Condensed Phenoxazine Dimer and Its Radical Cation

Miyamae, Takayuki; Haraguchi, Makoto; Tachi, Yoshimitsu; Suzuki, Shuichi; Kozaki, Masatoshi; Okada, Keiji

doi:10.1021/acs.orglett.0c02305

Cited by 9 publications

(4 citation statements)

References 21 publications

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“…for C 40 H 26 N 4 : m/z= 562.2152), indicating a dimeric product. To suppress dimerization, mild oxidation conditions were considered, and we employed a base‐promoted coupling under aerobic conditions, which has been used for the intramolecular NH−NH coupling of phenoxazine dimer [17] and azaanthracene dimers [18] . In the presence of 5 equivalents of potassium tert ‐butoxide in air, a solution of 5 a in THF was stirred for 36 h. After separation, orange solids of 6 a were obtained (13 % yield) along with white solids of 9 (38 % yield).…”

Section: Resultsmentioning

confidence: 99%

Dibenzodiazapyracylenes: Doubly N‐Doped Cyclopenta‐Fused Polycyclic Molecules That Exhibit High Carrier Mobility

et al. 2022

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Pyracylene is a unique cyclopenta-fused polycyclic aromatic hydrocarbon (CP-PAH) that exhibits dual aromatic characteristics. Herein we report the synthesis of doubly N-doped benzannulated pyracylenes, namely dibenzodiazapyracylenes, by oxidative NÀ N linking reaction of [2.2](2,5)pyrrolophane-type precursors. Dibenzodiazapyracylenes displayed well-ordered πstacked molecular packing in the solid state, which were feasible for effective hole-transporting along the stacking direction. High carrier mobility was estimated by microwave conductivity measurements as compared to dibenzoullazine. The high HOMO level of dibenzodiazapyracylene was verified by electrochemistry and its persistent radical cation species has been detected.

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Section: Resultsmentioning

confidence: 99%

Dibenzodiazapyracylenes: Doubly N‐Doped Cyclopenta‐Fused Polycyclic Molecules That Exhibit High Carrier Mobility

et al. 2022

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“…Herein, we report the synthesis, structural analysis, and electronic properties of O,C,C-bridged triarylamines 5 and 6 and their persistent radical cations. The radical cations 5 •+ and 6 •+ are sufficiently stable to be isolated in crystalline form due to the embedded phenoxazine (PXZ) moiety, as PXZ is known to be an electron donor that is as good as phenothiazine (PTZ). − The remarkable stability of 5 •+ and 6 •+ , together with that of 4 •+ , enabled us to study the relevant structure–property relationships via in-depth crystallographic and spectroscopic investigations. To the best of our knowledge, 6 •+ represents the first example of a structurally analyzed planar, bridged dinaphthylphenylamine radical cation.…”

Section: Introductionmentioning

confidence: 99%

S,C,C- and O,C,C-Bridged Triarylamines and Their Persistent Radical Cations

et al. 2021

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triarylamines were easily oxidized to afford the corresponding radical cations, which were obtained as hexachloroantimonate salts. X-ray crystallographic analyses showed almost planar structures for these O,C,C-bridged triarylamine radical cations, which represent new members of the family of planar triarylamine radical cations without substituents on the aryl rings. Detailed investigations of the electronic properties of the S,C,C-and O,C,C-bridged triarylamine radical cations demonstrated that the spin and positive charge are sufficiently delocalized over the planar triarylamine scaffolds. The results provide the following insights into the effects of the bridging unit (sulfur vs oxygen) and the dibenzo-annulation on the spin delocalization in the bridged triarylamine radical cations: (1) An effective decrease of the spin density on the nitrogen atom is observed for the sulfur bridge relative to the oxygen bridge; and (2) a moderate decrease of the spin density on the oxygen atom rather than the nitrogen atom is induced by the dibenzo-annulation.

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“…Interestingly, UV absorption and strong near-infrared absorption were observed at 368 and 768 nm, respectively, in the UV−vis-NIR spectrum of 4b (Figure 6). 17 The absorption at 368 nm is indicated as a intramolecular charge transfer and the absorption at 768 nm is mainly contributed by the transition from HOMO-4 to SOMO by TDDFT calculation (UB3LYP/6-311++G(d,p), CH 2 Cl 2 )(for the detail, see the Supporting Information).…”

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confidence: 99%