Linear Nonalternant Isomers of Acenes Fusing Multiple Azulene Units

A modular approach to azulene building blocks was developed starting from readily available aryl-substituted cyclopentadiene and ortho-haloaryl aldehyde by dehydration condensation followed by palladium-catalyzed C-H coupling. It facilitates the synthesis of four nonalternant isomers of pentacene and hexacene, namely, dibenzo[e,g]azulene, benzo[1,2-f : 5,4-f ']diazulene, benzo[1,2-f : 4,5-f ']diazulene, and naphtho[2,3-f : 6,7-f ']diazulene, which exhibit narrow band gaps with high stability in addition to protonation-caused enhanced near-infrared fluorescence. We discovered that in these isomers, i) constitutional isomerism influences significantly their photoelectric properties and (i) the elongation of the conjugation system does not necessarily lead to a narrowing in the band gap. Due to the easy modifiability of the nonazulene building blocks, this strategy can be extended to modularly prepare numerous multiazulene-fused aromatics.

Automated summary

A new modular approach for the synthesis of various azulene compounds with narrow band gaps and high stability has been developed, showing enhanced near-infrared fluorescence.