Abstract The fullerene C60, one of the largest molecules identified in the interstellar medium (ISM), has been proposed to form top-down through the photochemical processing of large (more than 60 C atoms) polycyclic aromatic hydrocarbon (PAH) molecules. In this article, we focus on the opposite process, investigating the possibility that fullerenes form from small PAHs, in which bowl-forming plays a central role. We combine laboratory experiments and quantum chemical calculations to study the formation of larger PAHs from charged fluorene clusters. The experiments show that with visible laser irradiation, the fluorene dimer cationâ[C13H9âC13H9]+âand the fluorene trimer cationâ[C13H9âC13H8âC13H9]+âundergo photodehydrogenation and photoisomerization, resulting in bowl-structured aromatic cluster ions, C26H12 + and C39H20 +, respectively. To study the details of this chemical process, we employ quantum chemistry that allows us to determine the structures of the newly formed cluster ions, to calculate the dissociation energies for hydrogen loss, and to derive the underlying reaction pathways. These results demonstrate that smaller PAH clusters (with less than 60 C atoms) can convert to larger bowled geometries that might act as building blocks for fullerenes, because the bowl-forming mechanism greatly facilitates the conversion from dehydrogenated PAHs to cages. Moreover, the bowl-forming induces a permanent dipole moment thatâin principleâallows one to search for such species using radio astronomy.