| The new oxidized phthalocyanine (pc) compounds Cu(pc)(ReO4) 2, Cu(pc)(ReO4), (Cu(pc))3(ReO4) 2, Cu(pc)(SbF6)2, [Ni(pc)]3[ReO 4]2·C10H7Cl, [Cu(pc)]3 [SbF6]2·C10H7Cl, [Cu(pc)]3[AsF6]2·C10H 7Cl, [H2(pc)]3[SbF6]2·C 10H7Cl, and [Ni(pc)]3[SbF6]2·C 10H7Cl, [H2(pc)]2[IBr2](Br)·C 10H7Br, and [H2(pc)][IBr2], were prepared and their crystal structures determined by X-ray diffraction methods. Crystal structures for [H2(pc)]2[IBr2](Br)·C 10H7Cl and [H2(pc)]3[AsF6] 2·C10H7Cl were reexamined and improved. The C–C and C–N distances in the pc rings do not differ significantly between compounds, reflecting the delocalization of the π-electrons.; Crystals of Cu(pc)(ReO4)2, Cu(pc)(ReO4), (Cu(pc))3(ReO4)2, and Cu(pc)(SbF6) 2 comprise discrete molecular units. EPR studies of Cu(pc)(ReO 4)2 and Cu(pc)(ReO4) reveal that the oxidations are ring-centered. The double ring-oxidations of Cu(pc)(ReO4) 2 and Cu(pc)(SbF6)2 are electronically interesting. The discrete molecular structure of (Cu(pc))3(ReO4) 2 is in contrast to the stacked structure of other partially-oxidized porphyrinic compounds.; The members of the [M(pc)]3[A]2·C10 H7Cl (M = Cu, Ni, H2; A = ReO4, AsF 6, SbF6) series of compounds are essentially isostructural, comprising stacks of 2/3-oxidized M(pc) rings segregated into centrosymmetric trimers with counterions and 1-chloronaphthalene solvent molecules occupying the adjacent channels. They are semiconductors with an activation energy of approximately 0.22 eV and room-temperature conductivity of 2 × 10 −3 S/cm. The extended structures of [H2(pc)] 2[IBr2](Br)·C10H7Br and [H 2(pc)][IBr2] comprise jagged stacks of singly oxidized H 2(pc) rings with the other constituents well separated. |
