Sinha Narayan, Wegeberg Christina, Häussinger Daniel, Prescimone Alessandro, Wenger Oliver S
Department of Chemistry, University of Basel, Basel, Switzerland.
Nat Chem. 2023 Dec;15(12):1730-1736. doi: 10.1038/s41557-023-01297-9. Epub 2023 Aug 14.
Coordination complexes of precious metals with the d valence electron configuration such as Ru(II), Os(II) and Ir(III) are used for lighting applications, solar energy conversion and photocatalysis. Until now, d complexes made from abundant first-row transition metals with competitive photophysical and photochemical properties have been elusive. While previous research efforts focused mostly on Fe(II), we disclose that isoelectronic Cr(0) gives access to higher photoluminescence quantum yields and excited-state lifetimes when compared with any other first-row d metal complex reported so far. The luminescence behaviour of the metal-to-ligand charge transfer excited states of these Cr(0) complexes is competitive with Os(II) polypyridines. With these Cr(0) complexes, the metal-to-ligand charge transfer states of first-row d metal complexes become exploitable in photoredox catalysis, and benchmark chemical reductions proceed efficiently under low-energy red illumination. Here we demonstrate that appropriate molecular design strategies open up new perspectives for photophysics and photochemistry with abundant first-row d metals.
具有d价电子构型的贵金属(如Ru(II)、Os(II)和Ir(III))的配位络合物被用于照明应用、太阳能转换和光催化。到目前为止,由具有竞争性光物理和光化学性质的丰富的第一行过渡金属制成的d络合物一直难以实现。虽然之前的研究主要集中在Fe(II)上,但我们发现,与迄今为止报道的任何其他第一行d金属络合物相比,等电子的Cr(0)能产生更高的光致发光量子产率和激发态寿命。这些Cr(0)络合物的金属到配体电荷转移激发态的发光行为与Os(II)多吡啶具有竞争力。有了这些Cr(0)络合物,第一行d金属络合物的金属到配体电荷转移态在光氧化还原催化中变得可利用,并且在低能量红色光照下基准化学还原反应能高效进行。在这里,我们证明了适当的分子设计策略为丰富的第一行d金属的光物理和光化学开辟了新的前景。