Synthesis and Properties of Donor–Acceptor‐Type Cyclobisbiphenylenecarbonyls

The scalable synthesis of figure-eight π-systems is challenging for the conventional bottom-up approach. We have recently reported that the oxidative inner-bond cleavage of commercially available dibenzo[g,p]chrysene efficiently furnishes a figure-eight π-acceptor, cyclobisbiphenylenecarbonyl (CBBC), in large quantity. Furthermore, its donor-acceptor-type derivative with four N-carbazolyl substituents at the meta-positions of the carbonyl groups exhibited thermally activated delayed fluorescence (TADF) and circularly polarized luminescence (CPL) with a high |g_CPL| value of 1.0×10^-2. Herein, we synthesized nine donor-acceptor-type CBBC derivatives by changing the donor substituents and their positions. Compared to previously reported carbazole-substituted CBBC, tetramethylcarbazole- and 9,10-dihydro-9,9-dimethylacridine-substituted derivatives exhibited enhanced emission quantum yields and accelerated reverse intersystem crossing. The functionalization of the para-positions of the carbonyl groups resulted in better tunability of emission colors rather than meta-functionalization, whose color variation ranges from light blue to red. The incorporation of bulky substituents at the meta-positions of the carbonyl groups induced the conformational change to a distorted ring structure. Investigation of the substituent effect on the chiroptical properties revealed that the introduction of less bulky donor units such as carbazole at the meta-positions of the carbonyl groups is effective in achieving high |g_CPL| values.