Synthesis and properties of diphthalocyaninates of bismuth, [Bi(Pc)(2)](k) (k=1-, 0, 1+); Crystal structure of mixed-valent [Bi(Pc)(2)]center dot CH2Cl2

Blue di(phthalocyaninato(2-))bismuthate(III), [Bi(Pc(2-))(2)](-), is obtained by the reaction of BiO(NO3) with molten 1,2-dicyanobenzene in the presence of potassium methylate and isolated as tetra-n-butylammonium ((n)Bu(4)N)(+) and bis(triphenylphosphine)iminium (PNP)(+) salt. Green mixed-valent [Bi(Pc)(2)] . CH2Cl2 is prepared by anodic oxidation of [Bi(Pc(2-))(2)](-). It crystallizes in the orthorhombic gamma modification (Pnma; a = 28.176(5), b = 22.913(3), c = 7.925(1) Angstrom, Z = 4). The Bi-III ion is eightfold coordinated by the N-iso atoms of the slightly distorted Pc ligands in a square antiprismatic manner. The average Bi-N-iso bond distance is 2.467 Angstrom. The complex is paramagnetic (mu(eff) = 1.84 mu(B)). Oxidation of [Bi(Pc(2-))(2)](-) with bromine yields purple, diamagnetic [Bi(Pc(-))(2)]Br-x (1.5 less than or equal to x less than or equal to 2.5). The redox properties are investigated electrochemically. UV-Vis-NIR, MIR/FIR and resonance Raman spectra of the new bismuth(III) complexes are discussed and compared with those of diphthalocyaninates of the lanthanides.