Journal
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Volume 2022, Issue 8, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.202101056
Keywords
Cyclic trinuclear complexes; Cluster compounds; Heterometallic clusters; Metallophilicty; Photoluminescence
Categories
Funding
- University of Camerino
- Robert A. Welch Foundation [B-1542]
- U.S. National Science Foundation [CHE-1413641, CHE-1545934]
- National Science Foundation [CHE-1531468]
- Universita degli Studi di Camerino within the CRUICARE Agreement
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The formation of heterobimetallic complexes from cyclic trinuclear complexes (CTCs) of gold(I) is a straightforward strategy that leads to strengthened bonding and improved optoelectronic properties. This study investigates a new gold(I)-vinylimidazolate CTC and its highly emissive sandwich adducts with soft metal cations. The research provides valuable insights for designing and synthesizing metal complexes with unique optoelectronic properties.
The formation of heterobimetallic complexes from parent cyclic trinuclear complexes (CTCs) of gold(I) has become straightforward in recent years with this team and others showing that the strategy leads to strengthened Au M' bonding and optoelectronic properties. A new gold(I)-vinylimidazolate CTC, 1, was prepared and the formation of highly emissive sandwich adducts with the soft metal cations Cu+, Ag+, and Tl+, 2-4, respectively, was investigated. Compound 1 does not exhibit peculiar emissive properties at room or cryogenic temperatures as the adducts do. Its unit cell packing displays an unprecedented collection of repeating units for CTCs. While the intermolecular Au.Au distances are versatile (3.470, 3.673, and 4.045 A), they connect only single Au centres from adjacent CTCs and form extended circular networks. Hirshfeld surface analyses mapped the new CTC contours underlining the possible cooperative effects of not only metallophilic interactions but also C H.p and hydrogen bonding in the packing of 1 (as opposed to the dominance of the former in most other reported CTCs). DFT calculations validate the formation of sandwich-like structures for compounds 2-4 with averaged Au M distances of 2.665 A, 2.802 A, and 3.036 A, respectively, close by to experimental crystal data obtained for similar sandwich compounds.
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