König Alexandra, Naumann Robert, Förster Christoph, Klett Jan, Heinze Katja
Department of Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, Mainz 55128, Germany.
J Am Chem Soc. 2025 Jun 18;147(24):20833-20842. doi: 10.1021/jacs.5c04471. Epub 2025 Jun 3.
Ruthenium and iridium are key components in the most important applications of photoactive complexes, namely, light-emitting devices, photocatalysis, bioimaging, biosensing, and photodynamic therapy. Especially, near-infrared (NIR) emissive materials are required in fiber-optic telecommunications, anticounterfeit inks, night-vision readable displays, and bioimaging. Replacing rare and expensive precious metals with more abundant first-row transition metals is of great interest; however, photophysical properties and the chemical stability of 3d metal complexes are often insufficient. Here, we tackle these challenges with a nonprecious metal polypyridine vanadium(II) complex that shows emission above 1300 nm with excited state lifetimes of up to 760 ns. Strong light absorption in the visible spectral region and exceptional stability in the presence of oxygen enable photocatalysis in water and acetonitrile using green to orange-red light for excitation. This study unravels a new design principle for NIR-II luminescent and photoactive complexes based on the abundant first-row transition metal vanadium.
钌和铱是光活性配合物最重要应用中的关键成分，这些应用包括发光器件、光催化、生物成像、生物传感和光动力疗法。特别是，光纤通信、防伪油墨、夜视可读显示器和生物成像需要近红外（NIR）发光材料。用更丰富的第一排过渡金属取代稀有且昂贵的贵金属备受关注；然而，3d金属配合物的光物理性质和化学稳定性往往不足。在此，我们用一种非贵金属多吡啶钒（II）配合物应对这些挑战，该配合物在1300 nm以上发光，激发态寿命长达760 ns。在可见光谱区域有强烈的光吸收，并且在有氧存在时具有出色的稳定性，这使得在水和乙腈中使用绿色到橙红色光进行激发就能实现光催化。这项研究揭示了基于丰富的第一排过渡金属钒的近红外二区发光和光活性配合物的新设计原理。
