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

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 =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.

Efficient one-pot green synthesis of tetrakis(acetonitrile)copper(i) complex in aqueous media

“…The products obtained were fully characterized by elemental analysis, X-ray powder diffraction analysis, 1 H, 19 F NMR and IR spectroscopy, UV-VIS spectroscopy. All these analyses conrm formation of high purity targeted compounds.…”

“…6 , LiClO 4 and all the solvents were used as received. The solution 1D 1 H, 19 F NMR spectra were recorded on a Bruker Avance 400 spectrometer. Microanalyses were carried out in the analytical laboratory of the University of Eastern Finland.…”

“…The obtained precipitate was dried at 50 C in air for 2 hours and then in vacuum at RT to give 4.34 g of the product as white crystalline solid (yield 86%). 19 6 mmol, other alkali metal perchlorate can be used instead), acetonitrile (2.68 g, 65.4 mmol), distilled water (ca. 9 ml) were used as starting reagents.…”

“…used in research laboratories and industrial processes as catalysts in cycloaddition 3,4 and Ullmann 5 reactions, intramolecular aromatic annulations, 6,7 oxidation of primary alcohols 8 and many other popular reactions of organic synthesis. [9][10][11][12][13] At the same time they serve as important precursors for the synthesis of overwhelming majority of mononuclear [14][15][16] and homo- 17 and hetero-polynuclear 18,19 copper(I) complexes, which also have numerous practical applications, [20][21][22] one of which is large-scale production of emitting materials for OLED fabrication. 23 Total number of references related to these compounds as reagents/reactants exceeds 3100 (over 100 of them during 2018 year), including the papers in journals of highest rank.…”

Tripodal gold(i) polypyridyl complexes and their Cu+and Zn2+heterometallic derivatives. Effects on luminescence

“…This coordination mode of alkynyl ligand provides additional opportunities for fine tuning of the photophysical characteristics of the resulting compounds. [12,13] This fact, together with the tripodal shape of the TPA ligand makes the resulting complexes particularly interesting due to their luminescent properties able to be modulated by the presence or absence of aurophilic contacts. The coordination of a second metal atom can play an important role in this process.…”