Bimetallic d10 -Metal Complexes of a Bipyridine Substituted N-Heterocyclic Carbene

Abstract

The hybrid ligand 3-(2,2'-bipyridine-6-ylmethyl)-1-mesityl-1H-imidazolylidene (NHC^Bipy ) featuring both carbene and N-donor sites, was selectively complexed with various d¹⁰ metal cations in order to examine its coordination behavior with regard to homo and heterometallic structures. Respective silver complexes can be obtained by the silver oxide route and are suitable transmetallation reagents for the synthesis of gold(I) compounds. Starting from the mononuclear complexes [(NHC^Bipy )AuCl], [(NHC^Bipy )Au(C₆ F₅ )] and [(NHC^Bipy )₂ Au][ClO₄ ], open-chain as well as cyclic heterobimetallic complexes containing Cu⁺ , Ag⁺ , Zn²⁺ , Cd²⁺ , and Hg²⁺ were synthesized. Furthermore, the homobimetallic species [(NHC^Bipy )₂ M₂ ][ClO₄ ]₂ (M=Cu, Ag) were obtained. All bimetallic compounds were fully characterized including single-crystal X-ray analysis. Their photoluminescence (PL) properties were investigated in the solid state at temperatures between 15 and 295 K and compared with those of the mononuclear species. There is a clear difference in PL properties between the open chain and the cyclic heterobimetallic complexes. The latter species show different PL properties, depending on the metals involved. In addition, collision-induced dissociation (CID) experiments were performed on electrosprayed cations of the cyclic heterobimetallic compounds, to compare the metal binding at the carbene and N-donor sites.

Keywords: N-heterocyclic carbenes; coinage metals; metallophilicity; photoluminescence; silver.