期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 143, 期 3, 页码 1651-1663出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.0c12805
关键词
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资金
- Swiss National Science Foundation [200021_178760]
- NCCR Molecular Systems Engineering
- Novartis University of Basel Excellence Scholarship for Life Sciences by the Research Fund of the University of Basel
A new homoleptic Mo(0) complex with a unique diisocyanide ligand was developed, exhibiting deep red emission and high upconversion quantum yield. This complex serves as a potent irradiation source and has potential applications in red-light-driven photocatalysis and light-harvesting.
Osmium(II) polypyridines are a well-known class of complexes with luminescent metal-to-ligand charge-transfer (MLCT) excited states that are currently experiencing a revival due to their application potential in organic photoredox catalysis, triplet-triplet annihilation upconversion, and phototherapy. At the same time, there is increased interest in the development of photoactive complexes made from Earth-abundant rather than precious metals. Against this background, we present a homoleptic Mo(0) complex with a new diisocyanide ligand exhibiting different bite angles and a greater extent of pi-conjugation than previously reported related chelates. This new design leads to deep red emission, which is unprecedented for homoleptic arylisocyanide complexes of group 6 metals. With a (MLCT)-M-3 lifetime of 56 ns, an emission band maximum at 720 nm, and a photoluminescence quantum yield of 1.5% in deaerated toluene at room temperature, the photophysical properties are reminiscent of the prototypical [Os(2,2'-bipyridine)(3)](2+) complex. Under 635 nm irradiation with a cw-laser, the new Mo(0) complex sensitizes triplet-triplet annihilation upconversion of 9,10-diphenylanthracene (DPA), resulting in delayed blue fluorescence with an anti-Stokes shift of 0.93 eV. The photorobustness of the Mo(0) complex and the upconversion quantum yield are high enough to generate a flux of upconverted light that can serve as a sufficiently potent irradiation source for a blue-light-driven photoisomerization reaction. These findings are relevant in the greater contexts of designing new luminophores and photosensitizers for use in red-light-driven photocatalysis, photochemical upconversion, light-harvesting, and phototherapy.
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