Chirality transfer in 1D self-assemblies: influence of H-bonding vs metal coordination between dicyano[7]helicene enantiomers.

Chiral recognition as well as chirality transfer in supramolecular self-assembly and on-surface coordination is studied for the enantiopure 6,13-dicyano[7]helicene building block. It is remarkable that, with this helical molecule, both H-bonded chains and metal-coordinated chains can be formed on the same substrate, thereby allowing for a direct comparison of the chain bonding motifs and their effects on the self-assembly in experiment and theory. Conformational flexure and both adsorbate/adsorbent and intermolecular interactions can be identified as factors influencing the chiral recognition at the binding site. The observed H-bonded chains are chiral, however, the overall appearance of Cu-coordinated chains is no longer chiral. The study was performed via scanning tunneling microscopy, X-ray-photoelectron spectroscopy and density functional theory calculations. We show a significant influence of the molecular flexibility and the type of bonding motif on the chirality transfer in the 1D self-assembly.

[1]  K. Ernst,et al.  Chiral conflict among different helicenes suppresses formation of one enantiomorph in 2D crystallization. , 2013, Journal of the American Chemical Society.

[2]  R. Lazzaroni,et al.  Self-assembly of an asymmetrically functionalized [6]helicene at liquid/solid interfaces. , 2013, Chemical communications.

[3]  J. Barth,et al.  Formation of fe cluster superlattice in a metal-organic quantum-box network. , 2013, Physical review letters.

[4]  Marc Gingras,et al.  One hundred years of helicene chemistry. Part 3: applications and properties of carbohelicenes. , 2013, Chemical Society reviews.

[5]  K. Reuter,et al.  Control of intermolecular bonds by deposition rates at room temperature: hydrogen bonds versus metal coordination in trinitrile monolayers. , 2013, Journal of the American Chemical Society.

[6]  K. Ernst.  Molecular chirality at surfaces , 2012 .

[7]  Chuan-feng Chen,et al.  Helicenes: synthesis and applications. , 2012, Chemical reviews.

[8]  A. Kühnle,et al.  Molecular Self-Assembly of Enantiopure Heptahelicene-2-Carboxylic Acid on Calcite (101̅4) , 2012 .

[9]  E. W. Meijer,et al.  Induction of chirality in an achiral monolayer at the liquid/solid interface by a supramolecular chiral auxiliary. , 2012, Journal of the American Chemical Society.

[10]  F. Diederich,et al.  Self-assembly and two-dimensional spontaneous resolution of cyano-functionalized [7]helicenes on Cu111. , 2011, Angewandte Chemie.

[11]  Xingqiang Shi,et al.  Single-molecule resolution of an organometallic intermediate in a surface-supported Ullmann coupling reaction. , 2011, Journal of the American Chemical Society.

[12]  A. Kühnle,et al.  Racemic and Optically Pure Heptahelicene‐2‐carboxylic Acid: Its Synthesis and Self‐Assembly into Nanowire‐Like Aggregates , 2011 .

[13]  P. Ordejón,et al.  Orbital specific chirality and homochiral self-assembly of achiral molecules induced by charge transfer and spontaneous symmetry breaking. , 2010, Physical review letters.

[14]  C. Joachim,et al.  Self-assembly of hydrogen-bonded chains of molecular landers. , 2010, Chemical communications.

[15]  J. Barth,et al.  Self-assembly of flexible one-dimensional coordination polymers on metal surfaces. , 2010, Journal of the American Chemical Society.

[16]  M. Nardelli,et al.  Chiral Steering of Molecular Organization in the Limit of Weak Adsorbate−Substrate Interactions: Enantiopure and Racemic Tartaric Acid Domains on Ag(111) , 2010 .

[17]  M. Rohlfing,et al.  Toward Molecular Nanowires Self-Assembled on an Insulating Substrate: Heptahelicene-2-carboxylic acid on Calcite (1014) , 2010 .

[18]  W. Kuch,et al.  Temperature, Surface, and Coverage-Induced Conformational Changes of Azobenzene Derivatives on Cu(001) , 2009 .

[19]  H. D. Flack,et al.  Louis Pasteur's discovery of molecular chirality and spontaneous resolution in 1848, together with a complete review of his crystallographic and chemical work. , 2009, Acta crystallographica. Section A, Foundations of crystallography.

[20]  Talat S. Rahman,et al.  A surface coordination network based on substrate-derived metal adatoms with local charge excess. , 2008, Angewandte Chemie.

[21]  F. Diederich,et al.  Supramolecular synthons on surfaces: controlling dimensionality and periodicity of tetraarylporphyrin assemblies by the interplay of cyano and alkoxy substituents. , 2008, Chemistry.

[22]  R. Fasel,et al.  Coverage and Enantiomeric Excess Dependent Enantiomorphism in Two-Dimensional Molecular Crystals† , 2008 .

[23]  N. Lorente,et al.  Long-range repulsive interaction between molecules on a metal surface induced by charge transfer. , 2007, Physical review letters.

[24]  J. Gómez‐Herrero,et al.  WSXM: a software for scanning probe microscopy and a tool for nanotechnology. , 2007, The Review of scientific instruments.

[25]  R. Fasel,et al.  Amplification of chirality in two-dimensional enantiomorphous lattices , 2006, Nature.

[26]  K. Ernst,et al.  Homochirality in monolayers of achiral meso tartaric acid , 2005 .

[27]  K. Ernst,et al.  Induction of homochirality in achiral enantiomorphous monolayers. , 2004, Journal of the American Chemical Society.

[28]  S. M. Barlow,et al.  Supramolecular assembly of strongly chemisorbed size- and shape-defined chiral clusters: S- and R-alanine on Cu(110). , 2004, Langmuir : the ACS journal of surfaces and colloids.

[29]  R. Fasel,et al.  Chirality transfer from single molecules into self-assembled monolayers. , 2003, Angewandte Chemie.

[30]  A. Yamagishi,et al.  STM observation of molecular chirality and alignment on solid surface , 2003 .

[31]  R. Raval,et al.  Extended surface chirality from supramolecular assemblies of adsorbed chiral molecules , 2000, Nature.

[32]  R. Berndt,et al.  Self-assembly of 1-nitronaphthalene on Au(111) , 2000 .

[33]  A. Hughes,et al.  A comparison of weak molecular adsorption of organic molecules on clean copper and platinum surfaces , 1984 .