RESUMO
Although λ5-phosphinine derivatives are known as a promising class of blue fluorescent emitters, those photoluminescent quantum yield (PLQY) values have been reached up to 92 %, however, only a few examples have been explored as an emitter for blue organic light-emitting device (OLED), and the external quantum efficiency (EQE) has been below 2.4 % so far. In this study, we newly developed two types of blue λ5-phosphinine derivatives namely CN-COCF3 and CO2Me-CHO, and investigated the photophysical properties in the solid states. The photophysical analyses in solid state films suggested that the strong electron-accepting nature of these λ5-phosphinine derivatives caused the inferior PLQY values, and the exciplex formation with the host and neighboring materials should be avoided to improve the device efficiency. By choosing suitable host and neighboring materials with deep ionization potentials, we successfully realized efficient blue fluorescent OLEDs with EQE of over 4 % and CIE (0.14, 0.18). This is among the best in λ5-phosphinine-based blue OLEDs so far.
RESUMO
Organophosphorus heterocycles have long been acknowledged for their significant potential across diverse fields, including catalysis, material science, and drug development. Incorporating phosphorus functionalities into organic compounds offers a means to effectively tailor their medicinal properties, augment biological responses, and enhance selectivity and bioavailability. The distinctive physical and photoelectric characteristics of phosphorus-containing conjugated compounds have garnered considerable interest as promising materials for organic optoelectronics. These compounds find extensive utility in various applications such as light-emitting diodes, photovoltaic cells, phosphole-based fluorophores, and semiconductors.
RESUMO
A phosphinine-borane adduct of a Me3 Si-functionalized phosphinine and the Lewis acid B(C6 F5 )3 has been synthesized and characterized crystallographically for the first time. The reaction strongly depends on the nature of the substituents in the α-position of the phosphorus heterocycle. In contrast, the reaction of B2 H6 with various substituted phosphinines leads to an equilibrium between the starting materials and the phosphinine-borane adducts that is determined by the Lewis basicity of the phosphinine. The novel phosphinine borane adduct (6-B(C6 F5 )3 ) shows rapid and facile insertion and [4+2] cycloaddition reactivity towards phenylacetylene. A hitherto unknown dihydro-1-phosphabarrelene is formed with styrene. The reaction with an ester provides a new, facile and selective route to 1-R-phosphininium salts. These salts then undergo a [4+2] cycloaddition in the presence of Me3 Si-C≡CH and styrene to cleanly form unprecedented derivatives of 1-R-phosphabarrelenium salts.
RESUMO
Herein, we report a novel method for the synthesis of metallabenzenes by swapping the phosphorus atom in an aromatic phosphinine ring with transition metal fragments. The oxidation of a phosphine-phosphinine-phosphine pincer iridium complex by O2 triggered the replacement of the phosphorus atom of the phosphinine ring by an iridium fragment to afford iridabenzene. Dianionic rhodabenzene was also synthesized from a phosphinine rhodium complex by oxidation of the phosphorus atom, followed by subsequent reduction using metallic potassium. The aromaticity of the newly synthesized irida- and rhoda-benzenes was evaluated both experimentally and theoretically.
RESUMO
The synthesis and isolation of a phosphinine selenide was achieved for the first time by reacting red selenium with 2,6-bis(trimethylsilyl)phosphinine. The rather large coupling constant of 1 JP,Se =883â Hz is in line with a P-Se bond of high s-character. The σ-electron donating Me3 Si-substituents significantly increase the energy of the phosphorus lone pair and hence its basicity, making the heterocycle considerably more basic and nucleophilic than the unsubstituted phosphinine C5 H5 P, as confirmed by the calculated gas phase basicities. NBO calculations further reveal that the lone pairs of the selenium atom are stabilized through donor-acceptor interactions with antibonding orbitals of the aromatic ring. The novel phosphinine selenide shows a distinct reactivity towards hexafluoro-2-butyne, Au(I)Cl as well as i PrOH. Our results pave the way for new perspectives in the chemistry of phosphorus in low coordination.
