Crystallographic evidence for global aromaticity in the di-anion and tetra-anion of a cyclophane hydrocarbon

[2(4)]Paracyclophanetetraene is a classic example of a macrocyclic hydrocarbon that becomes globally aromatic on reduction to the di-anion, and switches to globally anti-aromatic in the tetra-anion. This redox activity makes it promising as an electrode material for batteries. Here, we report the solid-state structures of the di- and tetra-anions of this cyclophane, in several coordination environments. The changes in bond length on reduction yield insights into the global aromaticity of the di-anion (26 π electrons), and anti-aromaticity of the tetra-anion (28 π electrons), that were previously deduced from NMR spectra of species generated in situ. The experimental geometries of the aromatic di-anion and anti-aromatic tetra-anion from X-ray crystallographic data match well with gas-phase calculated structures, and reproduce the low symmetry expected in the anti-aromatic ring. Comparison of coordinated and naked anions confirms that metal coordination has little effect on the bond lengths. The UV-vis-NIR absorption spectra show a sharp intense peak at 878 nm for the di-anion, whereas the tetra-anion gives a broad spectrum typical of an anti-aromatic system.