Selenoamides modulate dipole–dipole interactions in hydrogen bonded supramolecular polymers of 1,3,5-substituted benzenes

Berrocal, José Augusto; Mabesoone, Mathijs F. J.; García‐Iglesias, Miguel; Huizinga, A.; Meijer, E. W.; Palmans, Anja R. A.

doi:10.1039/c9cc08423a

Cited by 22 publications

(13 citation statements)

References 40 publications

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“…Nevertheless, the model accurately describes the elongation temperatures of all mixtures, which directly correspond to the enthalpies of the homo- and heterointeractions . We calculated the enthalpy of the heterointeraction between ( S )-1 and n -1 to be −83 kJ·mol –1 , which is slightly different than that of the homointeractions of ( S )-1 (Δ H e = −86 kJ·mol –1 ), agreeing with observations for similar systems. − …”

Section: Results and Discussionsupporting

confidence: 83%

Biasing the Screw-Sense of Supramolecular Coassemblies Featuring Multiple Helical States

et al. 2020

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By enchaining a small fraction of chiral monomer units, the helical sense of a dynamic polymer constructed from achiral monomer units can be disproportionately biased. This phenomenon, known as the sergeants-and-soldiers (S&S) effect, has been found to be widely applicable to dynamic covalent and supramolecular polymers. However, it has not been exemplified with a supramolecular polymer that features multiple helical states. Herein, we demonstrate the S&S effect in the context of the temperature-controlled supramolecular copolymerization of chiral and achiral biphenyl tetracarboxamides in alkanes. The one-dimensional helical structures presented in this study are unique because they exhibit three distinct helical states, two of which are triggered by coassembling with monomeric water that is codissolved in the solvent. The self-assembly pathways are rationalized using a combination of mathematical fitting and simulations with a thermodynamic mass-balance model. We observe an unprecedented case of an “abnormal” S&S effect by changing the side chains of the achiral soldier. Although the molecular structure of these aggregates remains elusive, the coassembly of water is found to have a profound impact on the helical excess.

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Section: Results and Discussionsupporting

confidence: 83%

Biasing the Screw-Sense of Supramolecular Coassemblies Featuring Multiple Helical States

et al. 2020

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“…In contrast, for several other systems, much larger m -values have been obtained. In a selenoderivative of BTA, an m -value of 600 kJ/mol was observed, 110 while porphyrin-based polymers showed m -values between 100 and 200 kJ/mol. 111 Folded bismerocyanins showed m -values on the order of 150 kJ/mol upon destabilization by THF.…”

Section: Solvent-dependent Stability Of Ordered Supramolecular Polymementioning

confidence: 99%

Solute–Solvent Interactions in Modern Physical Organic Chemistry: Supramolecular Polymers as a Muse

2020

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Interactions between solvents and solutes are a cornerstone of physical organic chemistry and have been the subject of investigations over the last century. In recent years, a renewed interest in fundamental aspects of solute–solvent interactions has been sparked in the field of supramolecular chemistry in general and that of supramolecular polymers in particular. Although solvent effects in supramolecular chemistry have been recognized for a long time, the unique opportunities that supramolecular polymers offer to gain insight into solute–solvent interactions have become clear relatively recently. The multiple interactions that hold the supramolecular polymeric structure together are similar in strength to those between solute and solvent. The cooperativity found in ordered supramolecular polymers leads to the possibility of amplifying these solute–solvent effects and will shed light on extremely subtle solvation phenomena. As a result, many exciting effects of solute–solvent interactions in modern physical organic chemistry can be studied using supramolecular polymers. Our aim is to put the recent progress into a historical context and provide avenues toward a more comprehensive understanding of solvents in multicomponent supramolecular systems.

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“…The exploitation of the enhanced hydrogen‐bond strengths for amides containing the heavier chalcogens extends to the field of supramolecular polymer chemistry as recently it became evident that the replacement of oxygen in the amide bond for the heavier chalcogens, sulfur and selenium, can produce supramolecular polymers with similar or even stronger hydrogen bonds [5] . As the arguments based on the electronegativity differences of O, S, and Se cannot rationalize the enhanced hydrogen‐bond strength for amides comprising heavier chalcogens, most studies use explanations in terms of increasing polarizability and charge capacity [5a,6] . Using an oversimplified resonance model, the highly polarizable heavy chalcogen atoms would be able to carry more negative charge.…”

Section: Introductionmentioning

confidence: 99%

How the Chalcogen Atom Size Dictates the Hydrogen‐Bond Donor Capability of Carboxamides, Thioamides, and Selenoamides

Nieuwland

Guerra

2022

Chemistry A European J

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The amino groups of thio-and selenoamides can act as stronger hydrogen-bond donors than of carboxamides, despite the lower electronegativity of S and Se. This phenomenon has been experimentally explored, particularly in organocatalysis, but a sound electronic explanation is lacking. Our quantum chemical investigations show that the NH 2 groups in thio-and selenoamides are more positively charged than in carboxamides. This originates from the larger electronic density flow from the nitrogen lone pair of the NH 2 group towards the lower-lying π* C=S and π* C=Se orbitals than to the high-lying π* C=O orbital. The relative energies of the π* orbitals result from the overlap between the chalcogen np and carbon 2p atomic orbitals, which is set by the carbonchalcogen equilibrium distance, a consequence of the Pauli repulsion between the two bonded atoms. Thus, neither the electronegativity nor the often-suggested polarizability but the steric size of the chalcogen atom determines the amide's hydrogen-bond donor capability.

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Selenoamides modulate dipole–dipole interactions in hydrogen bonded supramolecular polymers of 1,3,5-substituted benzenes

Abstract: Selenoamide moieties introduced into C3-symmetrical molecules enhance supramolecular interactions and confer a remarkable thermal stability to the supramolecular polymers.

Cited by 22 publications

References 40 publications

Biasing the Screw-Sense of Supramolecular Coassemblies Featuring Multiple Helical States

Biasing the Screw-Sense of Supramolecular Coassemblies Featuring Multiple Helical States

Solute–Solvent Interactions in Modern Physical Organic Chemistry: Supramolecular Polymers as a Muse

How the Chalcogen Atom Size Dictates the Hydrogen‐Bond Donor Capability of Carboxamides, Thioamides, and Selenoamides

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