Pentagonal tiling with buckybowls: pentamethylcorannulene on Cu(111).

We present scanning tunnelling microscopy studies and first principles calculation on the 2D crystallization of pentagonal pentamethylcorannulene on a Cu(111) surface under ultrahigh vacuum in the temperature range of 50 K to 400 K. The observed 2D crystal phases and their packing densities are compared to tiling options of hard pentagons. Temperature change-induced reversible phase transitions reveal entropic effects in 2D crystallization. Only inclusion of dispersion interactions into density functional theory yields structures observed experimentally at low temperatures.