One‐Dimensionally Disordered Chiral Sorting by Racemic Tiling in a Surface‐Confined Supramolecular Assembly of Achiral Tectons

Surface-confined covalent coupling reactions of the linear compound 4-(but-3-en-1-ynyl)-4'-ethynyl-1,1'-biphenyl (1), which contains one alkyne and one enyne group on opposing ends,h ave been investigated using scanning tunneling microscopy( STM) and density functional theory (DFT) calculations.T he reactions showasurface-dependent chemoselectivity:o nA u(111),c ompound 1 preferentially yields cyclotrimerization products,w hile on Cu(111), as elective coupling between the enyne and alkyne groups is observed. Linear,V -shaped string formations combined with Y-shaped bifurcation motifs result in arandom reticulation on the entire surface.D FT calculations show that the CÀH···p dÀ transition state of the reaction between the deprotonated alkyne group and anearby H-donor of the alkene group plays akey role in the mechanism and high chemoselectivity.This study highlights ac oncept that opens new avenues to the surface-confined synthesis of covalent carbon-based sp-sp 2 polymers.

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Surface‐Dependent Chemoselectivity in C−C Coupling Reactions

Chen

Lin

Zhang

et al. 2019

Angewandte Chemie

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Metastable Chiral Azobenzenes Stabilized in a Double Racemate

et al. 2020

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The self‐assembly of chiral organic chromophores is gaining huge significance due to the abundance of supramolecular chirality found in natural systems. We report an interdigitated molecular assembly involving axially chiral octabrominated perylenediimide (OBPDI) which transfers chiral information to achiral aromatic moieties. The crystalline two‐component assemblies of OBPDI and electron‐rich aromatic units were facilitated through π‐hole⋅⋅⋅π donor–acceptor interactions, and the charge‐transfer characteristics in the ground and excited states of the OBPDI cocrystals were established through spectroscopic and theoretical techniques. The OBPDI cocrystals entail a remarkable homochiral segregation of P and M enantiomers of both molecular entities in the same crystal system, leading to twisted double‐racemic arrangements. Synergistically engendered cavities with the stored chiral information of the twisted OBPDI stabilize higher‐energy P/M enantiomers of trans‐azobenzene through non‐covalent interactions.

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Snapshots of Dynamic Adaptation: Two‐Dimensional Molecular Architectonics with Linear Bis‐Hydroxamic Acid Modules

et al. 2019

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Linear modules equipped with two terminal hydroxamic acid groups act as the building block of diverse two‐dimensional supramolecular motifs and patterns with room‐temperature stability on the close‐packed single‐crystal surfaces of silver and gold, revealing a complex self‐assembly scenario. By combining multiple investigation techniques (scanning tunneling microscopy, atomic force microscopy, X‐ray photoelectron spectroscopy, and density functional theory calculations), we analyze the characteristics of the ordered assemblies which range from close‐packed structures to polyporous networks featuring an exceptionally extended primitive unit cell with a side length exceeding 7 nm. The polyporous network shows potential for hosting and promoting the formation of chiral supramolecules, whereas a transition from 1D chiral randomness to an ordered racemate is discovered in a different porous phase. We correlate the observed structural changes to the adaptivity of the building block and surface‐induced changes in the chemical state of the hydroxamic acid functional group.

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One‐Dimensionally Disordered Chiral Sorting by Racemic Tiling in a Surface‐Confined Supramolecular Assembly of Achiral Tectons

Cited by 6 publications

References 41 publications

Surface‐Dependent Chemoselectivity in C−C Coupling Reactions

Surface‐Dependent Chemoselectivity in C−C Coupling Reactions

Metastable Chiral Azobenzenes Stabilized in a Double Racemate

Snapshots of Dynamic Adaptation: Two‐Dimensional Molecular Architectonics with Linear Bis‐Hydroxamic Acid Modules

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