Ambipolar organic semiconductors from electron-accepting cyclopenta-fused anthracene

Abstract

Reported here are a new group of cyclopent[hi]aceanthrylene derivatives, which have a cyclopentadiene moiety to accept electrons and thus function as ambipolar organic semiconductors in thin film transistors.

Tunable electron acceptors based on cyclopenta[hi]aceanthrylenes

“…[2][3][4][5][6][7] These substitution strategies provide opportunities to tune frontier orbitals, such as the Lowest Unoccupied Molecular Level (LUMO), to beneficially interface with donor materials in organic photovoltaics [8][9][10] or to access stable ambipolar or n-type organic field-effect transistors (OFETs). [11][12][13][14][15] Here we demonstrate that the electronic properties of cyclopenta[hi]aceanthrylenes (CPAA) based materials can be systematically varied depending on the substituent constant of an attached arylene ethynylene.…”

2,3‐Di(thiophen‐2‐yl)quinoxaline Amine Derivatives: Yellow‐Blue Fluorescent Materials for Applications in Organic Electronics

“…In principle the ambipolar characteristic in a molecule have HOMO energy level must be equal or greater than 5.6 eV and LUMO value must be around 3.15 eV . The energy levels of the HOMO and LUMO for reported small organic ambipolar materials such as Tyrian Purple (HOMO= − 5.5 eV; LUMO=− 3.8 eV), 6,13‐bis(triisopropylsilylethynyl)‐1,4,8,11‐tetraazapentacene (TIPS‐PEN) (HOMO=− 5.49 eV; LUMO=− 3.68 eV), 2,7‐bis(trimethylsilyl)ethynyl)cyclopenta[ h,i ]aceanthrylene (HOMO=−5.32 eV; LUMO=−3.67 eV), 1,4–diketo–2,5–dihexyl–3,6–bis(4–ethylendioxythienyl)phenyl)pyrrolo[3,4– c ]pyrrole (HOMO=−5.40 eV; LUMO=−3.68 eV), 2,2’‐bis{5‐[2,5‐(2‐ethylhexyl)‐6‐(5‐cyano‐thiophene‐2‐yl)‐pyrrolo[3,4‐c]pyrrole‐1,4‐dione‐3‐yl]thiophene}(HOMO=− 5.45 eV; LUMO=−3.74 eV), and polymers such as Poly[2‐methoxy‐5’3’7’dimethyloctyloxyl)‐1,4‐phenylenevinylene) (MDMO‐PPV) (HOMO=− 5.4 eV; LUMO=− 3.2 eV), Poly[2,6‐(4,4‐bis‐2‐ethylhexyl)‐4 H ‐cyclopenta‐[2,1‐b‐3,4‐ b ]dithiophene‐alt‐4,7(2,1,3‐ benzothiadazole) (PCPDTBT) (HOMO=− 5.3 eV; LUMO=− 3.55 eV) . The HOMO and LUMO energies of 2–10 were calculated from the first oxidation and reduction potentials.…”

Metal‐Catalyzed Annulation Reactions for π‐Conjugated Polycycles

“…Similar to the aforementioned internal CP-PAHs, peripheral CP-PAHs as subunits of fullerenes also exhibit high electron affinity and relatively low LUMO energy levels with respect to those of acene-type PAHs, making them attractive to use as potential ntype and ambipolar semiconductors. [32] Nowadays, the Pd-catalyzed intermolecular pentannulation of arenyl halides with alkynes is one of the most efficient protocols for synthesis of the peripheral CP-PAHs. This reaction has been developed by Grigg et al in 1993 using a Pd(OAc) 2 /PPh 3 catalyst system combined with TiOAc in the reaction of 1-iodonaphthalene (56) and 1,2-diphenylacetylene, giving 1,2-diphenylacenaphthylene (57) in 45 % yield (Scheme 20).…”

“…1,2,6,7-Tetraphenylcyclopenta[hi]aceanthrylene (67 c) has been prepared by Miao et al following this approach and applied in thin film transistors, which exhibited a high ambipolar behavior with a hole mobility of 0.21 cm À2 V À1 s À1 and an electron mobility of 0.02 cm À2 V À1 s À1 . [32] Most recently, Wu and co-workers have reported the first synthetic methodology of [8]circulenes by using the Pd-catalyzed CÀH/alkyne annulation (Scheme 24). [37] Several substituted [8]circulenes 69 were synthesized in comparable yields through the reaction of tetraiodo-substituted tetraphenylenes 68 with symmetric 1,2-diarylalkynes in the presence of Pd(OAc) 2 catalyst, NaOAc base, and nBu 4 NCl at 110 8C.…”