General Synthetic Route to Chiral Flexible Biphenylphosphine Ligands: The Use of a Chiral Additive Enables the Preparation and Observation of Metal Complexes Incorporating the Enantiopure Form
enantio- and diastereomerically pure metal complex of a chirally flexible BIPHEP ligand is obtained through enantiomer-selective coordination of a BIPHEP-Ru complex with enantiopure 3,3'-dimethyldiaminobinaphthyl, DM-DBN, followed by epimerization of the remaining BIPHEP-Ru enantiomer to complex with DM-DABN. Thus, an efficient and generalsyntheticroute to a variety of substituted BIPHEP ligands from biphenol
The reaction between 2,2′-dilithiobiphenyl and two equivalents of chlorodiphenylphosphine is confirmed to afford equal amounts of 9-phenyl-9-phosphafluorene (2) and triphenylphosphine. 2,2′-Bis(diphenylphosphino)biphenyl (1,1′-biphenyl-2,2′-dilbis(diphenylphosphine) (1)) can be conveniently prepared by Ullmann coupling of 2-iodophenyldiphenylphosphine oxide and subsequent reduction with trichlorosilane
Near-infrared (NIR) luminescent Yb(III) complexes composed of low-vibrational frequency (LVF) fluorinated acetylacetonate and phosphine oxide ligands are reported. Their structures are determined using X-ray single-crystal analyses and categorized as eight-coordinated square antiprism. The radiative rate constants (kr), the nonradiative rate constants (knr), and the 4f–4f emission quantum efficiency (ΦEm) are estimated using their absorption spectra of magnetic dipole transition in Yb(III) complexes (2F5/2 → 2F7/2) and the observed emission lifetimes. Characteristic NIR luminescence properties of Yb(III) complexes with LVF phosphine oxide and fluorinated acetylacetonate ligands are elucidated in terms of the radiative and nonradiative rate constants.
The luminescent and lasing properties of Eu(III) complexes were enhanced by using an dissymmetric Eu(III) complex. The photophysical properties (the emission spectral shapes, the emission lifetimes, the emission quantum yields, and the stimulated emission cross section (SEC)) were found to be dependent on the geometrical structures of Eu(III) complexes. The geometrical structures of Eu(III) complexes
Eu(III)配合物的发光和激光发射性能通过使用不对称Eu(III)配合物得到增强。发现光物理性质(发射光谱形状,发射寿命,发射量子产率和受激发射截面(SEC))取决于Eu(III)配合物的几何结构。Eu(III)配合物的几何结构通过X射线单晶分析确定。发现Eu(hfa)3(BIPHEPO)的对称基团(三(六氟乙酰丙酮))(III)1,1'-联苯-2,2'-二基双(二苯基膦氧化物))比C1更不对称Eu(hfa)3(TPPO)2(三(六氟乙酰丙酮化)eur(III)1,2-亚苯基双(二苯基膦氧化物):C2对称)和Eu(hfa)3(OPPO)2(三(六氟乙酰丙酮化)eur(III) 1,2-亚苯基双(二苯基氧化膦):C2对称)。分析数据得到Judd-Ofelt分析的支持。最不对称的Eu(III)络合物Eu(hfa)3(BIPHEPO)显示出大的电子跃迁几率和SEC(4.64 x 10(-20)