Substituent Effects on the Edge-to-Face Aromatic Interactions

Lee, Eun Cheol; Hong, Byung Hee; Lee, Ju Young; Kim, Jong Chan; Kim, Dong-Wook; Kim, Yu‐Kyung; Tarakeshwar, P.; Kim, Kwang S.

doi:10.1021/ja037454r

Cited by 183 publications

(166 citation statements)

References 47 publications

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“…The benzene pair geometry in Table 1 is the parallel-displaced configuration. These studies also indicate that substituents, typically make the stacking stronger with respect to benzene stacking, which is confirmed in our results for methyl and chlorine substituents [44][45][46].…”

Section: Guest-guest Interactions In Gas Phasesupporting

confidence: 90%

Host–guest and guest–guest interactions between xylene isomers confined in the MIL-47(V) pore system

et al. 2012

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The porous MIL-47 material shows a selective adsorption behavior for para, ortho, and meta-isomers of xylenes, making the material a serious candidate for separation applications.The origin of the selectivity lies in the differences in interactions (energetic) and confining (entropic). This paper investigates the xylene-framework interactions and the xylene-xylene interactions with quantum mechanical calculations, using a dispersion corrected density functional and periodic boundary conditions to describe the crystal. First, the strength and geometrical characteristics of the optimal xylene-xylene interactions are quantified by studying the pure and mixed pairs in gas phase. An extended set of initial structures is created and optimized to sample as many relative orientations and distances as possible. Next, the pairs are brought in the pores of MIL-47. The interaction with the terephthalic linkers and other xylenes, increases the stacking energy in gas phase (-31.7 kJ/mol per pair) by roughly a factor four in the fully-loaded state (-58.3 kJ/mol per xylene). Our decomposition of the adsorption energy shows various trends in the contributing xylene-xylene interactions. The absence of a significant difference in energetics between the isomers indicates that entropic effects must be mainly responsible for the separation behavior.Corresponding authors: an.ghysels@ugent.be, veronique.vanspeybroeck@ugent.be 2

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Section: Guest-guest Interactions In Gas Phasesupporting

confidence: 90%

Host–guest and guest–guest interactions between xylene isomers confined in the MIL-47(V) pore system

et al. 2012

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“…2) as simple H-p and p-p interaction models with small binding energy ($1.5-3 kcal/mol) has received a great attention from both experiment and theory over last decades. [8,[26][27][28][29][30] The binding energy of the benzene dimer at the coupled cluster with single, double and perturbative triple excitations level [CCSD(T)] using the complete basis set (CBS) limit shows that the T-shaped edge-to-face conformer is nearly isoenergetic ($2.5 kcal/mol in zero-point-energy corrected binding energy) to the parallel-displaced face-to-face conformer. [8] The strength and configurational orientation of H-p and p-p interactions can be controlled by replacing H or C atoms (heteroatom effect) with other atoms or chemical groups.…”

Section: Factors Influencing P Interaction Strengths H-p and P-p Intementioning

confidence: 99%

“…Correlation of substituent effects on the stability of p-p stacking interactions is also investigated with computed electrostatic potentials (ESPs) and Hammett rconstants models. [8,27,[33][34][35] These models reveal that electronwithdrawing substituents enhance stacking interactions in benzene dimers while electron donating substituents give the opposite effect and hinder stacking interactions. Tarakeshwar et al studied the H-p interaction using the systems of an olefinic (ethene)/aromatic (benzene) p compound interacting with one of HX (X: halide), H 2 O, NH 3 , and CH 4 molecules.…”

Section: Factors Influencing P Interaction Strengths H-p and P-p Intementioning

confidence: 99%

Functional molecules and materials by π‐Interaction based quantum theoretical design

Tehrani

Kim

2016

Int J of Quantum Chemistry

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The intermolecular and intramolecular noncovalent interactions involving p-aromatic compounds have attracted increasing attention over the last decades in chemistry, biology and material sciences. In this review, we discuss contemporary computational studies on the nature and strength of H-p, p-p, and anion-p interactions. We emphasize how modern quantum theoretical approaches ahead of experiment can provide insight into the design of new materials and devices by tuning the p-interactions in cooperative and competitive manners. Usefulness of such approaches towards designing new materials is demonstrated with some examples of molecular recognition/sensing, self-assembly/engineering, receptors, catalysts, supramolecules, graphene, and other two-dimensional (2D) materials/devices.

