Absolute Helical Arrangement of Stacked Benzene Rings: Heterogeneous Double‐Helical Interaction Comprising a Hydrogen‐Bonding Belt and an Offset Parallel Aromatic–Aromatic‐Interaction Array

Azumaya, Isao; Uchida, Daisuke; Katō, Takako; Yokoyama, Akihiro; Tanatani, Aya; Takayanagi, Hiroaki; Yokozawa, Tsutomu

doi:10.1002/anie.200352788

Cited by 73 publications

(41 citation statements)

References 70 publications

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“…A common route to induce helicity in columnar arrangements is inclusion of chiral centers in discotic molecules (7). Helical columnar arrangements have also been realized in a few cases with achiral discotic molecules (8,9), although no general strategy seems to have emerged.…”

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confidence: 99%

“…S1 of the SI Appendix). This bias is conducive to columnar stacking, as for Ϫ interactions in aromatic systems (7)(8)(9).…”

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confidence: 99%

“…For identical ellipsoids, the potential involves a set of eight parameters, six of them, {a 1k } and {a 2k } (k ϭ 1,2,3), defining two different shape matrices for the repulsive and attractive parts of the interaction, and the other two, 0 PY and 0 GB , defining the length and energy scales, respectively. For the PY model, we tune the parameters so that the lowest-energy configuration for two axially symmetric discoids involves an offset geometry (8) (Fig. S1 of the SI Appendix).…”

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confidence: 99%

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Rational design of helical architectures

Chakrabarti¹,

Fejer²,

Wales³

2009

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

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Nature has mastered the art of creating complex structures through self-assembly of simpler building blocks. Adapting such a bottom-up view provides a potential route to the fabrication of novel materials. However, this approach suffers from the lack of a sufficiently detailed understanding of the noncovalent forces that hold the self-assembled structures together. Here we demonstrate that nature can indeed guide us, as we explore routes to helicity with achiral building blocks driven by the interplay between two competing length scales for the interactions, as in DNA. By characterizing global minima for clusters, we illustrate several realizations of helical architecture, the simplest one involving ellipsoids of revolution as building blocks. In particular, we show that axially symmetric soft discoids can self-assemble into helical columnar arrangements. Understanding the molecular origin of such spatial organisation has important implications for the rational design of materials with useful optoelectronic applications.anisotropic interactions ͉ columnar arrangements ͉ helix ͉ self-assembly N ature provides ubiquitous examples of helical architecture with diverse functions. Helical structures are common structural motifs in biomolecules and are involved in the storage of genetic information (1). They are also important in solid-and liquid-crystal engineering for fabricating functional materials with useful optoelectronic applications (2-5). For example, discotic molecules in crystalline or liquid crystalline states often exhibit helical order in columnar arrangements (2-6), and such materials are attractive for use in optoelectronic devices because of the exceptional 1D charge-carrier mobilities along the columns (2-4). A common route to induce helicity in columnar arrangements is inclusion of chiral centers in discotic molecules (7). Helical columnar arrangements have also been realized in a few cases with achiral discotic molecules (8, 9), although no general strategy seems to have emerged.Self-assembly is nature's prescription for the creation of complex structures from simpler building blocks (10, 11). Although many novel building blocks have been discovered for self-assembly, differing in shape, composition, and functionality (12, 13), the basic rules that govern this process are not yet understood in sufficient detail to realize target structures routinely through a priori design of building blocks. Here we ask the specific question: Can we learn from nature how to design building blocks that self-assemble into helical structures? In seeking a guiding principle from nature for obtaining helical architectures, we considered DNA, in which two competing length scales exist, one characterizing the distance between consecutive nucleotides in the sugar-phosphate backbone and the other governing the stacking of the base pairs (1). The present contribution thus explores realizations of helical architectures with achiral building blocks driven by the interplay between two competing length scales. To this end, we c...

