Two Synthetic Approaches to Coinage Metal(I) Mesocates: Electrochemical versus Chemical Synthesis.

We report two different approaches to isolate neutral and cationic mesocate-type metallosupramolecular architectures derived from coinage monovalent ions. For this purpose, we use a thiocarbohydrazone ligand, H 2 L ( 1 ), conveniently tuned with bulky phosphine groups to stabilize the M I ions and prevent ligand crossing to achieve the selective formation of mesocates. The neutral complexes [Cu 2 (HL) 2 ] ( 2 ), [Ag 2 (HL) 2 ] ( 3 ), and [Au 2 (HL) 2 ] ( 4 ) were prepared by an electrochemical method, while the cationic complexes [Cu 2 (H 2 L) 2 ](PF 6 ) 2 ( 5 ), [Cu 2 (H 2 L) 2 ](BF 4 ) 2 ( 6 ), [Ag 2 (H 2 L) 2 ](PF 6 ) 2 ( 7 ), [Ag 4 (HL) 2 ](NO 3 ) 2 ( 8 ), and [Au 2 (H 2 L) 2 ]Cl 2 ( 9 ) were obtained by using a metal salt as the precursor. All of the complexes are neutral or cationic dinuclear mesocates, except the silver nitrate derivative, which exhibits a tetranuclear cluster mesocate architecture. The crystal structures of the neutral and cationic copper(I), silver(I), and gold(I) complexes allow us to analyze the influence of synthetic methodology or the counterion role on both the micro- and macrostructures of the mesocates.