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Fine‐Tuning of Relative Metal–Metal Distances within Highly Ordered Chiral 2D Nanopatterns
Author(s) -
Zell Philipp,
Mögele Florian,
Ziener Ulrich,
Rieger Bernhard
Publication year - 2006
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200500992
Subject(s) - alkyl , van der waals force , steric effects , crystallography , intermolecular force , metal , alkoxy group , ligand (biochemistry) , chemistry , highly oriented pyrolytic graphite , chirality (physics) , scanning tunneling microscope , asymmetric carbon , palladium , materials science , stereochemistry , molecule , nanotechnology , organic chemistry , catalysis , biochemistry , receptor , nambu–jona lasinio model , chiral symmetry breaking , physics , quantum mechanics , quark
The two‐dimensional nanopatterning of a series of neutral alkoxy/alkyl‐functionalised bis(salicylaldehydato)/bis(aldiminato)copper( II ) and ‐palladium( II ) complexes at a liquid/solid (highly oriented pyrolytic graphite, HOPG) interface has been studied by scanning tunnelling microscopy (STM). The relative metal–metal distances were tuned stepwise in two dimensions by ligand design. Exchange of the carbonyl O‐atom for NH or N ‐alkyl units effects different intermolecular interactions such as weak hydrogen bonds and steric effects that determine, together with the van der Waals forces between the alkyl chains, the relative arrangements of the complexes. Further variation of the length and position of the alkoxy side chains as well as the exchange of Cu II for Pd II affords an absolute fine‐tuning of the surface structures. Highly resolved STM images of the resultant highly ordered adlayers allow us to establish detailed models of the molecular 2D arrays and to classify them into three basic chiral pattern types. Homochirality within the individual domains is induced by the highly regular deposition of the prochiral complexes from the same enantiotopic face. In the case of the C 12 O‐substituted bis(salicylaldiminato) (NH) Cu II complex Cu5 , a secondary structure occurs as a racemic mixture of two chiral surface species deposited in a distinct alternating order.