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confidence: 99%

“…S1 of the SI Appendix). This bias is conducive to columnar stacking, as for Ϫ interactions in aromatic systems (7)(8)(9).…”

mentioning

confidence: 99%

mentioning

confidence: 99%

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Rational design of helical architectures

Chakrabarti¹,

Fejer²,

Wales³

2009

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

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“…Pairs of amide molecules related by an inversion centre are connected into dimers via two N-H/O carbonyl and two N-H/N pyridyl intermolecular hydrogen bonds. The central aromatic rings of the two molecules additionally feature an offset p-p interaction [21], with a ring separation of 3.477 Å and a perpendicular slippage of 0.472 Å (Fig. 2).…”

Section: Resultsmentioning

confidence: 99%

An alternating chain of spider-like tris(peptides) stabilized by stacking and by N–H⋯N and N–H⋯OC hydrogen bonding

Kannappan

Tooke

Spek

et al. 2005

Journal of Molecular Structure

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The X-ray crystal structure of the novel spider-like trispeptide N,N 0 ,N 00 -tris(2-aminopyridine)benzene-1,3,5-tricarboxamide shows the unexpected formation of a new extended polymeric architecture. The structure is characterized by cooperative hydrogen bonding generating neighbouring pairs by self-assembly, and stacking between rings. Pairs of amide groups related by an inversion centre are connected into dimers via two N-H/O carbonyl and two N-H/N pyridyl intermolecular hydrogen bonds. The offset-stacked layers are tightly inter-linked (spacing of 3.477 Å ) by hydrogen bonding and aromatic p-p stacking interactions. These dimers are further linked into polymeric chains by hydrogen bonding through bridging methanol solvent molecules. The central aromatic rings of molecules in adjacent dimers are once again related by inversion symmetry, with a perpendicular separation of 3.619 Å .

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“…mp 156-157°C (Lit. 162°C [31] [32] or methyl glycolate (10 mmol), N-ethylperfluorooctanesulfonamide 4b (10 mmol) and triphenylphosphine (0.4 g, 15 mmol) in anhydrous ether (3 mL) at 0°C. After completion of the addition, the reaction mixture was sonicated at 25°C until the starting material had disappeared.…”

Section: Synthesis Of 2-(n-ethyl-perfluorooctanesulfonamido)acetic Acmentioning

confidence: 99%

Synthesis and structure of environmentally relevant perfluorinated sulfonamides

Lehmler

Rao

Nauduri

et al. 2007

Journal of Fluorine Chemistry

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Alkylated perfluorooctanesulfonamides are compounds of environmental concern. To make these compounds available for environmental and toxicological studies, a series of N-alkylated perfluorooctanesulfonamides and structurally related compounds were synthesized by reaction of the corresponding perfluoroalkanesulfonyl fluoride with a suitable primary or secondary amine. Perfluoroalkanesulfonamidoethanols were obtained from the N-alkyl perfluoroalkanesulfonamides either by direct alkylation with bromoethanol or alkylation with acetic acid 2-bromo-ethyl ester followed by hydrolysis of the acetate. N-Alkyl perfluorooctanesulfonamidoacetates were synthesized in an analogous way by alkylation of N-alkyl perfluoroalkanesulfonamides with a bromo acetic acid ester, followed by basic ester hydrolysis. Alternatively, N-alkyl perfluoroalkanesulfonamides can be alkylated with an appropriate alcohol using the Mitsunobu reaction. Perfluorooctanesulfonamide was synthesized from the perfluorooctanesulfonyl fluoride via the azide by reduction with Zn/HCl. All perfluorooctanesulfonamides contained linear as well as branched C 8 F 17 isomers, typically in a 20:1 to 30:1 ratio. The crystal structures of N-ethyl and N,N-diethyl perfluorooctanesulfonamide show that the S-N bond has considerable double bond character. This double bond character results in a significant rotational barrier around the S-N bond (ΔG ≠ = 62-71 kJ mol −1 ) and a preferred solid state and solution conformation in which the N-alkyl groups are oriented opposite to the perfluorooctyl group to minimize steric crowding around the S-N bond.

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Absolute Helical Arrangement of Stacked Benzene Rings: Heterogeneous Double‐Helical Interaction Comprising a Hydrogen‐Bonding Belt and an Offset Parallel Aromatic–Aromatic‐Interaction Array

Cited by 73 publications

References 70 publications

Rational design of helical architectures

Rational design of helical architectures

An alternating chain of spider-like tris(peptides) stabilized by stacking and by N–H⋯N and N–H⋯OC hydrogen bonding

Synthesis and structure of environmentally relevant perfluorinated sulfonamides

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