Fused Cycloalkyl Unit-Functionalized Tetradentate Pt(II) Complexes for Efficient and Narrow-Emitting Deep Blue Organic Light-Emitting Diodes.

A blue tetradentate Pt(II) complex named Pt-tmCyCz is developed by introducing a cycloalkyl unit fused to carbazole to improve the rigidity and bulkiness of the complex. The introduction of the tetramethylcyclohexyl (tmCy) group results in a narrow full width at half maximum (FWHM), a high horizontal emitting dipole orientation, doping concentration resistant stable spectrum, and extremely small efficiency roll-off, and little concentration quenching effect. Phosphorescent organic light-emitting diodes (OLEDs) doped with Pt-tmCyCz achieve a high external quantum efficiency (EQE) of 21.5%, with a small EQE roll-off of 3.8% up to 1000 cd m-2 , a small FWHM of 24 nm, and a color coordinate of (0.132, 0.138). Moreover, Pt-tmCyCz is investigated as a sensitizer in phosphor-sensitized OLEDs using N7 ,N7 ,N13 ,N13 ,5,9,11,15-octaphenyl-5,9,11,15-tetrahydro-5,9,11,15-tetraaza-19b,20b-diboradinaphtho[3,2,1-de:1',2',3'-jk]pentacene-7,13-diamine (νDABNA) as a terminal emitter. The Pt-tmCyCz:νDABNA device achieves a high EQE of 33.9%, with a small EQE roll-off of only 8.0% up to 1 000 cd m-2 . The results demonstrate that fused tmCy group in carbazole can be an effective building block for the development of high-performance Pt(II) complexes, which can be utilized as efficient phosphors or sensitizers in OLEDs.

Lifetime-Extending 3-(4-Phenylbenzo[4,5]thieno[3,2-d]pyrimidin-2-yl)benzonitrile Acceptor for Thermally Activated Delayed Fluorescence Emitters.

Highly efficient and long-living green thermally activated delayed fluorescence (TADF) organic light-emitting diodes (OLEDs) were developed using benzothienopyrimidine-4-benzonitrile acceptor-derived compounds as the TADF emitters. A molecular design merging the benzothienopyrimidine-4-benzonitrile acceptor with either indolocarbazole or diindolocarbazole was employed to prepare two TADF emitters, 5-(2-phenylbenzo[4,5]thieno[3,2-d]pyrimidin-4-yl)-2-(5-phenylindolo[3,2-a]carbazol-12(5H)-yl)benzonitrile and 2-(10,15-diphenyl-10,15-dihydro-5H-diindolo[3,2-a:3',2'-c]carbazol-5-yl)-5-(2-phenylbenzo[4,5]thieno[3,2-d]pyrimidin-4-yl)benzonitrile (BTPDIDCz), as the green and greenish-yellow emitters. Among the two emitters, BTPDIDCz with the diindolocarbazole donor combined with the benzothienopyrimidine-4-benzonitrile acceptor demonstrated a high external quantum efficiency of 24.5% and 3 times longer device lifetime than the state-of-the-art green emitter. This work proposed the potential of benzothienopyrimidine-4-benzonitrile as the acceptor for long lifetime in TADF emitters.

Practical one-pot amidation of N-Alloc-, N-Boc-, and N-Cbz protected amines under mild conditions.

A facile one-pot synthesis of amides from N-Alloc-, N-Boc-, and N-Cbz-protected amines has been described. The reactions involve the use of isocyanate intermediates, which are generated in situ in the presence of 2-chloropyridine and trifluoromethanesulfonyl anhydride, to react with Grignard reagents to produce the corresponding amides. Using this reaction protocol, a variety of N-Alloc-, N-Boc-, and N-Cbz-protected aliphatic amines and aryl amines were efficiently converted to amides with high yields. This method is highly effective for the synthesis of amides and offers a promising approach for facile amidation.

Recent Advances in One-Pot Modular Synthesis of 2-Quinolones.

It is known that 2-quinolones are broadly applicable chemical structures in medicinal and agrochemical research as well as various functional materials. A number of current publications about their synthesis and their applications emphasize the importance of these small molecules. The early synthetic chemistry originated from the same principle of the classical Friedländer and Knorr procedures for the preparation of quinolines. The analogous processes were developed by applying new synthetic tools such as novel catalysts, the microwave irradiation method, etc., whereas recent innovations in new bond forming reactions have allowed for novel strategies to construct the core structures of 2-quinolones beyond the bond disconnections based on two classical reactions. Over the last few decades, some reviews on structure-based, catalyst-based, and bioactivity-based studies have been released. In this focused review, we extensively surveyed recent examples of one-pot reactions, particularly in view of modular approaches. Thus, the contents are categorized as three major sections (two-, three-, and four-component reactions) according to the number of reagents that ultimately compose atoms of the core structures of 2-quinolones. The collected synthetic methods are discussed from the perspectives of strategy, efficiency, selectivity, and reaction mechanism.

