Hou Jinle, Huang Chen, Liu Yuxin, Fei Pengfei, Zhang Dongxu, Qu Konggang, Zi Wenwen, Huang Xianqiang
Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252000, China.
Molecules. 2024 May 30;29(11):2566. doi: 10.3390/molecules29112566.
Incorporating two organic ligands with different functionalities into a titanium-oxo cluster entity simultaneously can endow the material with their respective properties and provide synergistic performance enhancement, which is of great significance for enriching the structure and properties of titanium-oxo clusters (TOCs). However, the synthesis of such TOCs is highly challenging. In this work, we successfully synthesized a TBC4A-functionalized TOC, [Ti(TBC4A)(MeO)] (; MeOH = methanol, TBC4A = tert-butylcalix[4]arene). By adjusting the solvent system, we successfully introduced 1,10-phenanthroline (Phen) and prepared TBC4A and Phen co-protected [Ti(TBC4A)(Phen)] (). Moreover, when Phen was replaced with bulky 4,7-diphenyl-1,10-phenanthroline (Bphen), [Ti(TBC4A)(Bphen)] (), which is isostructural with , was obtained, demonstrating the generality of the synthetic method. Remarkably, demonstrates good stability and stronger light absorption, as well as superior photoelectric performance compared to . Density functional theory (DFT) calculations reveal that there exists ligand-to-core charge transfer (LCCT) in , while an unusual ligand-to-ligand charge transfer (LLCT) is present in , accompanied by partial LCCT. Therefore, the superior light absorption and photoelectric properties of are attributed to the existence of the unusual LLCT phenomenon. This study not only deeply explores the influence of Phen on the performance of the material but also provides a reference for the preparation of materials with excellent photoelectric performance.
将两种具有不同功能的有机配体同时引入到钛氧簇实体中，可以使材料具备它们各自的性质，并提供协同的性能增强，这对于丰富钛氧簇（TOCs）的结构和性质具有重要意义。然而，合成此类钛氧簇极具挑战性。在这项工作中，我们成功合成了一种TBC4A功能化的钛氧簇，[Ti(TBC4A)(MeO)]（；MeOH = 甲醇，TBC4A = 叔丁基杯[4]芳烃）。通过调整溶剂体系，我们成功引入了1,10 - 菲咯啉（Phen）并制备了TBC4A和Phen共同保护的[Ti(TBC4A)(Phen)]（）。此外，当用体积较大的4,7 - 二苯基 - 1,10 - 菲咯啉（Bphen）取代Phen时，得到了与结构同构的[Ti(TBC4A)(Bphen)]（），证明了该合成方法的通用性。值得注意的是，与相比，表现出良好的稳定性和更强的光吸收以及优异的光电性能。密度泛函理论（DFT）计算表明，中存在配体到核心的电荷转移（LCCT），而中存在不寻常的配体到配体的电荷转移（LLCT），同时伴有部分LCCT。因此，的优异光吸收和光电性能归因于不寻常的LLCT现象的存在。本研究不仅深入探讨了Phen对材料性能的影响，还为制备具有优异光电性能的材料提供了参考。