RESUMO
The yet unknown 2-amino-substituted λ3 ,σ2 -phosphinines are phosphorus-containing aniline derivatives. Calculations show that the strong interaction of the π-donating NR2 â group with the aromatic system results in a high π-density at the phosphorus atom. We could now synthesize 2-N(CH3 )2 -functionalized phosphinines, starting from a 3-N(CH3 )2 -substituted 2-pyrone and (CH3 )3 Si-C≡P. Their reaction with CuBrâ S(CH3 )2 affords CuI â complexes with the first example of a neutral phosphinine acting as a rare bridging µ2 -P-4e donor-ligand between two CuI â centers. Our experimental and theoretical investigations show that 2-aminophosphinines are missing links in the series of known 2-donor-functionalized phosphinines.
RESUMO
Salt metathesis of 1-methyl-2,4,6-triphenylphosphacyclohexadienyl lithium and chlorobis(pentafluorophenyl)borane affords a 1-phospha-7-bora-norbornadiene derivative 2. The C≡N triple bonds of nitriles insert into the P-B bond of 2 with concomitant C-B bond cleavage, whereas the C≡C bonds of phenylacetylenes react with 2 to form λ4 -phosphabarrelenes. Even though 2 must formally be regarded as a classical Lewis adduct, the C≡N and C≡C activation processes observed (and the mild conditions under which they occur) are reminiscent of the reactivity of frustrated Lewis pairs. Indeed, NMR and computational studies give insight into the mechanism of the reactions and reveal the labile nature of the phosphorus-boron bond in 2, which is also suggested by detailed NMR spectroscopic studies on this compound. Nitrile insertion is thus preceded by ring opening of the bicycle of 2 through P-B bond splitting with a low energy barrier. By contrast, the reaction with alkynes involves formation of a reactive zwitterionic methylphosphininium borate intermediate, which readily undergoes alkyne 1,4-addition.
RESUMO
Structural modularity of polymer frameworks is a key advantage of covalent organic polymers, however, only C, N, O, Si, and S have found their way into their building blocks so far. Here, the toolbox available to polymer and materials chemists is expanded by one additional nonmetal, phosphorus. Starting with a building block that contains a λ5 -phosphinine (C5 P) moiety, a number of polymerization protocols are evaluated, finally obtaining a π-conjugated, covalent phosphinine-based framework (CPF-1) through Suzuki-Miyaura coupling. CPF-1 is a weakly porous polymer glass (72.4â m2 g-1 BET at 77â K) with green fluorescence (λmax =546â nm) and extremely high thermal stability. The polymer catalyzes hydrogen evolution from water under UV and visible light irradiation without the need for additional co-catalyst at a rate of 33.3â µmol h-1 g-1 . These results demonstrate for the first time the incorporation of the phosphinine motif into a complex polymer framework. Phosphinine-based frameworks show promising electronic and optical properties, which might spark future interest in their applications in light-emitting devices and heterogeneous catalysis.
RESUMO
New iron complexes [Cp*FeL]- (1-σ and 1-π, Cp*=C5 Me5 ) containing the chelating phosphinine ligand 2-(2'-pyridyl)-4,6-diphenylphosphinine (L) have been prepared, and found to undergo facile reaction with CO2 under ambient conditions. The outcome of this reaction depends on the coordination mode of the versatile ligand L. Interaction of CO2 with the isomer 1-π, in which L binds to Fe through the phosphinine moiety in an η5 fashion, leads to the formation of 3-π, in which CO2 has undergone electrophilic addition to the phosphinine group. In contrast, interaction with 1-σ-in which L acts as a σ-chelating [P,N] ligand-leads to product 3-σ in which one C=O bond has been completely broken. Such CO2 cleavage reactions are extremely rare for late 3d metals, and this represents the first such example mediated by a single Fe centre.