Abstract The nine-coordinate complexes of tris(dibenzoylmetanato)La(III) and Sm(III) with tptz were synthesized and thoroughly characterized. The 1H NMR spectrum of [La(dbm)3(tptz)]∙CH3CN is consistent with the coordination of three dbm and one tptz. The tricapped trigonal prism geometry of [Sm(dbm)3(tptz)]∙CH3CN complex is revealed by single crystal X-ray diffraction analysis. The shape 2.1v analysis authenticates the tricapped trigonal prism geometry of [Sm(dbm)3(tptz)]∙CH3CN complex. The Sm(III) is coordinatively saturated by the coordination of six oxygen atoms from dbm units and two pyridyl and one triazine nitrogen atoms from tptz moiety. The steady-state and time resolved photoluminescence of the solid [Sm(dbm)3(tptz)]∙CH3CN and its PMMA hybrid films of different concentration are investigated and discussed. The complex has only one emitting center since the decay times are fitted by mono-exponential function. The higher PL intensity of 4G5/2 → 6H7/2 (ΔJ = 1, magnetic-dipole transition) transition compared to 4G5/2 → 6H9/2 (ΔJ = 2, electric-dipole transition), in the case of 3% (w/w) PMMA hybrid film is the result of strong vibrionic coupling. Although the PL intensity of two transition are different even then the decay times of the transition are roughly similar in magnitude. The stark splitting of electric-dipole 4G5/2 → 6H9/2 transition in the spectrum of 3% film is interesting and leads to believe a strong coupling between states of f-electrons and electric fields of the surrounding ligands.

中文翻译：

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来自高度不对称的九坐标三端三棱柱 Sm(III) 配合物的发光

摘要 合成并充分表征了三(二苯甲酰基间基)La(III)和Sm(III)与tptz的九配位配合物。[La(dbm)3(tptz)]∙CH3CN的1H NMR谱与3个dbm和1个tptz的配位一致。通过单晶X射线衍射分析揭示了[Sm(dbm)3(tptz)]∙CH3CN配合物的三棱柱几何结构。形状 2.1v 分析验证了 [Sm(dbm)3(tptz)]∙CH3CN 复合物的三棱柱几何形状。Sm(III) 被来自 dbm 单元的六个氧原子和来自 tptz 部分的两个吡啶基和一个三嗪氮原子配位而配位饱和。研究和讨论了固体 [Sm(dbm)3(tptz)]∙CH3CN 及其不同浓度 PMMA 混合薄膜的稳态和时间分辨光致发光。由于衰减时间由单指数函数拟合，因此该复合体只有一个发射中心。4G5/2 → 6H7/2（ΔJ = 1，磁偶极跃迁）跃迁的 PL 强度高于 4G5/2 → 6H9/2（ΔJ = 2，电偶极跃迁），在 3% 的情况下（ w/w) PMMA 混合膜是强振动耦合的结果。尽管两个跃迁的 PL 强度不同，但跃迁的衰减时间在幅度上大致相似。3% 薄膜光谱中电偶极子 4G5/2 → 6H9/2 跃迁的明显分裂是有趣的，并导致人们相信 f 电子的状态与周围配体的电场之间存在强耦合。磁偶极跃迁）跃迁与 4G5/2 → 6H9/2（ΔJ = 2，电偶极跃迁）相比，在 3% (w/w) PMMA 混合膜的情况下，是强振动耦合的结果。尽管两个跃迁的 PL 强度不同，但跃迁的衰减时间在幅度上大致相似。在 3% 薄膜的光谱中电偶极子 4G5/2 → 6H9/2 跃迁的明显分裂很有趣，并导致人们相信 f 电子的状态与周围配体的电场之间存在强耦合。磁偶极跃迁）跃迁与 4G5/2 → 6H9/2（ΔJ = 2，电偶极跃迁）相比，在 3% (w/w) PMMA 混合膜的情况下，是强振动耦合的结果。尽管两个跃迁的 PL 强度不同，但跃迁的衰减时间在幅度上大致相似。在 3% 薄膜的光谱中电偶极子 4G5/2 → 6H9/2 跃迁的明显分裂很有趣，并导致人们相信 f 电子的状态与周围配体的电场之间存在强耦合。