Fine-Tuned Visible and Near-Infrared Luminescence on Self-Assembled Lanthanide-Organic Tetrahedral Cages with Triazole-Based Chelates
Fine-Tuned Visible and Near-Infrared Luminescence on Self-Assembled Lanthanide-Organic Tetrahedral Cages with Triazole-Based Chelates
复制标题
具有三唑基螯合物的自组装镧系元素有机四面体笼的微调可见光和近红外发光
DOI：
10.1021/acs.inorgchem.9b00756
复制
发表时间：
2019
影响因子：
4.6
通讯作者：
Qing-Fu Sun
中科院分区：
文献类型：
--
作者：
Shi-Yu Wu;Xiao-Qing Guo;Li-Peng Zhou;Qing-Fu Sun
由于其在荧光粉、发光二极管、生物传感器/探针、光通信等领域的广泛应用，构建具有良好结构的镧系元素配合物具有重要意义。与单核和双核镧系元素配合物相比，具有明亮发光的多核镧系元素超分子结构还很少见。在此，我们报道了强发光的镧系元素-有机四面体Ln 4L 4笼与一系列基于三唑螯合物的三（三齿）配体的配位自组装。其中，三唑-吡啶-三唑（TPT）配合物L3对所有镧系离子（Ln = Pr，Nd，Sm，Eu，Tb，Dy，Ho，Er，Tm，Yb）都表现出良好的敏化作用，对Tb_4（L3）_4的荧光量子产率（Φ = 82%）达到了历史最高值。与此相反，配体与氨基吡啶三唑（APT）或TPA螯合物显示出弱得多的增感能力。所有配体的能级进行了测量，并采用TD-DFT计算阐明敏化机制。最后，通过组合所需的发光化合物形成的白光发射系统已被证明。我们的强发光LOPs为光化学超分子器件提供了新的候选者。
The construction of well-defined lanthanide complexes emitting in both the visible and near-infrared regions is of great importance due to their widespread applications in phosphors, light-emitting diodes, biosensors/probes, optical communications, etc. In comparison to the well-known mononuclear and dinuclear lanthanide complexes, multinuclear lanthanide supramolecular edifices with bright luminescence are still scarce. Herein, we report the coordination self-assembly of strongly luminescent lanthanide-organic tetrahedral Ln4L4cages with a series of tris(tridentate) ligands based on the triazole chelates. Among them, the new ligandL3with triazole-pyridine-triazole (TPT) chelates manifests an excellent sensitization toward all of the lanthanide ions (Ln = Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb) that emit in both the visible and near-infrared regions, with a record luminescent quantum yield for Tb4(L3)4(Φ = 82%) being obtained. In contrast, ligands with amido-pyridine-triazole (APT) orTPAchelates show much weaker sensitization ability. Energy levels for all ligands were measured, and TD-DFT calculations were employed to shed light on the sensitization mechanism. Finally, white-light emission systems formed by combining the desired luminescent compounds have been demonstrated. Our strongly luminescent LOPs provide new candidates for photochemical supramolecular devices.