pyridine derivatives on the graphite substrate using differential scanning calorimetry and X-ray and neutral diffraction. − Subsequently, Wan and co-workers has demonstrated the formation of an open porous network on HOPG using ethynylpyridine and aryl-halide-based building blocks, and they obtained four main supramolecular assemblies driven by the N···I interactions between terminal pyridyl moieties and iodoperfluorobenzenes . However, to the best of our knowledge, few theoretical studies concerning intermolecular X···N bonds in the binary network of X-PFCs and pyridyl derivatives on graphite surface have been reported to date.…”

Section: Introductionmentioning

confidence: 95%

Halogen-Bond-Based Molecular Self-Assembly on Graphene Surface: A First-Principles Study

Zhang

et al. 2017

J. Phys. Chem. C

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The formation of halogen-bond-based 2D supramolecular assemblies on solid surfaces has become a hot research topic in recent years. Herein, we report a theoretical study of the halogen-bonded network formation of pyridine derivatives and aryl−halide molecules on graphene surface using first-principles density functional theory (DFT) calculations. To unravel the characteristics of molecule−molecule and molecule−substrate interactions, the noncovalent interaction index (NCI), electron density difference (EDD), density of state (DOS), and topographical scan tunneling microscopy (STM) image analyses were undertaken. The N•••I interactions between terminal pyridyl groups and iodoperfluorobenzenes are predicted to be somewhat stronger than the molecule−surface stacking interactions and appear to be the primary interactions in the self-assembled networks, with geometries in good agreement with the experimental STM images. The results reported in this work should be of great importance in the applications of these interactions in molecular self-assembly on surfaces.

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Adsorption of iodoalkanes on graphite

Cited by 4 publications

References 32 publications

Combined Diffraction and Density Functional Theory Calculations of Halogen-Bonded Cocrystal Monolayers

Combined Diffraction and Density Functional Theory Calculations of Halogen-Bonded Cocrystal Monolayers

A Novel Study on the Role of Pressure on Surface Adsorption from Solutions

Halogen-Bond-Based Molecular Self-Assembly on Graphene Surface: A First-Principles Study

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