Schmitz Matthias, Naumann Robert, Heinze Katja, Kerzig Christoph
Department of Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, 55128, Mainz, Germany.
Angew Chem Int Ed Engl. 2025 Aug 25;64(35):e202502840. doi: 10.1002/anie.202502840. Epub 2025 Jul 15.
Photoactive osmium complexes are widely used sensitizers for the generation of singlet oxygen because they can be excited directly into their triplet states with low-energy red light. However, their short-lived excited states reduce quenching efficiencies and reaction quantum yields significantly. To elongate the excited state lifetime, osmium complexes have been linked to organic chromophores to form molecular dyads. This approach, although effective, is time- and resource-consuming, hampering larger-scale applications. Here, we demonstrate a straightforward approach by directly mixing a readily available cationic osmium complex and an anionic perylene derivative in solution. Strong Coulombic interactions facilitate rapid energy transfer (∼100 ps) from the excited osmium complex to the perylene derivative, mimicking a dyad-like system. Detailed spectroscopic investigations revealed an increased singlet oxygen formation rate by over one order of magnitude at sub-millimolar perylene concentrations, attributed to i) the three orders of magnitude longer lifetime of the perylene triplet state produced via intra-ion-pair energy transfer and ii) an inherently high singlet oxygen quantum yield of that key species. The novel catalyst system enables highly productive photooxygenations in water and in a MeOH/HO 10:1 mixture, highlighting the broad applicability and versatility of the Coulombic dyad approach for photocatalytic synthesis and wastewater treatment.
光活性锇配合物是广泛用于产生单线态氧的敏化剂,因为它们可以被低能量红光直接激发到三重态。然而,它们的短寿命激发态会显著降低猝灭效率和反应量子产率。为了延长激发态寿命,锇配合物已与有机发色团连接形成分子二元体。这种方法虽然有效,但耗时且耗费资源,阻碍了大规模应用。在这里,我们展示了一种直接的方法,即在溶液中直接混合一种易于获得的阳离子锇配合物和一种阴离子苝衍生物。强烈的库仑相互作用促进了从激发的锇配合物到苝衍生物的快速能量转移(约100皮秒),模拟了二元体样系统。详细的光谱研究表明,在亚毫摩尔苝浓度下,单线态氧的形成速率提高了一个多数量级,这归因于:i)通过离子对内能量转移产生的苝三重态寿命延长了三个数量级;ii)该关键物种固有的高单线态氧量子产率。这种新型催化剂体系能够在水中以及甲醇/水10:1的混合物中高效地进行光氧化反应,突出了库仑二元体方法在光催化合成和废水处理方面的广泛适用性和多功能性。
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