Pyrene‐Based Bisazolium Salts: From Luminescence Properties to Janus‐Type Bis‐N‐Heterocyclic Carbenes

A series of pyrene‐based bisazolium salts have been obtained starting from 4,5,9,10‐tetrabromo‐2,7‐di‐tert‐butylpyrene. The synthetic procedure to the pyrene‐bisazoliums (PBIs) reveals an unexpected behavior, as a consequence of the presence of the alkyl groups (alkyl=Me, Et, n‐Pr, and n‐Bu) coming from the trisalkoxyformate in the final products, instead of the expected tBu of tAmyl groups from the starting tetra‐aminated pyrenes. All bisazoliums show fluorescence properties, with emissions in the range of 370–420 nm, and quantum yields ranging from 0.29 to 0.41. The PBIs were used as bis‐NHC precursors in the preparation of a series of dirhodium and diiridium complexes, which have been fully characterized. The electrochemical studies on selected dimetallic complexes reveal that the electronic communication between the metals through the polyaromatic linker is negligible.