1440513-11-0Relevant articles and documents
Twist to Boost: Circumventing Quantum Yield and Dissymmetry Factor Trade-Off in Circularly Polarized Luminescence
Lee, Sumin,Lee, Yongmoon,Kim, Kyungmin,Heo, Seunga,Jeong, Dong Yeun,Kim, Sangsub,Cho, Jaeheung,Kim, Changsoon,You, Youngmin
, p. 7738 - 7752 (2021)
Circularly polarized luminescence (CPL) enables promising applications in asymmetric photonics. However, the performances of CPL molecules do not yet meet the requirements of these applications. The shortcoming originates from the trade-off in CPL between the photoluminescence quantum yield (PLQY) and the photoluminescence dissymmetry factor (gPL). In this study, we developed a molecular strategy to circumvent this trade-off. Our approach takes advantage of the strong propensity of [Pt(N^C^N)Cl], where the N^C^N ligand is 1-(2-oxazoline)-3-(2-pyridyl)phenylate, to form face-to-face stacks. We introduced chiral substituents, including (S)-methyl, (R)- and (S)-isopropyl, and (S)-indanyl groups, into the ligand framework. This asymmetric control induces torsional displacements that give homohelical stacks of the Pt(II) complexes. X-ray single-crystal structure analyses for the (S)-isopropyl Pt(II) complex reveal the formation of a homohelical dimer with a Pt···Pt distance of 3.48 ?, which is less than the sum of the van der Waals radii of Pt. This helical stack elicits the metal-metal-to-ligand charge-transfer (MMLCT) transition that exhibits strong chiroptical activity due to the electric transition moment making an acute angle to the magnetic transition moment. The PLQY and gPL values of the MMLCT phosphorescence emission of the (S)-isopropyl Pt(II) complex are 0.49 and 8.4 × 10-4, which are improved by factors of ca. 6 and 4, respectively, relative to the values of the unimolecular emission (PLQY, 0.078; gPL, 2.4 × 10-4). Our photophysical measurements for the systematically controlled Pt(II) complexes reveal that the CPL amplifications depend on the chiral substituent. Our investigations also indicate that excimers are not responsible for the enhanced chiroptical activity. To demonstrate the effectiveness of our approach, organic electroluminescence devices were fabricated. The MMLCT emission devices were found to exhibit simultaneous enhancements in the external quantum efficiency (EQE, 9.7%) and the electroluminescence dissymmetry factor (gEL, 1.2 × 10-4) over the unimolecular emission devices (EQE, 5.8%; gEL, 0.3 × 10-4). These results demonstrate the usefulness of using the chiroptically active MMLCT emission for achieving an amplified CPL.
NCN palladium pincer via transmercuration. Synthesis of [2-(2-oxazoliny)-6-(2-pyridyl)] phenylpalladium(II) chloride and its catalytic activity in Suzuki coupling
Li, Ping,Zhou, Hai-Feng,Liu, Fang,Hu, Zhao-Xia,Wang, Hong-Xing
, p. 78 - 81 (2013/07/19)
The unsymmetrical NCN ligand 1-(2-oxazolinyl)-3-(2-pyridyl)benzene 6 was synthesized starting from m-bromotoluene after a series of transformations. The reaction of 6 and mercury (II) acetate resulted in mercurial derivative 7 which was transformed into the corresponding NCN palladium pincer 8 via transmercuration. The ultraviolet spectra of 6-8 in acetonitrile were also studied. The structures of 6 and 8 were further confirmed by X-ray single crystal diffraction. The carbon-carbon cross coupling reactions between aryl halides and phenylboronic acid catalyzed by 8 were investigated. The results indicate that this palladium pincer is more highly active to the coupling of aryl bromides than aryl chlorides.
