Control of the dual emission from a thermally activated delayed fluorescence emitter containing phenothiazine units in organic light-emitting diodes.

The development of single-component organic dual light-emitting molecules is of interest for a range of applications including white organic light-emitting diodes. Herein, a new thermally-activated delayed fluorescent molecule containing 4,6-bis-phenyl phenothiazine as donor units and 2-thiophene-1,3,5-triazine as acceptor unit was synthesized using a simple cost-effective method. This compound shows two stable molecular conformations due to the presence of the phenothiazine units in its molecular structure. These conformers exhibit different photophysical properties in both solution and thin films. The electroluminescence properties of this novel emitter were then examined in organic light-emitting diodes and the results provide useful insights into the influence of the device architecture on the dual emission characteristics. The experimental results were consistent with the optical simulations and the optimized architecture led to the fabrication of electroluminescent devices with an external quantum efficiency of 11.5% and a maximum luminance value of 10 370 cd m-2.

Synthesis of Complex Druglike Molecules by the Use of Highly Functionalized Bench-Stable Organozinc Reagents.

The reactivity of a representative set of 17 organozinc pivalates with 18 polyfunctional druglike electrophiles (informers) in Negishi cross-coupling reactions was evaluated by high-throughput experimentation protocols. The high-fidelity scaleup of successful reactions in parallel enabled the isolation of sufficient material for biological testing, thus demonstrating the high value of these new solid zinc reagents in a drug-discovery setting and potentially for many other applications in chemistry. Principal component analysis (PCA) clearly defined the independent roles of the zincates and the informers toward druggable-space coverage.

Characterization of the ultraviolet-visible photoproducts of thiophanate-methyl using high performance liquid chromatography coupled with high resolution tandem mass spectrometry-Detection in grapes and tomatoes.

UV-visible irradiation of thiophanate-methyl (TM) led to the formation of nine photoproducts that were characterized by high performance liquid chromatography coupled with high resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). Although carbendazime has been reported in the literature to be the major metabolite and photoproduct of thiophanate-methyl, it was not detected in this study. However, an isomer of carbendazime referred as PP2, which was unambiguously characterized owing to CID experiments, was found in great abundance. Grape berries and cherry tomatoes treated with aqueous solutions of thiophanate-methyl were submitted to irradiation under laboratory conditions. TM and PP2 were detected in both peel and flesh of berries. The ability of TM and PP2 to pass through the fruit skin has been shown to be highly compound and matrix dependent. In vitro bioassays on Vibrio fischeri bacteria showed that the global ecotoxicity of the TM solution increases significantly with the irradiation time. PP2 should likely contribute to this ecotoxicity enhancement since in silico estimations for Daphnia magna provide a LC50 value seven times lower for PP2 than for the parent molecule.

Air-stable solid aryl and heteroaryl organozinc pivalates: syntheses and applications in organic synthesis.

A wide range of air-stable, solid, polyfunctional aryl and heteroarylzinc pivalates were efficiently prepared by either magnesium insertion or Hal/Mg exchange followed by transmetalation with Zn(OPiv)2 (OPiv = pivalate). By reducing the amount of LiCl the air stability could be significantly enhanced compared with previously prepared reagents. An alternative route is directed magnesiation using TMPMgCl⋅LiCl (TMP = 2,2,6,6-tetramethylpiperidyl) followed by transmetalation with Zn(OPiv)2 or, for very sensitive substrates, direct zincation by using TMPZnOPiv. These zinc reagents not only show excellent stability towards air, but they also undergo a broad range of C-C bond-formation reactions, such as allylation and carbocupration reactions, as well as addition to aldehydes and 1,4-addition reactions. Acylation reactions can be performed by using an excess of TMSCl to overcome side reactions of the omnipresent pivalate anion.

Organozinc pivalate reagents: segregation, solubility, stabilization, and structural insights.

The pivalates RZnOPiv⋅Mg(OPiv)X⋅n LiCl (OPiv=pivalate; R=aryl; X=Cl, Br, I) stand out amongst salt-supported organometallic reagents, because apart from their effectiveness in Negishi cross-coupling reactions, they show more resistance to attack by moist air than conventional organometallic compounds. Herein a combination of synthesis, coupling applications, X-ray crystallographic studies, NMR (including DOSY) studies, and ESI mass spectrometric studies provide details of these pivalate reagents in their own right. A p-tolyl case system shows that in [D8]THF solution these reagents exist as separated Me(p-C6H4)ZnCl and Mg(OPiv)2 species. Air exposure tests and X-ray crystallographic studies indicate that Mg(OPiv)2 enhances the air stability of aryl zinc species by sequestering H2O contaminants. Coupling reactions of Me(p-C6H4)ZnX (where X=different salts) with 4-bromoanisole highlight the importance of the presence of Mg(OPiv)2. Insight into the role of LiCl in these multicomponent mixtures is provided by the molecular structure of [(THF)2Li2(Cl)2(OPiv)2Zn].

TMPZnOPiv•LiCl: a new base for the preparation of air-stable solid zinc pivalates of sensitive aromatics and heteroaromatics.

A wide range of aryl and heteroaryl zinc pivalates bearing sensitive functionalities were prepared by selective metalation using TMPZnOPiv•LiCl, a new hindered zinc amide base. The new zinc reagents are easy-to-handle solids, which maintain their activity almost entirely (>95%) after 4 h of air exposure and smoothly undergo Negishi cross-couplings and reactions with various electrophiles such as Cu(I)-catalyzed acylations and allylations.

Metalated N-heterocyclic reagents prepared by the frustrated Lewis pair TMPMgCl·BF3 and their addition to aromatic aldehydes and activated ketones.

Treatment of pyridines, quinoline and methylthiopyrazine with the frustrated Lewis pair TMPMgCl·BF(3) (1) leads to organotrifluoro borates which react readily with a variety of aromatic aldehydes in the absence of a transition metal catalyst.

Selective C-H activations using frustrated Lewis pairs. Applications in organic synthesis.

Frustrated Lewis pairs (FLPs), sterically encumbered Lewis acid and base combinations, gained importance due to their ability to activate molecular hydrogen. This property is used in organic synthesis to perform metal-free catalytic hydrogenation of imines, quinolines, or enamines. Moreover, it is possible to perform selective C-H activations using different sterically hindered Lewis acid/base pairs. Thus, the combination of organometallic reagents with different boranes can be used to functionalize selectively a variety of tertiary amines. By combination of sterically hindered metal amides of the type TMP-Met (TMP = 2,2,6,6-tetramethylpiperidyl, Met = Li, MgCl, ZnCl) with the Lewis-acid BF3·OEt2 it is possible to metalate selectively a large number of aromatic N-heterocycles, such as pyridines and quinolines.

Selective and multiple functionalization of pyridines and alkaloids via Mg- and Zn-organometallic intermediates.

Quinine, nicotine, and related electron-rich amino-substituted pyridines were readily metalated using LiCl-solubilized TMP (2,2,6,6-tetramethylpiperidyl) bases in the presence of BF(3)·OEt(2). A full pyridine functionalization of all five positions of the pyridine ring can be realized by using an appropriate combination of TMP bases in the presence or absence of BF(3)·OEt(2).