High‐Fidelity Noncovalent Synthesis of Hydrogen‐Bonded Macrocyclic Assemblies

Montoro‐García, Carlos; Camacho-García, Jorge; López-Pérez, Ana; Bilbao, Nerea; Romero-Pérez, Sonia; Muñoz, Marı́a A.; González‐Rodríguez, David

doi:10.1002/ange.201501321

Cited by 25 publications

(5 citation statements)

References 39 publications

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“…However, the strength of a single H‐bond is generally too weak to render supramolecules with enough stability in the 2D plane, e.g., for H‐bonded 2D networks, no matter whether assembled in crystals or at a surface, when the number of H‐bonds between moieties is limited, free‐standing has never been reported. In order to enhance the stability, contiguous multipoint H‐bonding could be a solution, e.g., a quadruple H‐bonded array and a guanosine‐cytosine paired macrocycle have good stability. In the present work, we report a H‐bonded 2DSM exfoliated[27a,b] from a layered polymer crystal that comprises hierarchical bonding, namely alternating in‐plane strong covalent and moderate H‐bonding, along with van der Waals interaction between layers.…”

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A Free‐Standing and Self‐Healable 2D Supramolecular Material Based on Hydrogen Bonding: A Nanowire Array with Sub‐2‐nm Resolution

Song

et al. 2017

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In many 2D materials reported thus far, the forces confining atoms in a 2D plane are often strong interactions, such as covalent bonding. Herein, the first demonstration that hydrogen (H)-bonding can be utilized to assemble polydiacetylene (a conductive polymer) toward a 2D material, which is stable enough to be free-standing, is shown. The 2D material is well characterized by a large number of techniques (mainly different microscopy techniques). The H-bonding allows splitting of the material into ribbons, which can reassemble, similar to a zipper, leading to the first example of a healable 2D material. Moreover, such technology can easily create 2D, organic, conductive nanowire arrays with sub-2-nm resolution. This material may have potential applications in stretchable electronics and nanowire cross-bar arrays.

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A Free‐Standing and Self‐Healable 2D Supramolecular Material Based on Hydrogen Bonding: A Nanowire Array with Sub‐2‐nm Resolution

Song

et al. 2017

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“…This rigid and linear structure,t ogether with the 908 8 angle provided by Watson-Crick pairing, resulted in the quantitative formation of unstrained square-shaped tetrameric assemblies (Figure 1b)o ver ab road concentration, temperature,a nd solvent-polarity range,a sp reviously demonstrated by us in solution experiments (see also the Supporting Information, Figure S1). [8] Theexceptional stability,w hich was particularly evident for the G-C couple,w as ascribed to the strong chelate effect measured upon cyclotetramerization, which originates mainly from the optimally preorganized monomer structure.…”

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Two‐Dimensional Nanoporous Networks Formed by Liquid‐to‐Solid Transfer of Hydrogen‐Bonded Macrocycles Built from DNA Bases

et al. 2015

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Esta es la versión de autor del artículo publicado en: This is an author produced version of a paper published in: Copyright: © 2016 WILEY-VCH VerlagEl acceso a la versión del editor puede requerir la suscripción del recurso Access to the published version may require subscription Self-assembly provides the guidelines to engineer twodimensional (2D) molecular networks on flat surfaces. Two-Dimensional Nanoporous Networks Formed by Liquid-to-[1] Those presenting void spaces, the so-called "2D porous networks", [2] are especially interesting since they offer the possibility of immobilizing, in a repetitive and ordered way, different functional guest units that are complementary in size and shape. Such networks can be produced from the deposition of persistent covalent macrocycles.[3] Pore size and shape is in this way predefined during synthesis, but this approach can be tedious and time-consuming if tunable systems that allow for small pore modifications are to be produced. A more appealing alternative is the generation of lattices with regular cavities from small monomers that, once on the surface, interact via weaker noncovalent bonds.[4] Upon physisorption, several degrees of translational, rotational and vibrational freedom are lost and, as a result, molecules that display very weak and ill-defined binding in solution can form well-ordered, yet dynamic assemblies held by multiple supramolecular interactions when confined in two dimensions. However, although much has been learned during the last years, this second approach has the limitation that the kind of network attained, which depends on a subtle interplay between molecule-molecule, molecule-solvent and moleculesubstrate interactions, cannot be always reliably predicted.An intermediate and ideal situation would be reached in the case of macrocycles that are assembled in solution from reversible noncovalent interactions, [5] but robust enough to survive as well-defined, monodisperse species after the transfer process from solution to a substrate. These are indeed highly challenging requirements for self-assembled macrocycles, since the self-assembling rules change drastically when molecules are concentrated on a surface. On one hand, intra-and intermolecular binding events are compensated and chelate cooperativity, the key factor promoting cycle formation in diluted solutions, is downgraded. On the other, the general tendency of physisorbed molecules is to maximize molecule-substrate interactions, so that networks with empty spaces are usually avoided if an alternative, more densely packed lattice can be accessed. All these issues ultimately result in a low-fidelity liquid-to-substrate transfer of supramolecular information. In other words, self-assembly in solution is typically not reproduced at the surface and vice versa.Herein, we present a bioinspired approach that makes use of DNA-base [1g] pairing to produce tunable macrocycles (Figure 1) in solution whose supramolecular identity is reliably transferred to highly oriented pyrolytic graphite (HOPG)...

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“…52 Some of the molecules prepared in this work, for instance the halogenated and ethynylated nucleobases, can be regarded as a relevant collection of "supramolecular synthons" that may be useful in the field of chemical self-assembly. In this work we have just coupled a simple oligo(phenylene-ethynylene) unit, which is useful for further studies in our group, 53 but a wide diversity of functional units may in principle be attached to these nucleobases by means of metal-catalyzed cross-coupling reactions in order to direct their organization.…”

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Synthesis and complementary self-association of novel lipophilic π-conjugated nucleoside oligomers

et al. 2015

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Esta es la versión de autor del artículo publicado en: This is an author produced version of a paper published in: A series of lipophilic nucleosides comprising natural and non-natural bases that are -conjugated to a short oligophenylene-ethynylene fragment has been synthesized. These bases comprise guanosine, isoguanosine, 2-aminoadenosine as purine heterocycles, and cytidine, isocytosine and uridine as complementary pyrimidine bases. The hydrogen-bonding dimerization and association processes between complementary bases were as well studied by 1 H NMR and absorption spectroscopies in order to obtain the relevant association constants.

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High‐Fidelity Noncovalent Synthesis of Hydrogen‐Bonded Macrocyclic Assemblies

Cited by 25 publications

References 39 publications

A Free‐Standing and Self‐Healable 2D Supramolecular Material Based on Hydrogen Bonding: A Nanowire Array with Sub‐2‐nm Resolution

A Free‐Standing and Self‐Healable 2D Supramolecular Material Based on Hydrogen Bonding: A Nanowire Array with Sub‐2‐nm Resolution

Two‐Dimensional Nanoporous Networks Formed by Liquid‐to‐Solid Transfer of Hydrogen‐Bonded Macrocycles Built from DNA Bases

Synthesis and complementary self-association of novel lipophilic π-conjugated nucleoside oligomers

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