Helix-Rod Host-Guest Complexes with Shuttling Rates Much Faster than Disassembly

Gan, Quan; Ferrand, Yann; Bao, Chunyan; Kauffmann, Brice; Grélard, Axelle; Jiang, Hua; Huc, Ivan

doi:10.1126/science.1200143

Cited by 236 publications

(153 citation statements)

References 28 publications

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“…Aromatic poly-and oligo-amides, such as Huc's foldamers [49][50][51], provide incomparable venues for exploring biological types of structural motifs, the diversity of which expands beyond what the natural systems can offer [52][53][54][55][56]. Indeed, the rich π-conjugation of such foldamers governs their immensely promising CT characteristics [57].…”

Section: Introductionmentioning

confidence: 99%

Building blocks for bioinspired electrets: molecular-level approach to materials for energy and electronics

Larsen

Espinoza

Hartman

et al. 2015

Pure and Applied Chemistry

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In biology, an immense diversity of protein structural and functional motifs originates from only 20 common proteinogenic native amino acids arranged in various sequences. Is it possible to attain the same diversity in electronic materials based on organic macromolecules composed of non-native residues with different characteristics? This publication describes the design, preparation and characterization of non-native aromatic β-amino acid residues, i.e. derivatives of anthranilic acid, for polyamides that can efficiently mediate hole transfer. Chemical derivatization with three types of substituents at two positions of the aromatic ring allows for adjusting the energy levels of the frontier orbitals of the anthranilamide residues over a range of about one electronvolt. Most importantly, the anthranilamide residues possess permanent electric dipoles, adding to the electronic properties of the bioinspired conjugates they compose, making them molecular electrets.

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Section: Introductionmentioning

confidence: 99%

Building blocks for bioinspired electrets: molecular-level approach to materials for energy and electronics

Larsen

Espinoza

Hartman

et al. 2015

Pure and Applied Chemistry

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“…Synthetic monodisperse macromolecules with similar cooperative folding behaviour provide a viable approach to the programmed fabrication of 3D nanostructures [2][3][4][5] . Here we show that cyclic porphyrin polymers, with molecular weights of 30-60 kDa, self-assemble into nested structures on a gold surface.…”

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confidence: 99%

Supramolecular nesting of cyclic polymers

et al. 2015

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Monodisperse cyclic porphyrin polymers, with diameters of up to 21 nm (750 C-C bonds), have been prepared using Vernier template-directed synthesis. The ratio of the intrinsic viscosities for cyclic and linear topologies is 0.72, indicating that these polymers behave as almost ideal flexible chains in solution. When deposited on gold surfaces, the cyclic polymers display a new mode of two-dimensional supramolecular organisation, combining encapsulation and nesting: one nanoring adopts a near-circular conformation thus allowing a second nanoring to be captured within its perimeter, in a tightly folded conformation. Scanning tunnelling microscopy reveals that nesting occurs in combination with stacking when nanorings are deposited under vacuum, whereas when they are deposited directly from solution under ambient conditions, there is stacking or nesting, but not a combination of both.The tertiary structures of biological macromolecules are achieved through folding, coiling and multiplex formation, driven by the cooperative effect of many weak interactions 1 . Synthetic monodisperse macromolecules with similar cooperative folding behaviour provide a viable approach to the programmed fabrication of 3D nanostructures [2][3][4][5] . Here we show that cyclic porphyrin polymers, with molecular weights of 30-60 kDa, self-assemble into nested structures on a gold surface. These nested assemblies are only observed when the cyclic polymer has 30 or more repeat units, in keeping with the predictions of a simple geometrical model.The importance of non-covalent self-assembly in biology has inspired many studies of supramolecular organisation on surfaces [6][7][8] , generating 2D assemblies with progressively escalating complexity, from early work on simple structures such as clusters 9 and rows 10,11 , to nanoporous arrays 12,13 , host-guest architectures [14][15][16] , hierarchical arrangements 17 , and multicomponent assemblies [17][18][19] . However, cooperative conformational control has proved difficult to achieve, and this remains a significant gulf between artificial and biological systems. One reason for this difference is that biological macromolecules are much more flexible than the component molecules studied in 2D supramolecular assemblies which are small and, with some exceptions 20,21 , are often treated as quasi-rigid building blocks. Here we illustrate how interactions between large flexible molecules can result in biomimetic cooperative conformational organisation.Studies of linear and cyclic butadiyne-linked zinc porphyrin oligomers (structures l-PN THS and c-PN, Fig. 1) have shown that the distance between the centres of the porphyrin units along the chain is a = 1.35 nm 5,22,23 . Thus the contour length of a linear oligomer, or the perimeter of a nanoring, is Na, where N is the number of porphyrin repeat units. Previously we have shown that nanorings adsorbed on Au(111) exhibit flexibility [24][25][26] , and also that they can act as nanoscale traps for other adsorbed species, such as C 60 guest molecules 2...

