Heterometallic Cluster-Capped Tetrahedral Assemblies with Postsynthetic Modification of the Metal Cores

Julia R Shakirova; Elena V Grachova; Vladislav V Gurzhiy; Senthil Kumar Thangaraj; Janne Jänis; Alexey S Melnikov; Antti J Karttunen; Sergey P Tunik; Igor O Koshevoy

doi:10.1002/anie.201809058

Heterometallic Cluster-Capped Tetrahedral Assemblies with Postsynthetic Modification of the Metal Cores

Angew Chem Int Ed Engl. 2018 Oct 22;57(43):14154-14158. doi: 10.1002/anie.201809058. Epub 2018 Sep 26.

Authors

Julia R Shakirova¹, Elena V Grachova¹, Vladislav V Gurzhiy¹, Senthil Kumar Thangaraj², Janne Jänis², Alexey S Melnikov³, Antti J Karttunen⁴, Sergey P Tunik¹, Igor O Koshevoy²

Affiliations

¹ Department of Chemistry, St. Petersburg State University, Universitetskii pr. 26, 198504, St. Petersburg, Russia.
² Department of Chemistry, University of Eastern Finland, 80101, Joensuu, Finland.
³ Centre for Nano- and Biotechnologies, Peter the Great St. Petersburg Polytechnic University, 195251, St. Petersburg, Russia.
⁴ Department of Chemistry and Materials Science, Aalto University, 00076, Aalto, Finland.

PMID: 30195272
DOI: 10.1002/anie.201809058

Abstract

Combining the star-shaped alkynyl ligands with low-nuclearity gold-copper triphosphane clusters produces 3D metallocage aggregates, which demonstrate room temperature phosphorescence in solution (max Φ_em =0.6). Their luminescence mainly originates from cluster-localized metal-to-ligand charge transfer excited state. These supramolecular assemblies can be easily converted into the isostructural gold-silver congeners by the direct exchange of the metal ions. Such modification of the terminal metal cores switches the emission to the intraligand (alkyne) electronic transitions of the triplet manifold, that represents an unusual optical functionality among the metallocycle/metallocage complexes.

Keywords: alkyne ligands; cluster compounds; coinage metals; heterometallic complexes; phosphorescence.

Abstract

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