Electrochemistry of cyclic triimidazoles and their halo derivatives: A casebook for multiple equivalent centers and electrocatalysis

A family of cyclic triazines, based on the triimidazo[1,2-a:1′,2′-c:1″,2″-e][1,3,5]triazine scaffold, has recently caught attention due to its variegated solid state photoluminescent properties (e.g., crystallization induced emission, fluomechanochromism, dual fluorescence, room temperature ultralong phosphorescence), tuned by proper functionalization of the cyclic core. From an electrochemical point of view, this family of heteroaromatic cyclic triazines is unexplored. A cyclic voltammetry study is here performed aiming to clarify structure/electroactivity relationship. The peculiar molecular structure of this class of molecules offers a multi-approach case study, spanning from multiple equivalent redox site interactions in small hoops (due to ideally C3h symmetry) to carbon-halogen bond reactivity in the presence of catalytic metal electrode surfaces (for –Br and –I derivatives). Results point to a poor heteroannular aromaticity along the rigid, planar cyclotrimer, with each equivalent redox site acting quite independently. An unusually higher electrocatalytic performance of gold with respect to silver electrode for the electrocleavage of carbon-halogen bonds (that decreases by increasing number of halo substituents) is tentatively explained in term of a specific interaction between gold and the nitrogen-rich planar cyclotrimer platform.