Surfing π Clouds for Noncovalent Interactions: Arenes versus Alkenes

Aliev, Abil E.; Arendorf, Josephine R. T.; Pavlakos, Ilias; Moreno, Rafael B.; Porter, Michael J.; Rzepa, Henry; Motherwell, William B.

doi:10.1002/anie.201409672

Cited by 33 publications

(20 citation statements)

References 50 publications

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“…Important noncovalent interactions to which molecular torsion balance studies were applied include CH ··· π, − OH ··· π, ,, NH ··· π, CH ··· O, , and arene ··· arene − ,,, interactions as well as orthogonal dipolar and dispersive interactions, , and solvophobic contributions. ,, An example for the latter is shown in Figure .…”

Section: Strategies/methodsmentioning

confidence: 99%

“…Hydrogen bonds with aryl and other unsaturated moieties as acceptor were investigated with a series of molecular balances shown in Figure . With tertiary alcohols (Y = Me, Et, CHCH 2 , CCH), the conformer with the hydroxyl group facing downward, forming a hydrogen bond with the aryl group (1, 3), was more abundant than the conformer with an OH···π bridge toward the alkene (2, 4).…”

Section: Selected Interaction Energiesmentioning

confidence: 99%

“…Molecular balances for the evaluation of OH···π interactions, and the free-energy difference Δ G = – RT ln(p D /p U ) versus the solvent hydrogen-bond acceptor parameter β. Y = Me, Z = OH; see text …”

Section: Selected Interaction Energiesmentioning

confidence: 99%

“…The benzobicyclo[3.2.2]nonanes used for the investigation of OH ··· π hydrogen bonds (Figure ) show also the electrostatic nature of interactions between Y = CCH and CN groups with π-systems. In line with ab initio calculations, an increase in the p U value in molecular balances 1 – 4 was observed for Y = CCH and Y = CN as compared to the Y = CHCH 2 , ascribed to the charge at C α of the CX groups …”

Section: Selected Interaction Energiesmentioning

confidence: 99%

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Experimental Binding Energies in Supramolecular Complexes

2016

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On the basis of many literature measurements, a critical overview is given on essential noncovalent interactions in synthetic supramolecular complexes, accompanied by analyses with selected proteins. The methods, which can be applied to derive binding increments for single noncovalent interactions, start with the evaluation of consistency and additivity with a sufficiently large number of different host-guest complexes by applying linear free energy relations. Other strategies involve the use of double mutant cycles, of molecular balances, of dynamic combinatorial libraries, and of crystal structures. Promises and limitations of these strategies are discussed. Most of the analyses stem from solution studies, but a few also from gas phase. The empirically derived interactions are then presented on the basis of selected complexes with respect to ion pairing, hydrogen bonding, electrostatic contributions, halogen bonding, π-π-stacking, dispersive forces, cation-π and anion-π interactions, and contributions from the hydrophobic effect. Cooperativity in host-guest complexes as well as in self-assembly, and entropy factors are briefly highlighted. Tables with typical values for single noncovalent free energies and polarity parameters are in the Supporting Information.

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Section: Strategies/methodsmentioning

confidence: 99%

Section: Selected Interaction Energiesmentioning

confidence: 99%

Section: Selected Interaction Energiesmentioning

confidence: 99%

Section: Selected Interaction Energiesmentioning

confidence: 99%

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Experimental Binding Energies in Supramolecular Complexes

2016

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“…degree of antiparallel pairing associated with the incorporation of a terminal alkene. A weak interaction between a nitrile and alkene has been reported [48], and this may be the origin of the reduced Kirkwood factor (and thereby the reduction in dielectric anisotropy) in alkene-terminated nOCB compounds. Reentrant behaviour in liquid crystals, where a 'less' ordered mesophase is obtained on cooling a 'more' ordered mesophasealthough more correctly a phase of higher symmetry is obtained on cooling a phase of lower symmetryis a well-established phenomenon [49,50], and exists in analogy to similar reentrant behaviour observed in other systems [51], Binary mixtures of 6OCB in 8OCB exhibit the phase sequence N-SmA-N RE (where N RE is a reentrant nematic phase) when the concentration of 6OCB is in the range of 20-30 wt%.…”

Section: Resultsmentioning

confidence: 98%

An interplay between molecular pairing, smectic layer spacing, dielectric anisotropy and re-entrant phenomena in ω-alkenyloxy cyanobiphenyls

Mandle

Goodby

2016

Liquid Crystals

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In this article, we report on the liquid-crystalline properties of the 4-ω-alkenyloxy-4′-cyanobiphenyl series of compounds up to a total aliphatic chain length of eleven. When compared to the analogous fully saturated compounds, we find that the smectic layer spacing is significantly larger for the alkene-terminated materials; conversely the dielectric anisotropy in the nematic phase was found to be significantly smaller. The ability to manipulate bulk properties of nematic and smectic mesophases may have future relevance for display applications.

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Noncovalent Lone Pair⋅⋅⋅(No‐π!)‐Heteroarene Interactions: The Janus‐Faced Hydroxy Group

et al. 2015

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Ac omparative study using NMR spectroscopya nd designed top-pan molecular balances demonstrates that the noncovalent interaction of ah ydroxy group with p-deficient pyrazine and quinoxaline units involves al one pair-heteroarene interaction which is muchs tronger and solvent independent when measured relative to the classical p-facial hydrogen bond to ab enzener ing.A lkyl fluorides also prefer the heteroarene rings over the benzener ing. The attractive interaction between aquinoxaline and aterminal alkyne is also stronger than the intramolecular hydrogen bond to an arene.Noncovalent interactions [1] involving aromatic rings are essential elements for molecular recognition in avast array of chemical and biological processes.Consequently,quantifiable information on such phenomena as p stacking [2] and cationp [3] and anion-p [4] interactions,the ability of an arene to act as ah ydrogen-bond acceptor, [5] and solvation [6] are now regarded as essential for the rational design of organocatalysts and drugs.T he conformational analysis of designed molecular balances [2d, 7] with limited degrees of freedom has proven to be ap articularly powerful tool for probing the strength of the intramolecular variants of such weak interactions with precise control over the geometry of interacting partners.Nevertheless,wewere intrigued to note that there is ar elative dearth of quantifiable information using such molecular balances to probe noncovalent interactions with heteroaromatic systems,e specially given the overwhelming preponderance of such compounds in the pharmaceutical and agrochemical industries.

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Surfing π Clouds for Noncovalent Interactions: Arenes versus Alkenes

Cited by 33 publications

References 50 publications

Experimental Binding Energies in Supramolecular Complexes

Experimental Binding Energies in Supramolecular Complexes

An interplay between molecular pairing, smectic layer spacing, dielectric anisotropy and re-entrant phenomena in ω-alkenyloxy cyanobiphenyls

Noncovalent Lone Pair⋅⋅⋅(No‐π!)‐Heteroarene Interactions: The Janus‐Faced Hydroxy Group

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