Gas phase synthesis and X-ray crystal structures of supramolecular networks with bromocorannulene: Similarities and differences with their corannulene analogs

The reactivity of bowl-shaped mono-bromocorannulene (C20H9Br) has been examined and compared with that of corannulene (C20H10). Although bromination of corannulene was shown to flatten the bowl and change its electronic properties, it has not affected the outcome of coordination reactions toward the avid Lewis acidic [Rh2(O2CCF3)4] complex. Two new products have the same composition [{Rh2(O2CCF3)4}m · (C20H9Br)n] where m:n = 1:1 (1) and 3:2 (2), as the corresponding corannulene-based analogs. The X-ray diffraction studies of 1 and 2 revealed 1D chain and 2D layered structures built on η2-coordination of rhodium(II) to rim carbon sites of the C20H9Br-bowl, similar to those of C20H10. While no essential difference is found in 2D structures, the local coordination environments of the [Rh2(O2CCF3)4] unit differ in their 1D complexes.