Design Strategy of Decorating Phenylcarbazole with a Donor and Acceptor for Blue-Shifted Emission in Thermally Activated Delayed Fluorescent Emitters.

A series of blue thermally activated delayed fluorescent (TADF) emitters of 1''-(4,6-diphenyl-1,3,5-triazin-2-yl)-9,9''-diphenyl-9H,9''H-3,3':9',4''-tercarbazole (TrzCz1) and 3',6'-di-tert-butyl-1-(4,6-diphenyl-1,3,5-triazin-2-yl)-9-phenyl-9H-4,9'-bicarbazole (TrzCz2) were synthesized through a molecular design approach to decorate phenylcarbazole with a donor and an acceptor. The 1- and 4-positions of the phenylcarbazole core were modified with a diphenyltriazine acceptor and a bicarbazole or tert-butylcarbazole donor, respectively, through a synthetic strategy to introduce Br at the 1-position and F at the 4-position. The TrzCz1 and TrzCz2 emitters showed maximum photoluminescence emission bands at λ=443 and 433 nm, which were blueshifted relative to those of the corresponding TADF emitters with the same donor and acceptor, respectively. In the device application, the TrzCz1 emitter showed a maximum external quantum efficiency of 22.4 %, with a color coordinate of (0.16, 0.21), and the TrzCz2 emitter showed a maximum external quantum efficiency of 9.9 %, with a color coordinate of (0.14, 0.09). This work proved that the design strategy of decorating phenylcarbazole with a donor and an acceptor is effective at blueshifting the emission of TADF emitters.

Triggering Thermally Activated Delayed Fluorescence by Managing the Heteroatom in Donor Scaffolds: Intriguing Photophysical and Electroluminescence Properties.

Establishment of the structure-property relationships of thermally activated delayed fluorescence (TADF) materials has become a significant quest for the scientific community. Herein, two new donors, 10H-benzofuro[3,2-b]indole (BFI) and 10H-benzo[4,5]thieno[3,2-b]indole (BTI), have been developed and integrated with a aryltriazine acceptor to design the green TADF emitters benzofuro[3,2-b]indol-10-yl)-5-(4,6-diphenyl-1,3,5-triazin-2-yl)benzonitrile (BFICNTrz) and 2-(10H-benzo[4,5]thieno[3,2-b]indol-10-yl)-5-(4,6-diphenyl-1,3,5-triazin-2-yl)benzonitrile (BTICNTrz), respectively. The physicochemical and electroluminescence properties of the compounds were tuned by exchanging the heteroatom in the donor scaffold. Intriguingly, the electronegativity of the heteroatom and the ionization potential of the donor unit played vital roles in control of the singlet-triplet energy splitting and TADF mechanism of the compounds. Both compounds showed similar singlet excited states that originated from the charge transfer (CT) states (1 CT), whereas the triplet excited states were tuned by the heteroatom in the donor unit. The origin of phosphorescence in the BTICNTrz emitter was CT emission from the triplet state (3 CT), whereas that in the BFICNTrz emitter stemmed from the local triplet excited state (3 LE). Consequently, BTICNTrz showed a small singlet-triplet energy splitting of 0.08 eV, compared with 0.26 eV for BFICNTrz. Thus, BTICNTrz showed efficient delayed fluorescence with a high quantum yield and a short delayed exciton lifetime, whereas BFICNTrz displayed weak delayed fluorescence with a relatively long lifetime. Furthermore, a BTICNTrz-based device exhibited a maximum external quantum efficiency (EQE) of 15.2 % and reduced efficiency roll-off (12 %) compared with its BFICNTrz-based counterpart, which showed a maximum EQE of 6.4 % and severe efficiency roll-off (55 %) at a practical brightness range of 1000 cd m-2 . These results demonstrate that the choice of subunit plays a vital role in the design of efficient TADF emitters.

Pd-catalyzed Semmler-Wolff reactions for the conversion of substituted cyclohexenone oximes to primary anilines.

Homogeneous Pd catalysts have been identified for the conversion of cyclohexenone and tetralone O-pivaloyl oximes to the corresponding primary anilines and 1-aminonaphthalenes. This method is inspired by the Semmler-Wolff reaction, a classic method that exhibits limited synthetic utility owing to its forcing conditions, narrow scope, and low product yields. The oxime N-O bond undergoes oxidative addition to Pd(0)(PCy3)2, and the product of this step has been characterized by X-ray crystallography and shown to undergo dehydrogenation to afford the aniline product.

