Acene-Integrated Buckybowls with Near-Infrared II Absorption and over 90 % Photothermal Conversion Efficiency.

Tetracene and pentacene are large, promising building blocks for construction of complex molecular nanocarbons due to their extraordinary photophysical and electronic properties. Herein, two acene-integrated buckybowls, composed of two rows of tetracenes and pentacenes fused through s-indacene unit at the zigzag edges, have been synthesized and characterized. Compared to parent tetracene and pentacene, the buckybowls are extremely stable and show much smaller electrochemical band gaps. Kinetic studies gave the bowl-to-bowl inversion barriers of 11.7 and 13.3 kcal mol. Subsequent investigations on magnetic ring currents revealed two local diatropic currents at two rows of acenes and one paratropic current at the s-indacene unit, respectively. Notably, both buckybowls show a broad absorption that reaches into near-infrared II region, and a high photothermal conversion efficiency (>90 %) was achieved when exposed to near-infrared 1064 nm laser photo-irradiation. This study highlights the unusual nature of merging the intrinsic properties of acenes with the inherent properties of buckybowls and showcases a potential avenue for acene utilization for the design of novel complex nanocarbons with a broad range of applications.