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Heterometallic Cluster‐Capped Tetrahedral Assemblies with Postsynthetic Modification of the Metal Cores
Author(s) -
Shakirova Julia R.,
Grachova Elena V.,
Gurzhiy Vladislav V.,
Thangaraj Senthil Kumar,
Jänis Janne,
Melnikov Alexey S.,
Karttunen Antti J.,
Tunik Sergey P.,
Koshevoy Igor O.
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201809058
Subject(s) - isostructural , phosphorescence , cluster (spacecraft) , supramolecular chemistry , luminescence , metal , excited state , chemistry , ligand (biochemistry) , crystallography , alkyne , copper , photochemistry , materials science , crystal structure , fluorescence , optoelectronics , physics , atomic physics , biochemistry , receptor , organic chemistry , quantum mechanics , computer science , programming language , catalysis
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.