Photodecarbonylation of alpha-diketones: a mechanistic study of reactions leading to acenes

Abstract

Poly(acene)s are significant compounds for various electronic applications. A clean, one-step synthesis involves alpha-diketones (2-4), which undergo facile Strating-Zwanenburg photodecarbonylation producing the corresponding poly(acene)s (i.e., anthracene, hexacene, and heptacene, respectively). Compounds 2-4 show weak fluorescence (lambdaF=approximately 525-530 nm and PhiF=approximately 0.1-0.4%) and phosphorescence (lambdaPh=approximately 565-570 nm) and have a small singlet-triplet energy gap (S1-T1 gap, approximately 4 kcal/mol) that facilitates rapid intersystem crossing from the singlet to the triplet state. Both the singlet states (tauS=approximately 20-218 ps) and the triplet states (tauT=approximately 370 ps to <7 ns) of 2-4 are short-lived, while the decarbonylation of 2-4 is a rapid process occurring within 7 ns from both the singlet and the triplet manifolds. The nanosecond laser flash photolysis of 4 also reveals the T-T absorption of heptacene (580 nm, tau=approximately 11 micros).