An Unusual Organic Rearrangement Initiated by a Ligand-Metal Charge Transfer: The Synthesis and Characterization of the 5,9-dimethyl-5,9-dihydroquinoxalino-[3,2,1-de]phenazine Radical Cation
Beattie, Ross J.
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Although this project started off as a search for metal complexes of the small macrocyclic ligand N,N'-dimethyltribenzo-1,4,7-triazacyclononatriene (Me2N3-CTV), the end result was a oxidation-reduction reaction resulting in an organic rearrangement of the starting ligand. This rearrangement was shown by single crystal X-ray crystallography to be a ionic compound containing the dibromocuprate(I) anion and a radical cation, 5,9- dimethyl-5,9-dihydroquinoxalino-[3,2,1-de]phenazine. The structure suggest a highly delocalized system of bonds, which is confirmed by the use of Mulliken charge and spin density values found through density functional calculations done on the cation. The crystal structure also shows the pairing of cations within the crystal and the layering of both cations and anions. These pairs are likely to be involved in π–π stacking interactions with each other. IR, UV/Vis, and near IR spectra were also examined for the system in order to give a more complete view of the molecule products properties. These spectra may also show the existence of concentration dependent behavior indication the possibility of intermolecular interactions in solution as well as in the solid state.