A π-stacked phenylacetylene dimer

Maity, Surajit; Patwari, G. Naresh; Sedlák, Róbert; Hobza, Pavel

doi:10.1039/c1cp20677j

Cited by 38 publications

(71 citation statements)

References 83 publications

(104 reference statements)

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“…Previous studies concerning the structure of ethylbenzene, styrene and phenylacetylene, are limited. Ab initio studies of the structure of phenylacetylene showed that the most stable (global minimum) is the anti‐parallel arrangement; however, other parallel orientations were also found to be highly probable . In the present experimental investigation, the most preferable orientation for the closest coordinating molecules were found to be in a parallel arrangement.…”

Section: Resultscontrasting

confidence: 42%

The Structure of Ethylbenzene, Styrene and Phenylacetylene Determined by Total Neutron Scattering

et al. 2017

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Organic solvents such as phenylacetylene, styrene and ethylbenzene are widely used in industrial processes, especially in the production of rubber or thermoplastics. Despite their important applications detailed knowledge about their structure is limited. In this paper the structures of these three aromatic solvents were investigated using neutron diffraction. The results show that many of their structural characteristics are similar, although the structure of phenylacetylene is more ordered and has a smaller solvation sphere than either ethylbenzene or styrene. Two regions within the first coordination sphere, in which the surrounding molecules show different preferable orientations with respect to the central molecule, were found for each liquid. Additionally, the localisation of the aliphatic chains reveals that they tend to favour closer interactions with each other than to the aromatic rings of the adjacent molecules.

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Section: Resultscontrasting

confidence: 42%

The Structure of Ethylbenzene, Styrene and Phenylacetylene Determined by Total Neutron Scattering

et al. 2017

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“…8-10 Such a large broadening in the electronic spectra of these π -stacked complexes has been explained in terms of very short lifetime in the S 1 state due to rapid deactivation and or the presence of similar isomeric structures. [8][9][10] In the case of the indole · · · HFB complex reported here, the broadening (FWHM ∼ 300 cm −1 ) in the electronic spectrum could be due to the similar reason.…”

Section: A Electronic Spectramentioning

confidence: 52%

“…[6][7][8][9][10][11] On the other hand, there are extensive theoretical studies on the π -stacking interaction in the aromatic dimers. [12][13][14][15][16][17][18][19][20][21][22][23][24] The πstacked configuration is also not observed in the experiment in the case of the benzene dimer, which is undoubtedly the most thoroughly studied aromatic dimer in the literature.…”

Section: Introductionmentioning

confidence: 99%

Observation of exclusively π-stacked heterodimer of indole and hexafluorobenzene in the gas phase

Kumar

Das

2013

The Journal of Chemical Physics

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In this study, the structure of the indole···hexafluorobenzene dimer has been investigated in the gas phase by using resonant two photon ionzation (R2PI) and IR-UV double resonance spectroscopy combined with quantum chemistry calculations. We have confirmed the presence of exclusively π-stacked structure of the dimer from both experimental and theoretical IR spectra in the N-H stretching region. Observation of a single stable structure of the dimer has also been verified through 3D potential energy surface scan of the π-stacked dimer by varying the parallel displacement of the hexafluorobenzene unit simultaneously along the major and minor axes of the indole moiety. π-stacking interaction is present very often between the tryptophan and phenylalanine residues in proteins. But this interaction has not been observed earlier in the gas phase experiment by studying indole···benzene dimer because the N-H group of indole predominately directs towards the N-H···π hydrogen bonded T-shaped structure. The chosen molecular systems in this study not only rule out the possibility of the formation of the N-H···π bound T-shaped dimer but also enable the determination of the structure by probing the N-H group. The π-stacked indole···hexafluorobenzene dimer has a unique structure where the center of the hexafluorobenznene ring is aligned with the center of the shared bond of the indole ring. Our work provides useful insight in designing unnatural proteins having strong π-stacking interaction between the tryptophan and phenylalanine residues.

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“…PHA2-B, PHA2-C, and PHA2-G are minima, while, at the MP2/cc-pVTZ level, all other structures are transition states. 51 Structures are shown below in Figure 1. The nature of the interactions for the different isomers has been described previously.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The nature of the interactions for the different isomers has been described previously. 51 Performance of Popular DFT Methods for Binding Energies. Table 2 shows the errors in computed binding energies of popular DFT methods relative to the CCSD(T)/ CBS energies and the Mean Absolute Deviation (MAD) of the errors calculated for the CH···π bound dimers (PHA2-A,B), the π-stacked dimers (PHA2-(C−G)), and the entire set.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Stochastic Search of Molecular Cluster Interaction Energy Surfaces with Coupled Cluster Quality Prediction. The Phenylacetylene Dimer

Addicoat

Nishimura

Sato

et al. 2013

J. Chem. Theory Comput.

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We report a stochastic search methodology on the basis of dispersion-augmented density functional theory (DFT), aimed at finding low energy isomers of the phenylacetylene dimer as well as methane and benzene dimers. Stochastic search of the molecular cluster interaction energy surfaces was carried out with the computationally inexpensive dispersion-augmented, third-order self-consistent charge density functional tight-binding (DFTB3-D) method, and energetically low-lying molecular cluster geometries were identified, including several that had previously been optimized at the MP2/cc-pVTZ level of theory and had single point interaction energies evaluated at the coupled-cluster singles, doubles, and perturbative triples (CCSD(T)) level of theory in the complete basis set limit (Maity, S. et al. Phys. Chem. Chem. Phys 2011, 13, 16706). In addition, the search procedure identifies several additional low-energy isomers that map a reaction path, rotating one monomer through a full 360° relative to the first. We found that binding energies from long-range corrected functional combined with the local response dispersion correction (LC-BOP+LRD) yields binding energies that are within 1 kJ mol(-1) of the CCSD(T)/CBS results for both π-stacked and CH···π structures. In contrast, other functionals and second-order Møller-Plesset perturbation methods favored one binding motif or the other and therefore are not ideal to describe a global potential energy surface.

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A π-stacked phenylacetylene dimer

Cited by 38 publications

References 83 publications

The Structure of Ethylbenzene, Styrene and Phenylacetylene Determined by Total Neutron Scattering

The Structure of Ethylbenzene, Styrene and Phenylacetylene Determined by Total Neutron Scattering

Observation of exclusively π-stacked heterodimer of indole and hexafluorobenzene in the gas phase

Stochastic Search of Molecular Cluster Interaction Energy Surfaces with Coupled Cluster Quality Prediction. The Phenylacetylene Dimer

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