Complete asymmetric induction of supramolecular chirality in a hydrogen-bonded assembly

Prins, Leonard J.; Huskens, Jurriaan; Jong, Feike de; Timmerman, Peter; Reinhoudt, David N.

doi:10.1038/19053

Cited by 436 publications

(249 citation statements)

References 29 publications

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“…In synthetic systems, noncovalent interactions have been used to obtain well defined self-assembled architectures in organic solvents (2-7). Peripheral chiral centers in assemblies (8)(9)(10)(11) and chiral side chains attached to a polymer backbone (12)(13)(14)(15)(16)(17)(18)(19)(20) have been shown to bias chirality at the supramolecular level. Highly ordered multimolecular supramolecular structures stable in water, held together by hydrophobic interactions or with additional hydrogen bonding, are also known (21)(22)(23)(24)(25).…”

mentioning

confidence: 99%

Hierarchical formation of helical supramolecular polymers via stacking of hydrogen-bonded pairs in water

Brunsveld

Vekemans

Hirschberg

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

196

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Bifunctional ureido-s-triazines provided with penta(ethylene oxide) side chains are able to self assemble in water, leading to helical columns via cooperative stacking of the hydrogen-bonded pairs (DADA array). Monofunctional ureido-s-triazines do not form such helical architectures. The presence of a linker, covalently connecting the two ureido-s-triazine units, is essential as it generates a high local concentration of aromatic units, favorable for stacking interactions. This hydrophobic stacking of the aromatic units occurs at concentrations as low as 5⅐10 ؊6 M and can be visualized by using fluorescence spectroscopy. The stacking generates a hydrophobic microenvironment that allows intermolecular hydrogen bonding to occur at higher concentrations because the hydrogen bonds are shielded from competitive hydrogen bonding with water. This hierarchical process results in the formation of a helical self-assembled polymer in water at concentrations above 10 ؊4 M. Chiral side chains attached to the ureido-striazine units bias the helicity of these columns as concluded from CD spectroscopy and ''Sergeants and Soldiers'' experiments.I n DNA, the well known double helical motif originates from self assembly and is directed by lateral hydrogen bonds between bases and stabilized by solvophobic interactions between the covalently linked bases perpendicular to the hydrogen bonds (1). Control over the intrinsic helicity of the structure is governed by the peripheral chirality in the sugar-phosphate backbone. In synthetic systems, noncovalent interactions have been used to obtain well defined self-assembled architectures in organic solvents (2-7). Peripheral chiral centers in assemblies (8-11) and chiral side chains attached to a polymer backbone (12-20) have been shown to bias chirality at the supramolecular level. Highly ordered multimolecular supramolecular structures stable in water, held together by hydrophobic interactions or with additional hydrogen bonding, are also known (21-25). However, it remains difficult to exploit directional noncovalent interactions in a cooperative way for the formation of discrete multimolecular assemblies stable in water. In this solvent, water molecules strongly compete with directional polar interactions such as hydrogen bonds, resulting in low association constants.The formation of helical self-assembled polymers in solution by both stacking and hydrogen bonding has recently been demonstrated by us (26, 27). Self-complementary apolar molecules 1 and 2 dimerize via strong cooperative 4-fold hydrogen bonding (ADAD) in chloroform (28), giving rise to the formation of a dimer by 1 and a random coil polymer by 2, the latter featuring viscous solutions at higher concentrations. Additional to the hydrogen bonding, solvophobic interactions between the aromatic surfaces arise for 1 and 2 in alkanes. Association via hydrogen bonding of the ureido-s-triazine functional groups leads to the formation of a large and planar aromatic core surrounded by six flexible chains, a structure that is conduciv...

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mentioning

confidence: 99%

Hierarchical formation of helical supramolecular polymers via stacking of hydrogen-bonded pairs in water

Brunsveld

Vekemans

Hirschberg

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

196

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“…Recrystallization afforded 1 as an analytically pure white powder, as confirmed by 1 17 The relatively large P−Pt coupling constants in both complexes 2 and 3 are consistent with the predicted cis configurations of the ligands. 17,56 Fully closed complex 3 can be converted to semiopen complex 2 by the addition of 1 equiv of tetrabutylammonium chloride, demonstrating the ability to toggle between two coordination states in solution.…”

Section: ■ Introductionmentioning

confidence: 55%

“…Silica gel column chromatography (dichloromethane) afforded the product as an off-white solid (4.07 g, 75% yield). 1 N-Phenyl-N′-3-(2-Diphenylphosphanylethylthio)phenylurea (1). 3-(2−Diphenylphosphanylethylthio)phenylamine (2.0 g, 5.92 mmol) and phenyl isocyanate (0.78 g, 6.51 mmol) were dissolved in degassed anhydrous tetrahydrofuran and stirred at reflux for 12 h under nitrogen.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Small Molecule Regulation of Self-Association and Catalytic Activity in a Supramolecular Coordination Complex

2014

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“…Double rosette assembly 1a 3 ‚ (DEB) 6 in the staggered conformation (D 3 symmetry) displays supramolecular chirality, 44 caused by the antiparallel orientation of the two melamine units in each calix[4]arene, which can be oriented either clockwise (P) or counterclockwise (M). In the absence of any other source of chirality, assembly 1a 3 ‚(DEB) 6 exists as a racemic mixture of the (P) and (M) enantiomeric assemblies.…”

Section: Complexation By Chiral Receptorsmentioning

confidence: 99%

Selective Self-Organization of Guest Molecules in Self-Assembled Molecular Boxes

et al. 2005

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This article describes the synthesis and binding properties of highly selective noncovalent molecular receptors 13‚(DEB)6 and 33‚(DEB)6 for different hydroxyl functionalized anthraquinones 2. These receptors are formed by the self-assembly of three calix [4]arene dimelamine derivative molecules (1 or 3) and six diethylbarbiturate (DEB) molecules to give 13‚(DEB)6 or 33‚(DEB)6. Encapsulation of 2 occurs in a highly organized manner; that is, a noncovalent hydrogen-bonded trimer of 2 is formed within the hydrogenbonded receptors 13‚(DEB)6 and 33‚(DEB)6. Both receptors 13‚(DEB)6 and 33‚(DEB)6 change conformation from staggered to eclipsed upon complexation to afford a better fit for the 23 trimer. The receptor selectivity toward different anthraquinone derivatives 2 has been studied using 1 H NMR spectroscopy, X-ray crystallography, UV spectroscopy, and isothermal microcalorimetry (ITC). The π-π stacking between the electron-deficient center ring of the anthraquinone derivatives 2a-c and 2e-g and the relatively electronpoor melamine units of the receptor is the driving force for the encapsulation of the guest molecules. The selectivity of the hydrogen-bonded host for the anthraquinone derivatives is the result of steric interactions between the guest molecules and the calix[4]arene aromatic rings of the host.

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Complete asymmetric induction of supramolecular chirality in a hydrogen-bonded assembly

Cited by 436 publications

References 29 publications

Hierarchical formation of helical supramolecular polymers via stacking of hydrogen-bonded pairs in water

Hierarchical formation of helical supramolecular polymers via stacking of hydrogen-bonded pairs in water

Small Molecule Regulation of Self-Association and Catalytic Activity in a Supramolecular Coordination Complex

Selective Self-Organization of Guest Molecules in Self-Assembled Molecular Boxes

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