Evaluating the Role of Molecular Heredity in the Optical and Electronic Properties of Cross-Conjugated Benzo[1,2-d:4,5-d′]bisoxazoles

A series of eight benzo[1,2-d:4,5-d′]bisoxazole (BBOs) were synthesized using the heredity principle as a design motif, whereby we investigated which characteristics of the linear parents were inherited by their cross-conjugated children. Four linear parents bearing 4-tert-butylbenzene (P) or 1,3-bis(4-tert-butylphenyl)benzene (M) at either the 2,6- or 4,8-position on the BBO and four cross-conjugated children bearing various combinations of the two isoelectronic aryl substituents were evaluated. Due to the bulky nature of the M substituent compared to that of the P substituent, the influence of steric hindrance along the BBO axes was explored theoretically and experimentally. The optical and electronic properties of each molecule were investigated in the solution and solid state using density functional theory (DFT) and time-dependent DFT (TD-DFT) and characterized using ultraviolet photoelectron spectroscopy (UPS), ultraviolet–visible (UV–vis) spectroscopy, and photoluminescence (PL) spectroscopy. The well-correlated theoretical and experimental results showed that the selective tuning of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels was possible through the strategic placement of substituents without impacting the H → L transition energy. Specifically, the theoretical results demonstrated that for the BBO children the HOMO and LUMO energy levels were inherited from the 4,8- and 2,6-parents, respectively. Each molecule was found to exhibit emission maxima ≤451 nm, making them ideal candidates for blue organic light-emitting diode (OLED) materials.