151131-87-2Relevant articles and documents
Nonsymmetrical Bis-Azine Biaryls from Chloroazines: A Strategy Using Phosphorus Ligand-Coupling
Boyle, Benjamin T.,Hilton, Michael C.,McNally, Andrew
supporting information, p. 15441 - 15449 (2019/11/02)
Distinct approaches to synthesize bis-azine biaryls are in demand as these compounds have multiple applications in the chemical sciences and are challenging targets for metal-catalyzed cross-coupling reactions. Most approaches focus on developing new reagents as the formal nucleophilic coupling partner that can function in metal-catalyzed processes. We present an alternative approach using pyridine and diazine phosphines as nucleophilic partners and chloroazines where the heterobiaryl bond is formed via a tandem SNAr-phosphorus ligand-coupling sequence. The heteroaryl phosphines are prepared from chloroazines and are bench-stable solids. A range of bis-azine biaryls can be formed from abundant chloroazines using this strategy that would be challenging using traditional approaches. A one-pot cross-electrophile coupling of two chloroazines is feasible, and we also compared the phosphorus-mediated strategy with metal-catalyzed coupling reactions to show advantages and compatibility.
Synthesis, structure, and characterization of dinuclear copper(I) halide complexes with P^N ligands featuring exciting photoluminescence properties
Zink, Daniel M.,B?chle, Michael,Baumann, Thomas,Nieger, Martin,Kühn, Michael,Wang, Cong,Klopper, Wim,Monkowius, Uwe,Hofbeck, Thomas,Yersin, Hartmut,Br?se, Stefan
, p. 2292 - 2305 (2013/04/10)
A series of highly luminescent dinuclear copper(I) complexes has been synthesized in good yields using a modular ligand system of easily accessible diphenylphosphinopyridine-type P^N ligands. Characterization of these complexes via X-ray crystallographic studies and elemental analysis revealed a dinuclear complex structure with a butterfly-shaped metal-halide core. The complexes feature emission covering the visible spectrum from blue to red together with high quantum yields up to 96%. Density functional theory calculations show that the HOMO consists mainly of orbitals of both the metal core and the bridging halides, while the LUMO resides dominantly on the heterocyclic part of the P^N ligands. Therefore, modification of the heterocyclic moiety of the bridging ligand allows for systematic tuning of the luminescence wavelength. By increasing the aromatic system of the N-heterocycle or through functionalization of the pyridyl moiety, complexes with emission maxima from 481 to 713 nm are obtained. For a representative compound, it is shown that the ambient-temperature emission can be assigned as a thermally activated delayed fluorescence, featuring an attractively short emission decay time of only 6.5 μs at φPL = 0.8. It is proposed to apply these compounds for singlet harvesting in OLEDs.
