Direct Observation of Mixed-Valence and Radical Cation Dimer States of Tetrathiafulvalene in Solution at Room Temperature: Association and Dissociation of Molecular Clip Dimers Under Oxidative Control

We have observed the mixed‐valence and radical cation dimer states of a glycoluril‐based molecular clip with tetrathiafulvalene (TTF) sidewalls at low concentration (1 mM) at room temperature. This molecular clip has four consecutive anodic steps in its cyclic voltammogram, which suggests a sequential oxidation of these TTF sidewalls to generate species existing in several distinct charge states: neutral monomers, mixed‐valence dimers, radical cation dimers, and fully oxidized tetracationic monomers. The observation of characteristic NIR spectroscopic absorption bands at approximately 1650 and 830 nm in spectroelectrochemistry experiments supports the presence of intermediary mixed‐valence and radical cation dimers, respectively, during the oxidation process. The stacking of four TTF radical cations in the dimer led to the appearance of a charge‐transfer band at approximately 946 nm. Nanoelectrospray ionization mass spectrometry was used to verify the tricationic state and confirm the existence of other different charged dimers during the oxidation of the molecular clip. Radical dimers dude! Sequential oxidation of the tetrathiafulvalene sidewalls of a glycoluril‐based molecular clip generates its mixed‐valence and radical cationic dimers at low concentration (1 mM) and room temperature (see figure). Spectroelectrochemistry and nanoelectrospray ionization mass spectrometry confirmed the existence of these variously charged dimers during the oxidation process.