No abstract

Finding narrow-band, ultrapure blue thermally activated delayed fluorescence (TADF) materials is extremely important for developing highly efficient organic light-emitting diodes (OLEDs). Here, spin-vibronic coupling (SVC)-assisted ultrapure blue emitters obtained by joining two carbazole-derived moieties at a para position of a phenyl unit and performing substitutions using several blocking groups are presented. Despite a relatively large singlet-triplet gap (∆E ST ) of >0.2 eV, efficient triplet-to-singlet crossover can be realized, with assistance from resonant SVC. To enhance the spin crossover, electronic energy levels are fine-tuned, thereby causing ∆E ST to be in resonance with a triplet-triplet gap (∆E TT ). A sizable population transfer between spin multiplicities (>10 3 s −1 ) is achieved, and this result agrees well with theoretical predictions. An OLED fabricated using a multiple-resonance-type SVC-TADF emitter with CIE color coordinates of (0.15, 0.05) exhibits ultrapure blue emissions, with a narrow full-width-at-half-maximum of 21 nm and a high external quantum efficiency of 23.1%.

A novel violet emitter, 1,3-bis [10,10-dimethyl-10H-indeno[2,1-b]]indolo[3,2,1jk]indolo[1′,2′,3′:1,7]indolo[3,2-b]carbazole (m-FLDID), was designed and synthesized by meta-oriented bis-fusion of two 7,7-dimethyl-5,7-dihydroindeno[2,1-b]carbazole (DMID) subunits for use in a pure violet organic light-emitting diode (OLED). Incorporation of the DMID subunits effectively reduced the nonradiative recombination rate, improving the photoluminescence quantum yield of the m-FLDID emitter. The meta-oriented bis-fusion of the two DMID subunits not only triggered an alternative distribution of the frontier orbitals but also effectively locked the π-conjugation chain, which ultimately resulted in a narrow-band, pure violet emission of the m-FLDID emitter. Doped m-FLDID devices possessed an external quantum efficiency (EQE) of > 5%, pure violet emission with a maximum at 407 nm, a narrow full width at half-maximum of 17 nm, and a Commission Internationale de l'ećlairage y coordinate of less than 0.03. This is the first work reporting an EQE of > 5% and an extremely narrow emission spectrum for a pure violet emitter.

An efficient, rapid oxidation of various aliphatic amines to oximes using m-CPBA as an oxidant in ethyl acetate is described. High conversion (100%) with >90% oxime selectivity is achieved at room temperature under catalyst-free conditions. Mild reaction conditions along with an easy work up procedure offer lower byproduct formation and high selectivity for oximes in good yield and purity.

Unusual regio- and chemoselective oxidation of aromatic amines hindered with ortho substituents (except -NH2, -NHCH3, and -OH) to the corresponding nitro compounds is described by use of nonanebis(peroxoic acid). The mechanistic investigation for selective oxidation of amines ortho-substituted with -NH2 or -OH showed the involvement of H-bonding between the ortho hydrogen of the adjacent -XH group (where X = NH, NR, or O) and an oxygen atom from the diperoxy acid. Various mono- and diamines are oxidized into corresponding mononitro derivatives in high yield and purity without employing any protection strategies. The protocol was also found to successful on the gram scale.

No abstract

SummaryA new protocol for the oxidative bromination of aminoanthracene-9,10-dione, which is highly deactivated towards the electrophilic substitution is investigated. The peracid, nonanebis(peroxoic acid), possesses advantages such as better stability at room temperature, it is easy to prepare and non-shock sensitiv as compared to the conventional peracids. The present protocol has a broad scope for the bromination of various substituted and unsubstituted aminoanthracene-9,10-diones.

Scheme 1. Synthetic pathway for the ATDBF.