Chiral structures created through the adsorption of molecules onto achiral surfaces play pivotal roles in many fields of science and engineering.Here,wepresent asystematic study of an ovel chiral phenomenon on as urface in terms of organizational chirality,t hat is,m eso-isomerism, through coverage-driven hierarchical polymorphic transitions of supramolecular assemblies of highly symmetric p-conjugated molecules.F our coverage-dependent phases of dehydrobenzo-[12]annulene were uniformly fabricated on Ag(111), exhibiting unique chiral characteristics from the single-molecule level to two-dimensional supramolecular assemblies.A ll coveragedriven phase transitions stem from adsorption-induced pseudo-diastereomerism, and our observation of alemniscate-type (1)s upramolecular configuration clearly reveals ad rastic chiral phase transition from an enantiomeric chiral domain to am eso-isomeric achiral domain. These findings providen ew insights into controlling two-dimensional chiral architectures on surfaces.

Chiral structures created through the adsorption of molecules onto achiral surfaces play pivotal roles in many fields of science and engineering.Here,wepresent asystematic study of an ovel chiral phenomenon on as urface in terms of organizational chirality,t hat is,m eso-isomerism, through coverage-driven hierarchical polymorphic transitions of supramolecular assemblies of highly symmetric p-conjugated molecules.F our coverage-dependent phases of dehydrobenzo-[12]annulene were uniformly fabricated on Ag (111), exhibiting unique chiral characteristics from the single-molecule level to two-dimensional supramolecular assemblies.A ll coveragedriven phase transitions stem from adsorption-induced pseudo-diastereomerism, and our observation of alemniscate-type (1)s upramolecular configuration clearly reveals ad rastic chiral phase transition from an enantiomeric chiral domain to am eso-isomeric achiral domain. These findings providen ew insights into controlling two-dimensional chiral architectures on surfaces. Organizational chiralityRacemic mixture Racemic mixture Racemic mixture Meso-isomeric configuration (lemniscate-type (1)) [a] See Figure S8. AngewandteChemie Forschungsartikel 9717Angew.C hem. 2019, 131,9 713 -9720

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