In this study, we examined the photophysical properties of an azacrown-Iridium(III) complex while focusing on its interactions with calcium ions (Ca²⁺). We explored the dynamic processes within the complex combining time-dependent density functional theory (TDDFT) calculations and time-resolved spectroscopies. In the presence of Ca²⁺, the complex exhibits significant shifts in absorption and emission profiles, from 494 nm to 375 nm, aligning with theoretical predictions. Notably, we observed the ultrafast photo-ejection of Ca²⁺ within 70 femtoseconds, followed by its recapture in 250 nanoseconds, revealing a 10-million-fold timescale difference between the two phenomena. These behaviors confirm the established photophysical properties of polypyridyl Iridium(III) complexes and their intrinsic sensitivity to their surrounding environment. Our comprehensive kinetic analysis highlights the azacrown moiety's competitive binding and photo-release capabilities, suggesting practical sensing applications. The versatile properties of these Iridium(III) complexes offer promising prospects for advanced optoelectronic devices, targeted imaging, stimuli-responsive materials, and biomedical ion sensors and delivery systems.

中文翻译：

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通过时间分辨光谱和 TDDFT 计算研究 Ca2+ 阳离子的光喷射重捕获：氮冠-铱 (III) 复合物的案例研究。


在这项研究中，我们研究了氮杂冠-铱 (III) 复合物的光物理性质，同时重点关注其与钙离子 (Ca ²⁺ ) 的相互作用。我们结合时间相关密度泛函理论（TDDFT）计算和时间分辨光谱探索了复杂的动态过程。在存在 Ca ²⁺ 的情况下，该配合物的吸收和发射曲线表现出显着的变化，从 494 nm 到 375 nm，与理论预测一致。值得注意的是，我们在 70 飞秒内观察到 Ca ²⁺ 的超快光喷射，然后在 250 纳秒内重新捕获，揭示了两种现象之间 1000 万倍的时间尺度差异。这些行为证实了聚吡啶铱（III）配合物的既定光物理性质及其对周围环境的固有敏感性。我们的综合动力学分析强调了氮杂冠部分的竞争性结合和光释放能力，提示了实际的传感应用。这些铱（III）配合物的多功能特性为先进光电器件、靶向成像、刺激响应材料以及生物医学离子传感器和传输系统提供了广阔的前景。