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Unusual coordination for gold: An imidazolium salt was synthesized and used as a precursor for an N‐heterocyclic carbene, which can be considered as the carbene analogue of 1,10‐phenanthroline. Like the diimine congener, this ligand gives luminescent metal complexes. Remarkably, the AuIIIcomplex features a gold atom in an unusual environment: it is surrounded by six donor atoms, two of which interact electrostatically with the Au atom (see figure).