Preparation and Oxidation of the Bis(tetra-n-butylammonium) Salt of 2,2'-(2,7-Pyrenediyl)bis Dianion

Article abstract of DOI:10.1021/jo00345a024

2,2'-(2,7-Pyrenediyl)bis (2) is synthesized in 12 steps from 1,4,5,8-naphthalenetetracarboxylic dianhydride in 7percent overall yield.Upon oxidation with a variety of reagents an insoluble purple solid is formed whose infrared spectrum and elemental analysis imply it not to be 11,11,12,12-tetracyanopyreno-2,7-quinodimethane (TCNP) and whose insolubility suggests it to be polymeric.Upon oxidation at a platinum or vitreous carbon electrode the bis(tetra-n-butylammonium) salt (15) of the conjugate base of 2 (in 0.1 M tetra-n-butylammonium perchlorate inacetonitrile) undergoes a reversible one-electron oxidation pa1 = 0.075 V relative to Ag/AgCl(s)> and an irreversible second oxidation (E_pa2 = 0.340 V).At low temperatures (-20 deg C, 0.9 mM) the product of the first oxidation, the radical anion of TCNP, dimerizes.