Substituent Effects on Non‐Covalent Interactions with Aromatic Rings: Insights from Computational Chemistry

Raju, Rajesh K.; Bloom, Jacob W. G.; An, Yi; Wheeler, Steven E.

doi:10.1002/cphc.201100542

Cited by 137 publications

(113 citation statements)

References 215 publications

(102 reference statements)

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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

Ghysels

Vandichel

Verstraelen

et al. 2012

Highlights in Theoretical Chemistry

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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

Ghysels

Vandichel

Verstraelen

et al. 2012

Highlights in Theoretical Chemistry

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“…These results in relation to substituent effects on binding energies are in good agreement with results of Sherrill et al [58][59][60] and Wheeler et al [61][62][63]. Interactions for all substituted benzene dimers in comparison with the unsubstituted case enhanced.…”

Section: Resultssupporting

confidence: 91%

Theoretical investigation of the nature and strength of simultaneous interactions of π–π stacking and halogen bond including NMR, SAPT, AIM and NBO analysis

2016

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Ab initio MP2/aug-cc-pVDZ calculations were performed to investigate mutual effect between p-p stacking and halogen bond interactions in X-ben||pyrÁÁÁCl-F complexes (X = CN, F, Cl, Br, CH 3 , OH and H where || and ÁÁÁ denote p-p stacking and halogen bonds). The results indicate the cooperativity of p-p stacking and halogen bonds in these complexes. This effect was discussed in terms of the energetic, geometrical parameters and chargetransfer properties of the complexes. To explore on the two-bonded spin-spin coupling constant 2X

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“…These results lead to the conclusion that the gel formation is largely dictated by the position and nature of the substituents, rather than being dominated by the quinoxalinone framework. 32, 33 Solubility and Dissolution Parameters. We previously reported that gelators exhibit (on average) higher dissolution enthalpies (ΔH diss ) and entropies (ΔS diss ) than nongelators.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Improving Hg-Triggered Gelation via Structural Modifications

2014

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The relationship between chemical structure and gelation ability was examined for a series of nine Hg-containing compounds. Both solid-state properties (dissolution enthalpies/entropies and packing structure) and gel properties (strength, morphology, cation selectivity, and anion tolerance) were examined. Overall, the results reveal a complex relationship between chemical structure and properties. The remediation potential of these Hg-triggered gelations was also investigated, revealing that >98% of the Hg(2+) in water can be removed through gel formation.

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Substituent Effects on Non‐Covalent Interactions with Aromatic Rings: Insights from Computational Chemistry

Cited by 137 publications

References 215 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

Theoretical investigation of the nature and strength of simultaneous interactions of π–π stacking and halogen bond including NMR, SAPT, AIM and NBO analysis

Improving Hg-Triggered Gelation via Structural Modifications

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