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Increasing Excited State Lifetimes of Cu(I) Coordination Complexes via Strategic Surface Binding
Inorganic Chemistry Frontiers ( IF 6.1 ) Pub Date : 2024-12-19 , DOI: 10.1039/d4qi02410a Jiaqi Chen, Henry C. London, Dhruba Pattadar, Charlotte Worster, Sahan R. Salpage, Elena Jakubikova, S. Scott Saavedra, Kenneth Hanson
Inorganic Chemistry Frontiers ( IF 6.1 ) Pub Date : 2024-12-19 , DOI: 10.1039/d4qi02410a Jiaqi Chen, Henry C. London, Dhruba Pattadar, Charlotte Worster, Sahan R. Salpage, Elena Jakubikova, S. Scott Saavedra, Kenneth Hanson
Molecules undergo a structural change to minimize the energy of excited states generated via external stimuli such as light. This is particularly problematic for Cu(I) coordination complexes which are an intriguing alternative to the rare and expensive transition metal containing complexes (e.g., Pt, Ir, Ru, etc.) but suffer from short excited state lifetimes due to D2d to D2 distortion and solvent coordination. Here we investigate strategic surface binding as an approach to hinder this distortion and increase the excited state lifetime of Cu(I) polypyridyl complexes. Using transient absorption spectroscopy, we observe a more than 20-fold increase in excited state lifetime, relative to solution, for a Cu(I) complex that can coordinate to the ZrO2 via both carbox-ylated ligands. In contrast, the Cu(I) complex that coordinates via only one ligand has a less pronounced enhancement upon surface binding and exhibits greater sensitivity to coordinating solvents. A combination of ATR-IR and polarized visible ATR measurements as well as theoretical calculations suggest that the increased lifetime is due to surface binding which decreases the degrees of freedom for molecular distortion (e.g., D2d to D2), with the doubly bound complex exhibiting the most pronounced enhancement.
中文翻译:
通过战略表面结合增加 Cu(I) 配位配合物的激发态寿命
分子发生结构变化,以最小化通过外部刺激(如光)产生的激发态的能量。这对于 Cu(I) 配位配合物来说尤其成问题,Cu(I) 配位配合物是稀有且昂贵的含过渡金属配合物(例如 Pt、Ir、Ru 等)的有趣替代品,但由于 D2d 到 D2 的变形和溶剂配位,激发态寿命短。在这里,我们研究了策略性表面结合作为阻止这种扭曲并增加 Cu(I) 聚吡啶配合物的激发态寿命的方法。使用瞬态吸收光谱,我们观察到 Cu(I) 配合物的激发态寿命相对于溶液增加了 20 倍以上,该配合物可以通过两个羧基化配体与 ZrO2 配位。相比之下,仅通过一个配体配位的 Cu(I) 配合物在表面结合时具有不太明显的增强,并且对配位溶剂表现出更高的敏感性。ATR-IR 和偏振可见光 ATR 测量以及理论计算的结合表明,寿命的增加是由于表面结合降低了分子变形的自由度(例如,D2d 到 D2),其中双结合复合物表现出最明显的增强。
更新日期:2024-12-19
中文翻译:
通过战略表面结合增加 Cu(I) 配位配合物的激发态寿命
分子发生结构变化,以最小化通过外部刺激(如光)产生的激发态的能量。这对于 Cu(I) 配位配合物来说尤其成问题,Cu(I) 配位配合物是稀有且昂贵的含过渡金属配合物(例如 Pt、Ir、Ru 等)的有趣替代品,但由于 D2d 到 D2 的变形和溶剂配位,激发态寿命短。在这里,我们研究了策略性表面结合作为阻止这种扭曲并增加 Cu(I) 聚吡啶配合物的激发态寿命的方法。使用瞬态吸收光谱,我们观察到 Cu(I) 配合物的激发态寿命相对于溶液增加了 20 倍以上,该配合物可以通过两个羧基化配体与 ZrO2 配位。相比之下,仅通过一个配体配位的 Cu(I) 配合物在表面结合时具有不太明显的增强,并且对配位溶剂表现出更高的敏感性。ATR-IR 和偏振可见光 ATR 测量以及理论计算的结合表明,寿命的增加是由于表面结合降低了分子变形的自由度(例如,D2d 到 D2),其中双结合复合物表现出最明显的增强。