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Long-Lived, Strongly Emissive, and Highly Reducing Excited States in Mo(0) Complexes with Chelating Isocyanides

Herr, Patrick and Glaser, Felix and Büldt, Laura A. and Larsen, Christopher B. and Wenger, Oliver S.. (2019) Long-Lived, Strongly Emissive, and Highly Reducing Excited States in Mo(0) Complexes with Chelating Isocyanides. Journal of the American Chemical Society, 141 (36). pp. 14394-14402.

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Official URL: https://edoc.unibas.ch/73102/

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Abstract

Newly discovered tris(diisocyanide)molybdenum(0) complexes are Earth-abundant isoelectronic analogues of the well-known class of [Ru(α-diimine)3]2+ compounds with long-lived 3MLCT (metal-to-ligand charge transfer) excited states that lead to rich photophysics and photochemistry. Depending on ligand design, luminescence quantum yields up to 0.20 and microsecond excited state lifetimes are achieved in solution at room temperature, both significantly better than those for [Ru(2,2′-bipyridine)3]2+. The excited Mo(0) complexes can induce chemical reactions that are thermodynamically too demanding for common precious metal-based photosensitizers, including the widely employed fac-[Ir(2-phenylpyridine)3] complex, as demonstrated on a series of light-driven aryl–aryl coupling reactions. The most robust Mo(0) complex exhibits stable photoluminescence and remains photoactive after continuous irradiation exceeding 2 months. Our comprehensive optical spectroscopic and photochemical study shows that Mo(0) complexes with diisocyanide chelate ligands constitute a new family of luminophores and photosensitizers, which is complementary to precious metal-based 4d6 and 5d6 complexes and represents an alternative to nonemissive Fe(II) compounds. This is relevant in the greater context of sustainable photophysics and photochemistry, as well as for possible applications in lighting, sensing, and catalysis.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Wenger)
UniBasel Contributors:Wenger, Oliver and Herr, Patrick and Glaser, Felix and Büldt, Laura Allegra and Larsen, Christopher Bryan
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:American Chemical Society
ISSN:0002-7863
e-ISSN:1520-5126
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
Identification Number:
Last Modified:11 Sep 2020 01:30
Deposited On:10 Dec 2019 15:41

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