Synthesis of the C1-C20 and C15-C27 segments of aplyronine A.

The synthesis of C1-C20 and C15-C27 segments of Aplyronine A is described. Oxidative cleavage of cyclic vinyl sulfones has been used to prepare key fragments of Aplyronine A. Key precursors are united by Horner-Wadsworth-Emmons and Julia-Kociensky olefination for the respective elaboration of the C1-C20 and C15-C27 segments.

Reagent-directed allylic quadraselection. Chemoselective anti- and syn-Lawton S(N)2' methylation of seven-membered epoxyvinylsulfones.

Methods have been developed for regio- and stereoselective 1,4-syn or 1,4-anti methylation of seven-membered epoxyvinylsulfones. 1,4-Syn addition is achieved via the combination of Me(2)Zn and catalytic Li(2)CuCl(4), a hitherto unexplored reagent combination. The complementary 1,4-anti addition relies on Cu(I) catalyzed methyl Grignard addition or (CH(3))(3)Al assisted CH(3)Cu addition. The methods described were assayed on four diastereomeric stereodiads and on their parent epoxide.

A cell number-counting factor regulates levels of a novel protein, SslA, as part of a group size regulation mechanism in Dictyostelium.

Developing Dictyostelium cells form aggregation streams that break into groups of approximately 2 x 10(4) cells. The breakup and subsequent group size are regulated by a secreted multisubunit counting factor (CF). To elucidate how CF regulates group size, we isolated second-site suppressors of smlA(-), a transformant that forms small groups due to oversecretion of CF. smlA(-) sslA1(CR11) cells form roughly wild-type-size groups due to an insertion in the beginning of the coding region of sslA1, one of two highly similar genes encoding a novel protein. The insertion increases levels of SslA. In wild-type cells, the sslA1(CR11) mutation forms abnormally large groups. Reducing SslA levels by antisense causes the formation of smaller groups. The sslA(CR11) mutation does not affect the extracellular accumulation of CF activity or the CF components countin and CF50, suggesting that SslA does not regulate CF secretion. However, CF represses levels of SslA. Wild-type cells starved in the presence of smlA(-) cells, recombinant countin, or recombinant CF50 form smaller groups, whereas sslA1(CR11) cells appear to be insensitive to the presence of smlA(-) cells, countin, or CF50, suggesting that the sslA1(CR11) insertion affects CF signal transduction. We previously found that CF reduces intracellular glucose levels. sslA(CR11) does not significantly affect glucose levels, while glucose increases SslA levels. Together, the data suggest that SslA is a novel protein involved in part of a signal transduction pathway regulating group size.

Disruption of aldehyde reductase increases group size in dictyostelium.

Developing Dictyostelium cells form structures containing approximately 20,000 cells. The size regulation mechanism involves a secreted counting factor (CF) repressing cytosolic glucose levels. Glucose or a glucose metabolite affects cell-cell adhesion and motility; these in turn affect whether a group stays together, loses cells, or even breaks up. NADPH-coupled aldehyde reductase reduces a wide variety of aldehydes to the corresponding alcohols, including converting glucose to sorbitol. The levels of this enzyme previously appeared to be regulated by CF. We find that disrupting alrA, the gene encoding aldehyde reductase, results in the loss of alrA mRNA and AlrA protein and a decrease in the ability of cell lysates to reduce both glyceraldehyde and glucose in an NADPH-coupled reaction. Counterintuitively, alrA- cells grow normally and have decreased glucose levels compared with parental cells. The alrA- cells form long unbroken streams and huge groups. Expression of AlrA in alrA- cells causes cells to form normal fruiting bodies, indicating that AlrA affects group size. alrA- cells have normal adhesion but a reduced motility, and computer simulations suggest that this could indeed result in the formation of large groups. alrA- cells secrete low levels of countin and CF50, two components of CF, and this could partially account for why alrA- cells form large groups. alrA- cells are responsive to CF and are partially responsive to recombinant countin and CF50, suggesting that disrupting alrA inhibits but does not completely block the CF signal transduction pathway. Gas chromatography/mass spectroscopy indicates that the concentrations of several metabolites are altered in alrA- cells, suggesting that the Dictyostelium aldehyde reductase affects several metabolic pathways in addition to converting glucose to sorbitol. Together, our data suggest that disrupting alrA affects CF secretion, causes many effects on cellular metabolism, and has a major effect on group size.