This work is a part of a broad program in our laboratory dedicated to the investigation of a new class of non-planar polyaromatic hydrocarbons that map onto the surfaces of fullerenes (and referred to as buckybowls). It focuses on the preparation of buckybowls, their molecular and solid state structures, and reactivity in metal binding reactions. For the first time, the structures of all available buckybowls have been analyzed using X-ray diffraction data collected in the course of this work, as well as data previously obtained in our group or reported by others (and dearchived from the Cambridge Structural Database). Forces governing the packing arrangements of nonplanar polyaromatic surfaces into three-dimensional solid-state networks have been discussed. Furthermore, the reactivity of bowl-shaped polyarenes toward coordinatively unsaturated electrophilic dirhodium(II) and trimercury(II) complexes have been tested. Bromocorannulene and monoindenocorannulene were selected to react with the volatile dirhodium(II) tetratrifluoroacetate complex in a solvent-free environment. Several new products were isolated and fully characterized, including the first complex in which rhodium(II) centers coordinate to the interior part of a p-bowl. To probe the interactions between planar and non-planar surfaces, a planar trimercury(II) complex was chosen to react with a number of bowl-shaped polyarenes. In the solid state, the interacting moieties form binary stacks of alternating planar and non-planar surfaces and exhibit a very strong mutual effect on each other. Thus, one can tune the amount of strain energy imposed at the molecular level by using non-planar polyarenes as templates for bending planar metal complexes. The extent of this effect is discussed in detail.