Simple Synthetic Routes to Carbene‐M‐Amido (M=Cu, Ag, Au) Complexes for Luminescence and Photocatalysis Applications. Issue 46 (28th June 2021)

• Record Type: Journal Article
• Authors: Tzouras, Nikolaos V.; Martynova, Ekaterina A.; Ma, Xinyuan; Scattolin, Thomas; Hupp, Benjamin; Busen, Hendrik; Saab, Marina; Zhang, Ziyun; Falivene, Laura; Pisanò, Gianmarco; Van Hecke, Kristof; Cavallo, Luigi; Cazin, Catherine S. J.; Steffen, Andreas; Nolan, Steven P.
• Is Part Of: Chemistry. Volume 27:Issue 46(2021)
• Page Start: 11904
• Page End: 11911
• Publication Date: 2021-06-28
• Subjects: carbene-metal-amides -- coinage metal-N-heterocyclic carbene complexes -- mechanochemistry -- photocatalysis -- synthetic methods; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202101476
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The development of novel and operationally simple synthetic routes to carbene‐metal‐amido (CMA) complexes of copper, silver and gold relevant for photonic applications are reported. A mild base and sustainable solvents allow all reactions to be conducted in air and at room temperature, leading to high yields of the targeted compounds even on multigram scales. The effect of various mild bases on the N−H metallation was studied in silico and experimentally, while a mechanochemical, solvent‐free synthetic approach was also developed. Our photophysical studies on [M(NHC)(Cbz)] (Cbz=carbazolyl) indicate that the occurrence of fluorescent or phosphorescent states is determined primarily by the metal, providing control over the excited state properties. Consequently, we demonstrate the potential of the new CMAs beyond luminescence applications by employing a selected CMA as a photocatalyst. The exemplified synthetic ease is expected to accelerate the applications of CMAs in photocatalysis and materials chemistry. Abstract : N−H metallation routes : Interest in carbene‐metal‐amido (CMA) complexes of the coinage metals has inspired comprehensive efforts towards simplifying their synthesis. We now showcase simple and sustainable routes to various CMAs, using mild conditions for the N−H metallation of carbazole and other amines. The action of a mild base is studied computationally and the photophysical properties of some new CMA complexes are examined.