Bowl-Shaped Symmetric and Non-symmetric Bis-functionalized Indacenopicenes

Abstract

Regioselective arrangement of two groups of orthogonal reactivity in bowl-shaped as-indaceno[3,2,1,8,7,6-pqrstuv]picene (Idpc) was key for the synthesis of hetero-bis-functionalized Idpc derivatives. Halogen and methyl groups were positioned at specific positions in the rim area of Idpc at an early stage during the synthesis by functionalization of suitable precursors. Regioselective functionalization of the bowl’s rim was then finally achieved either via consecutive Cu(I)-catalyzed azide–alkyne coupling (CuAAC) and C–C cross-coupling reactions or by C–C cross-coupling alone, giving access to either symmetric or non-symmetric bis-functionalized Idpc derivatives. The self-aggregation behavior of 9c in solution was investigated by recording a series of concentration-dependent NMR spectra. The aggregation constant of 9c was determined by a nonlinear least-squares treatment of the 1H NMR shift data to be 2.9 ± 0.2 M–1, and the formation of dimers was found to be the prevailing process.