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“…Given the well-established coupling reactions of primary amines, this compound provides a generalized route to furnish 120°donors functionalized with any moiety that is compatible with amine couplings. Herein, we linked amineterminated compound 13 with a 1,1′-carbonyldiimidazole-activated alkyl-substituted pyrimidinone (14), delivering the 120°UPy-functionalized dipyridyl ligand (4) 2 ]diphenyl ketone (7; forming hexagon 3), in a 1:1 ratio in DMSO-d 6 at 50°C for 8 h (Scheme 1B). Multinuclear NMR ( 1 H and 31 P) analyses of the reaction mixtures supported the formation of discrete, highly symmetric species ( Fig.…”

Section: Resultsmentioning

confidence: 99%

Supramolecular polymers with tunable topologies via hierarchical coordination-driven self-assembly and hydrogen bonding interfaces

Yan

Pollock

et al. 2013

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

223

115

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A powerful strategy to obtain complex supramolecular materials is the bottom-up construction of noncovalently bound materials by hierarchical self-assembly. This assembly process involves stepwise, uniform increases to the architectural complexity of a substrate, starting from discrete precursors and growing in dimensionality through controlled reactivity to a final product. Herein, two orthogonal processes are exploited: coordination-driven self-assembly and hydrogen bonding. The former relies on the predictable formation of metal-ligand bonds wherein the directionalities of the rigid precursors used determines the structural outcome. The latter uses 2-ureido-4-pyrimidinone interfaces that are structurally robust by virtue of the quadruple hydrogen bonding that can occur between subunits. By combining these two processes into a single system, it is possible to generate hierarchical materials that preserve the attractive tunability associated with discrete supramolecular coordination complexes. For instance, the synthesis of a one-dimensional chain comprising linked metalla-rhomboids is readily adapted to a 2D cross-linked hexagonal network by simply selecting a different metal acceptor precursor as an assembly component. The specific interactions between subunits, in this case platinum(II)-pyridyl bonds and the quadruple H-bonding of ureidopyrimidinone, are unchanged, establishing a unique strategy to obtain supramolecular polymers with marked topological differences with minimal synthetic redesign. In addition, the structural rigidity imposed by the inclusion of the platinum metallacycles serves to minimize the formation of cyclic oligomers, increasing the efficacy of formation and improving the properties of the resultant materials. Furthermore, this study taps the potential of organoplatinum(II) metallacycles in materials science.

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Helix-Rod Host-Guest Complexes with Shuttling Rates Much Faster than Disassembly

Cited by 236 publications

References 28 publications

Building blocks for bioinspired electrets: molecular-level approach to materials for energy and electronics

Building blocks for bioinspired electrets: molecular-level approach to materials for energy and electronics

Supramolecular nesting of cyclic polymers

Supramolecular polymers with tunable topologies via hierarchical coordination-driven self-assembly and hydrogen bonding interfaces

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