Ahmed Zubair, Iftikhar Khalid
Lanthanide Research Laboratory, Department of Chemistry, Jamia Millia Islamia University, New Delhi 110 025, India.
Dalton Trans. 2019 Apr 9;48(15):4973-4986. doi: 10.1039/c9dt00198k.
This paper presents three crystallographically and solution NMR (one- and two-dimensional) characterised ternary Ln(iii) complexes, and their photo-physical and opto-electronic properties in the visible and NIR regions. The single crystal X-ray diffraction analysis indicates that the complexes are nona-coordinate with a chemical composition of [Ln(hfaa)3(Hind)3] (hfaa = anion of hexafluoroacetylacetone, Hind = indazole and Ln = Pr, Nd and Sm). The Ln ions, in the complexes, are coordinated to six O-atoms of three hfaa and three N-atoms of three monodentate Hind ligands, making the coordination polyhedra LnO6N3 with distorted monocapped square antiprismatic geometries, low symmetry structures that promote radiative transitions, suggesting efficient energy transfer from the organic ligands to the metal ion. The NMR analysis confirms the nona-coordinate structures and shows the isostructurality of the complexes in solution. The excitation of the complexes at 310 nm led to the characteristic of both visible and near infrared luminescence of the Pr, Nd and Sm complexes. The samarium complex displayed very strong orange-red luminescence. In contrast to the solution, the PMMA doped samples of the complexes showed an enhancement in the emission lifetime and the quantum yield. A triple layered NIR-emitting OLED, fabricated using the Nd-complex as an emitting layer, showed good optical and electrical performances.
本文介绍了三种通过晶体学和溶液核磁共振(一维和二维)表征的三元Ln(iii)配合物,以及它们在可见光和近红外区域的光物理和光电性质。单晶X射线衍射分析表明,这些配合物为九配位,化学组成为[Ln(hfaa)3(Hind)3](hfaa = 六氟乙酰丙酮阴离子,Hind = 吲唑,Ln = Pr、Nd和Sm)。配合物中的Ln离子与三个hfaa的六个O原子和三个单齿Hind配体的三个N原子配位,形成配位多面体LnO6N3,具有扭曲的单帽四方反棱柱几何形状,这种低对称结构促进辐射跃迁,表明从有机配体到金属离子的有效能量转移。核磁共振分析证实了九配位结构,并表明配合物在溶液中的同构性。配合物在310 nm处的激发导致Pr、Nd和Sm配合物的可见光和近红外发光特性。钐配合物表现出非常强的橙红色发光。与溶液相比,配合物的PMMA掺杂样品的发射寿命和量子产率有所提高。使用Nd配合物作为发光层制备的三层近红外发光OLED表现出良好的光学和电学性能。