Benzo[e]pyrene Skeleton Dipyrylium Dication with a Strong Donor–Acceptor–Donor Interaction, and Its Two‐Electron Reduced Molecule

Abstract

The donor-acceptor-donor (D-A-D) conjugated molecules 1,4-bis(diarylaminophenylethynyl)anthraquinone (1,4-Am(2)Aq) and 1,4-bis(ferrocenylethynyl)anthraquinone (1,4-Fc(2)Aq), undergo a double proton cyclization reaction with bis(trifluoromethanesulfone)imide acid (TFSIH) to yield 1,4-bis(diarylaminophenyl or ferrocenyl) dipyrylium salts [1,4-R(2)Pyl(2)](TFSI)(2) (R=Am or Fc) with novel planar pentacyclic structures similar to the aromatic benzo[e]pyrene-type skeleton. [1,4-Am(2)Pyl(2)](TFSI)(2) could be reduced to give the neutral molecule [1,4-Am(2)Pyl(2)](0), which is stable and maintains the benzo[e]pyrene-type skeleton. To the best of our knowledge, this is the first oxygen-atom-containing polycyclic aromatic hydrocarbon with 22 (4n+2) π-electrons. The obtained condensed-ring benzo[e]pyrene-type skeleton compounds show physical and chemical properties that are significantly different from those of [1,5-Am(2)Pyl(2)](TFSI)(2), which has a perylene-type skeleton.

Design and Synthesis of Antimicrobial Active (E)‐(3‐(Substituted‐styryl)‐7H‐furo[2,3‐f]chromen‐2‐yl)(phenyl)methanone Derivatives and Their In Silico Molecular Docking Studies

“…Heterocyclic compoundscontaining nitrogen and oxygen atoms play an important role in pharmaceutical, agrochemical, and materials chemistry . Recent years, by utilizing varieties of heterocyclic moieties, a large number of drugs and agrochemical products were reported in the literature.…”

“…Another important aspect is that the lipophilic nature of the chromene derivatives helps to peeve the cell membrane effectively . Additionally, benzopyran derivatives also played imperative performance in organic material chemistry like fluorescent dyes, pigments, synthetic fibers, molecular devices , and electrophotographic.…”

Synthesis and Properties of the Doubly Oxonium-Embedded Picenes as Electron-Deficient Polycyclic Aromatic Hydrocarbons

“…Moreover, pyrylium-containing π-conjugated molecules are used as not only synthetic intermediates , but also photofunctional materials such as laser dyes, fluorescent probes, and photoredox catalysts . Indeed, most of oxonium-modified PAHs has a pyrylium skeleton. , However, PAHs incorporating two or more pyrylium rings are scarce because of their synthetic difficulties and instability. − Although Nishihara and co-workers have reported the synthesis of pentacyclic perylene and benzo­[ e ]­pyrene analogues containing two pyrylium rings, , molecular design for multiple pyrylium-containing PAHs has not been established.…”

Protonation-induced Cyclization of 1,8-Bis(arylethynyl)anthraquinones: Monopyrylium Salt Formation and Intensification of Donor–Acceptor Interaction

“…8 We have also described novel DAD molecules, 1,4-Ar 2 Aq and 1,5-Ar 2 Aq, which experienced unprecedented protonation-induced double cyclization reactions to yield the dipyrylium salts, [1,4-Ar 2 -Pyl 2 ]X 2 and [1,5-Ar 2 Pyl 2 ]X 2 (Schemes 1b and 1c). 9,10 These compounds possessed new types of quintuply fused-ring structures, which were isoelectronic with benzo[e]pyrene and perylene-type skeletons with 20³ electrons. 10 These doublycondensed phases showed unique physical, chemical, and magnetic properties.…”

“…9,10 These compounds possessed new types of quintuply fused-ring structures, which were isoelectronic with benzo[e]pyrene and perylene-type skeletons with 20³ electrons. 10 These doublycondensed phases showed unique physical, chemical, and magnetic properties. Our successful studies on DAD 1,4-Ar 2 Aq and 1,5-Ar 2 Aq systems have prompted us to examine the 1,8-Ar 2 Aq system (Scheme 1d).…”