‘Sergeants-and-Corporals’ principle in chiral induction at an interface

Destoop, Iris; Xu, Hong; Oliveras-González, Cristina; Ghijsens, Elke; Amabilino, David B.; Feyter, Steven De

doi:10.1039/c3cc42584c

Cited by 40 publications

(31 citation statements)

References 26 publications

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“…The remaining four reversible peaks observed in Fig. However, while the effects of chirality on the absorption geometry of 2D lattices on surfaces was previously observed [64][65][66] , chiral discrimination in electrochemical experiments is rare and associated with electrodes with an inherent enantiorecognition ability towards different chiral redox probes as that obtained, e.g., by surface modification by chiral conducting thiophene oligomers 67 Interestingly, the first forward scan of each voltammetric curve in Figure 2a shows two separate peaks, variously overlapping at different scan rates, which might in principle be associated to the above anisotropy. 60 No interaction was evidenced between ferrocenyls and porphyrin, as expected due to the absence of any conjugation between them.…”

Section: Electrochemical Measurementssupporting

confidence: 61%

Molecular design driving tetraporphyrin self-assembly on graphite: a joint STM, electrochemical and computational study

et al. 2016

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Tuning the intermolecular interactions among suitably designed molecules forming highly ordered self-assembled monolayers is a viable approach to control their organization at the supramolecular level. Such a tuning is particularly important when applied to sophisticated molecules combining functional units which possess specific electronic properties, such as electron/energy transfer, in order to develop multifunctional systems. Here we have synthesized two tetraferrocene-porphyrin derivatives that by design can selectively self-assemble at the graphite/liquid interface into either face-on or edge-on monolayer-thick architectures. The former supramolecular arrangement consists of two-dimensional planar networks based on hydrogen bonding among adjacent molecules whereas the latter relies on columnar assembly generated through intermolecular van der Waals interactions. Scanning Tunneling Microscopy (STM) at the solid-liquid interface has been corroborated by cyclic voltammetry measurements and assessed by theoretical calculations to gain multiscale insight into the arrangement of the molecule with respect to the basal plane of the surface. The STM analysis allowed the visualization of these assemblies with a sub-nanometer resolution, and cyclic voltammetry measurements provided direct evidence of the interactions of porphyrin and ferrocene with the graphite surface and offered also insight into the dynamics within the face-on and edge-on assemblies. The experimental findings were supported by theoretical calculations to shed light on the electronic and other physical properties of both assemblies. The capability to engineer the functional nanopatterns through self-assembly of porphyrins containing ferrocene units is a key step toward the bottom-up construction of multifunctional molecular nanostructures and nanodevices.

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Section: Electrochemical Measurementssupporting

confidence: 61%

Molecular design driving tetraporphyrin self-assembly on graphite: a joint STM, electrochemical and computational study

et al. 2016

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“…Typical STM images of the homochiral networks of BIC‐C6 and 1S‐H or 1R‐H are shown in Figure S3 of the Supporting Information. Although chiral‐solvent‐mediated asymmetric molecular assembly at a liquid/solid interface has been reported previously,7a,b,f,g the role of chiral alcohols in the present system can be unambiguously identified as that of a coadsorber on the basis of the high‐resolution STM image 7e…”

Section: Results Of the Supramolecular Assembly Of Bic Analogues Codesupporting

confidence: 51%

Remote Chiral Communication in Coadsorber‐Induced Enantioselective 2D Supramolecular Assembly at a Liquid/Solid Interface

Chen

Wang

et al. 2015

Angewandte Chemie

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Remote chiral communication in 2D supramolecular assembly at a liquid/solid interface was investigated at the molecular level. The stereochemical information in a chiral coadsorber was transmitted over a flexible spacer with a length of up to five methylene groups to a 2D supramolecular assembly of achiral building blocks with the cooperation of specific hydrogen bonding between the chiral coadsorber and achiral building blocks and the confinement effect during 2D crystallization. When the position of the stereogenic center was changed with respect to the stereocontrolling moiety, an odd–even effect was found. A stereogenic center closer to the stereocontrolling moiety transmitted the stereochemical information to the 2D supramolecular assembly more reliably. This result is beneficial not only for mechanistic understanding of chiral communication in 2D supramolecular assembly on surfaces but also for the rational design of homochiral supramolecular assemblies on surfaces.

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“…[9][10][11][12][13][14][15] To efficiently design and predict the formationo ft hermodynamically stable molecular ordering formed through self-assembly processes, interplays of various interactions,s uch as molecule-substrate interactions,i ntermoleculari nteraction, [16][17][18][19][20] solvent effects, [21][22][23][24][25] and the balance of enthalpy and entropyt erms, [26][27][28][29] must be taken into account. Various systems employing these interactions, such as chiral assemblies, [21,[30][31][32][33] post-assembly manipulation, [34][35][36][37] and porous networks, [2,17,38] have recentlyb een intensively investigated by many groups.…”

Section: Introductionmentioning

confidence: 99%

Effects of Alkyl Chain Length and Hydrogen Bonds on the Cooperative Self‐Assembly of 2‐Thienyl‐Type Diarylethenes at a Liquid/Highly Oriented Pyrolytic Graphite (HOPG) Interface

Yokoyama

Hirose

Matsuda

2015

Chemistry A European J

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An appropriate understanding of the process of self-assembly is of critical importance to tailor nanostructured order on 2D surfaces with functional molecules. Photochromic compounds are promising candidates for building blocks of advanced photoresponsive surfaces. To investigate the relationship between molecular structure and the mechanism of ordering formation, 2-thienyl-type diarylethenes with various lengths of alkyl side chains linked through an amide or ester group were synthesized. Their self-assemblies at a liquid/solid interface were investigated by scanning tunneling microscopy (STM). The concentration dependence of the surface coverage was analyzed by using a cooperative model for a 2D surface based on two characteristic parameters: the nucleation equilibrium constant (Kn) and the elongation equilibrium constant (Ke). The following conclusions can be drawn. 1) The concentration at which a stable 2D molecular ordering is observed by STM exponentially decreases with increasing length of the alkyl chain. 2) Compounds bearing amide groups have higher degrees of cooperativity in self-assembly on 2D surfaces (i.e., σ, which is defined as Kn/Ke) than compounds with ester groups. 3) The self-assembly process of the open-ring isomer of an ester derivative is close to isodesmic, whereas that of the closed-ring isomer is cooperative because of the difference in equilibrium constants for the nucleation step (i.e., Kn) between the two isomers.

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‘Sergeants-and-Corporals’ principle in chiral induction at an interface

Abstract: Self-assembly of an achiral porphyrin at the interface between a chiral solvent and an atomically flat substrate renders the monolayer chiral, and a non-racemic solvent can even overrule the intrinsic expression of chirality in the self-assembly of chiral molecules.

Cited by 40 publications

References 26 publications

Molecular design driving tetraporphyrin self-assembly on graphite: a joint STM, electrochemical and computational study

Molecular design driving tetraporphyrin self-assembly on graphite: a joint STM, electrochemical and computational study

Remote Chiral Communication in Coadsorber‐Induced Enantioselective 2D Supramolecular Assembly at a Liquid/Solid Interface

Effects of Alkyl Chain Length and Hydrogen Bonds on the Cooperative Self‐Assembly of 2‐Thienyl‐Type Diarylethenes at a Liquid/Highly Oriented Pyrolytic Graphite (HOPG) Interface

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