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Asymmetry Induction by Cooperative Intermolecular Hydrogen Bonds in Surface‐Anchored Layers of Achiral Molecules
Author(s) -
Dmitriev Alexandre,
Spillmann Hannes,
Stepanow Sebastian,
Strunskus Thomas,
Wöll Christof,
Seitsonen Ari P.,
Lingenfelder Magali,
Lin Nian,
Barth Johannes V.,
Kern Klaus
Publication year - 2006
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200600110
Subject(s) - chemistry , crystallography , carboxylate , density functional theory , hydrogen bond , molecule , scanning tunneling microscope , intermolecular force , supramolecular chemistry , chirality (physics) , substrate (aquarium) , x ray photoelectron spectroscopy , stereochemistry , materials science , computational chemistry , crystal structure , nanotechnology , organic chemistry , symmetry breaking , nuclear magnetic resonance , nambu–jona lasinio model , chiral symmetry breaking , quantum mechanics , physics , oceanography , geology
The mesoscale induction of two‐dimensional supramolecular chirality (formation of 2D organic domains with a single handedness) was achieved by self‐assembly of 1,2,4‐benzenetricarboxylic (trimellitic) acid on a Cu(100) surface at elevated temperatures. The combination of spectroscopic [X‐ray photoelectron spectroscopy (XPS) and near‐edge X‐ray absorption fine structure (NEXAFS)], real‐space‐probe [scanning tunneling microscopy (STM)], and computational [density functional theory (DFT)] methods allows a comprehensive characterization of the obtained organic adlayers, where details of molecular adsorption geometry, intermolecular coupling, and surface chemical bonding are elucidated. The trimellitic acid species, comprising three functional carboxylic groups, form distinct stable mirror‐symmetric hydrogen‐bonded domains. The chiral ordering is associated with conformational restriction in the domains: molecules anchor to the substrate with an ortho carboxylate group, providing two para carboxylic acid moieties for collective lateral interweaving through H bonding, which induces a specific tilt of the molecular plane. The ease of molecular symmetry switching in domain formation makes homochiral‐signature propagation solely limited by the terrace width. The molecular layer modifies the morphology of the underlying copper substrate and induces μm‐sized strictly homochiral terraces.