Fusion of Phosphole and 1,1′‐Biacenaphthene: Phosphorus(V)‐Containing Extended π‐Systems with High Electron Affinity and Electron Mobility

Abstract

A profusion of phospholes: Diacenaphtho[1,2-b:1',2'-d]phospholes, a new class of arene-fused phosphole π-systems, were synthesized and their structural and electrochemical properties studied. The P-sulfide derivative has a high electron-transporting ability (μ(E) =2.4×10(-3) cm(2) V(-1) s(-1)) in a vacuum-deposited film.

Blue Electrofluorescence Properties of Furan–Silole Ladder Pi-Conjugated Systems

“…Following the successful incorporation of thiophene oligomers and polymers in opto-electronic devices, [1][2][3] new derivatives featuring B [4,5], N [6,7], O [8,9], Si [10] or P [11][12][13][14][15][16][17][18][19] have been developed. In particular, siloles (silacyclopentadienes) found promising applications in the field of organic light emitting devices (OLEDs) [20][21][22][23].…”

Palladium‐Catalyzed Direct Synthesis of Phosphole Derivatives from Triarylphosphines through Cleavage of Carbon–Hydrogen and Carbon–Phosphorus Bonds

“…[1] The method most frequently used for the synthesis of phospholes involves the nucleophilic substitution of a P À X bond with a stoichiometric amount of an organometallic species such as organolithium or organomagnesium reagents. [1] The method most frequently used for the synthesis of phospholes involves the nucleophilic substitution of a P À X bond with a stoichiometric amount of an organometallic species such as organolithium or organomagnesium reagents.…”

Fusing Porphyrins and Phospholes: Synthesis and Analysis of a Phosphorus‐Containing Porphyrin

“…Bis-(pyrrolo)phosphole 7 gave rise to an oxidation peak at 0.73 Vwhereas no reduction peak was visible at potentials up to À2.5 V. Thee lectrochemical properties of 7 are similar to those of other bis(pyrrolo)heteroles. [14] Given that the energy level of Fc/Fc + is À4.8 eV under vacuum, the LUMO level of 12 was estimated to be À3.61 eV. Theeffective p-expansion over the two porphyrins lowers the oxidation potentials while they are shifted in the positive direction by the electron-withdrawing effect of the phosphorus(V) center, offsetting the effects;t herefore, the oxidation potentials of 12 are comparable to those of 13 and 7.I nc ontrast, the three reduction peaks,i ncluding the unexpected new one,a re significantly shifted in the positive direction, probably owing to the strongly electron-accepting character arising from the phosphole moiety (see below).…”

“…HOMO and HOMO-1 of 12 a originate from the HOMO of 13.Ast he phosphole ring is located on the node of HOMO/ HOMO-1, these orbitals mainly exhibit porphyrin character. [8,14] This is ac onsequence of the stabilization solely by the fusion of the two porphyrins and the phosphole ring. On the other hand, the LUMO of 12 a is well delocalized over the two porphyrin moieties as well as the phosphole ring (Figure 5b).…”