The phenomenon of chiral crystallization into homochiral crystals is known for more than 170 years, yet it is still poorly understood. Studying crystallization on surfaces under well-defined condition seems a promising approach towards better understanding the intermolecular chiral recognition mechanisms during nucleation and growth. The two-dimensional aggregation of racemic trioxaundecahelicene on the single crystalline silver(100) surface has been investigated with scanning tunneling microscopy and with non-contact atomic force microscopy, as well as molecular modeling simulations. A transition from homochiral cluster motifs to heterochiral assembly into large islands with increasing coverage is observed. Force field modelling confirms higher stability of heterochiral arrangements from twelve molecules on. Results are discussed with respect to previous findings for the all-carbon heptahelicene on the same surface.

Department of Chemistry The Maharaja Sayajirao University of Baroda Vadodara 390 002 India

Institute of Organic Chemistry and Biochemistry The Czech Academy of Sciences Flemingovo náměstí 2 16610 Prague Czech Republic

Nanosurf Laboratory Institute of Physics The Czech Academy of Sciences Cukrovarnická 10 162 00 Prague Czech Republic

Surface Science and Coating Technologies Empa Swiss Federal Laboratories for Materials Science and Technology Überlandstrasse 129 8600 Dübendorf Switzerland

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