Steering the Achiral into Chiral with a Self-Assembly Strategy.

Chirality transfer from self-assembly of achiral titanyl phthalocyanine (TiOPc) to its top-sitting TiOPc molecule has been successfully achieved. The TiOPc molecules first assemble into a porous network on Au(111) that contains periodic chiral voids, each being fenced by four axially rotating TiOPc molecules in upward adsorption geometry where their ending O atoms exclusively point away from the substrate. The additional top-sitting TiOPc molecule turns out to be chiral upon adsorption on a chiral void with its ending O atom toward the substrate. The chirality of the top-sitting TiOPc is associated with a charge transfer between its indole rings and the ending O atoms of the underlying TiOPc molecules that form the chiral void, resulting in asymmetric electronic density of the indole rings in the top-sitting molecule and accordingly the chirality of the molecular orbitals. Such a scenario also validates other planar achiral metallophthalocyanines such as copper phthalocyanine that become chiral upon adsorption on the chiral voids in the underlying TiOPc assembly, indicating that the chirality transfer mechanism from assembly to the top-sitting molecule is not uncommon.