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“…Eqn (1) has the main importance in interpreting the values of the parameters 2 s and r; less in predicting the unknown values of E. Nevertheless, it serves still as reference when investigating reactivities or activities of benzene derivatives. 3 The exact range of validity is of central importance for any empirical relationship 2 and numerous attempts were made to delimit it for eqn (1) with more precision. 2,4 In kinetics, the deviations encountered were mostly attributed to complex reaction mechanism.…”

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confidence: 99%

Range of validity of the Hammett equation: acidity of substituted ethynylbenzenes

2006

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Acidities of 19 meta-and para-substituted ethynylbenzenes were calculated at the B3LYP/6-311þG(d,p) level and correlated within the framework of the Hammett equation with the calculated acidities of equally substituted benzoic acids. The substituent effects were decomposed in terms of isodesmic reactions into those operating in the anions and in the uncharged molecules. Characteristic deviations from the Hammett equation were found for para-substituents, both for acceptors and donors; the former can be interpreted by the resonance formula only with an electron sextet. With reference to the series of ionization reactions investigated previously, it was possible to reinvestigate the validity of the Hammett equation on the basis of calculated reaction energies using a more homogeneous data set than had been ever accessible from the experimental reactivities. The equation was fulfilled for all meta-substituents with a higher accuracy than commonly attainable with the experimental data. When para-substituents were included, deviations occurred according to the character of the functional group: When this group was an acceptor, the donor substituents showed deviations and vice versa. Another series of reactions proceeding between uncharged groups bonded directly on the benzene ring was investigated in the same way: The Hammett equation held with a similar precision, although its original range of validity was surpassed. The properties of a set of common substituents were investigated by principal component analysis and cluster analysis. There is a fundamental difference between uniform acceptors and more discriminated donors but clustering is not so strong to depreciate common statistical analysis.The Hammett equation has become popular, in spite of its restricted applicability, as the first attempt to predict reactivity by means of an empirical formula. For many years, it has remained the most general and simplest structure-property relationship.1,2 In energy terms, it is expressed by eqn (1).The symbol E(X) may mean the reaction energy or enthalpy but in most cases it stands for the Gibbs energy, or activation Gibbs energy, in a series of reactions of meta-or para-substituted benzene derivatives. The empirical parameter s m or s p characterizes the substituent X, the parameter r is pertinent to the given reaction, E(H) relates to the unsubstituted compound (X = H). In simple terms of organic chemistry, eqn (1) means that the variable substituents X raise changes of reactivity always in the same succession: for instance the substituent effect of 4-CO 2 CH 3 is always twice the effect of 4-Cl. Eqn (1) has the main importance in interpreting the values of the parameters 2 s and r; less in predicting the unknown values of E. Nevertheless, it serves still as reference when investigating reactivities or activities of benzene derivatives. 3The exact range of validity is of central importance for any empirical relationship 2 and numerous attempts were made to delimit it for eqn (1) with more precision. 2,4 In kinetics, the...

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Substituent Effects on the Edge-to-Face Aromatic Interactions

Cited by 183 publications

References 47 publications

Host–guest and guest–guest interactions between xylene isomers confined in the MIL-47(V) pore system

Host–guest and guest–guest interactions between xylene isomers confined in the MIL-47(V) pore system

Functional molecules and materials by π‐Interaction based quantum theoretical design

Range of validity of the Hammett equation: acidity of substituted ethynylbenzenes

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