Abstract

We demonstrate the self-assembly of C60_{60} and pentacene (Pn) molecules into acceptor-donor heterostructures which are well-ordered and -- despite the high degree of symmetry of the constituent molecules -- {\it chiral}. Pn was deposited on Cu(111) to monolayer coverage, producing the random-tiling (RR) phase as previously described. Atop RR-phase Pn, post-deposited C60_{60} molecules cause rearrangement of the Pn molecules into domains based on chiral supramolecular `pinwheels'. These two molecules are the highest-symmetry achiral molecules so far observed to coalesce into chiral heterostructures. Also, the chiral pinwheels (composed of 1 C60_{60} and 6 Pn each) may share Pn molecules in different ways to produce structures with different lattice parameters and degree of chirality. High-resolution scanning tunneling microscopy (STM) results and knowledge of adsorption sites allow the determination of these structures to a high degree of confidence. The measurement of chiral angles identical to those predicted is a further demonstration of the accuracy of the models. Van der Waals density functional theory calculations reveal that the Pn molecules around each C60_{60} are torsionally flexed around their long molecular axes and that there is charge transfer from C60_{60} to Pn in each pinwheel.

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