LITHIUMPHTHALOCYANINES - SYNTHESIS, PROPE RTIES, AND CRYSTAL-STRUCTURE OF TRIPHENYLPHOSPHINE)IMINIUMPHTHALOCYANINATOLITHATES WITH DIFFERENTCONFORMATIONS OF THE CATION

Reaction of (n-dodecyl)n-butylammoniumphthalocyaninatolithate, (TDBA)[ LiPc(2-)] with bis(triphenylphosphin)iminiumbromide, (PNP)Br in dichlo romethane yields (PNP)[LiPc(2-)]. It crystallizes in the triclinic spa ce group P ($) over bar 1 as dichloromethane solvate (1) and in the mo noclinic space group P2(1)/n as hydrate (2). The crystal structures of (1) and (2) are reported. Each salt contains two crystallographically slightly different discrete [LiPc(2-)](-) anions, in which the square -planar coordinated Li+ cation is centered within the planar Pc(2-) li gand (D-av.(Li-Ni-iso) = 1.945 Angstrom). There are three different co nformations for the (PNP) cation: (1) only contains the bent conformer (d(av)(P-N) = 1.575 Angstrom; phi(P-N-P) = 140.8 degrees), while in ( 2) an hybrid (d(av)(P-N) = 1.562 Angstrom; phi(P-N-P) = 158.1 degrees) and the linear conformer (d(av)(P-N) = 1.547 Angstrom; phi(P-N-P) = 1 76.8 degrees) are present. The very soluble, blue-green salts melt at 265 degrees C without decomposition. In accordance with cyclovoltammet ric data thin films of (PNP)[LiPc(2-)] are oxidized by NO2 or Br-2 to yield brown violet [LiPc(-)]. The electronic absorption spectra and th e vibrational spectra are discussed.