Charge-transfer complexes of PXX (PXX=6,12-dioxaanthanthrene). The formal charge and molecular geometry

Three kinds of charge-transfer (CT) complexes of PXX (PXX = 6, 12-dioxaanth anthrene) have been newly prepared and structurally characterized. In the 1 :2 CT complex with TNP (TNP = 2,4,6-trinitrophenol), PXX is practically neu tral. In the semiconducting partially oxidized salt with I-3,the PXX molecu les form a trimer and each PXX is formally oxidized by e/3. In the 3:2 salt with [Ni(mnt)(2)](-) (mnt = maleonitriledithiolate),the PXX molecules agai n form a trimer unit and each PXX is formally oxidized by 2e/3. Together wi th the structural data obtained from the PXX single component crystal, the molecular geometry change by the formal charge on PXX has been examined. A noticeable change has been found in the aromatic ring framework, which is c onsistent with the distribution of the HOMO coefficients obtained from the extended Huckel calculation.