Systematic control of the excited-state dynamics and carrier-transport properties of functionalized benzo[ghi]perylene and coronene derivatives

A series of benzo[ghi]perylene (Bp) and coronene (Cor) derivatives substituted with electron-withdrawing methoxycarbonyl (COOMe) or electron-donating methoxyl (MeO) groups was synthesized. The electrochemical, spectroscopic, and photophysical properties of these compounds were investigated by cyclic voltammetry, steady-state and time-resolved spectroscopy, and quantum-yield measurements. Introduction of suitable substituents onto the aromatic rings enabled control of electrochemical and spectroscopic behavior. Examination of excited-state dynamics revealed that fluorescence quantum yields increased with increasing number of COOMe groups in both Bp and Cor derivatives, consistent with the findings of DFT calculations. Single-crystal analysis allowed the performance of field-effect transistors containing single crystals of the derivatives to be rationalized. Crown decoration: A series of benzo[ghi]perylene and coronene derivatives decorated with different numbers of electron-donating or electron-withdrawing substituents was synthesized in order to control their fluorescence quantum yields and carrier-transport properties (see figure).