Synthesis and structural characterization of integrally oxidized, metal-free phthalocyanine compounds: [H(2)(pc)][IBr(2)] and [H(2)(pc)](2)[IBr(2)]Br.C(10)H(7)Br.

The first integrally oxidized metal-free phthalocyanine compounds have been synthesized by chemical oxidation. Phthalocyanine (H(2)(pc), pc = phthalocyaninato) was oxidized with IBr to afford the compounds [H(2)(pc)][IBr(2)] (1) and [H(2)(pc)](2)[IBr(2)]BrAC(10)H(7)Br (2), whose structures were determined by means of single-crystal X-ray diffraction methods: [H(2)(pc)][IBr(2)], P2(1)/c, a = 8.0272(9) A, b = 21.258(2) A, c = 18.1439(2) A, beta = 113.975(2) degrees, V = 2828.8(5) A(3), T = 153 K, Z = 4; [H(2)(pc)](2)[IBr(2)]Br.C(10)H(7)Br, P, a = 8.4724(6) A, b = 13.5794(10) A, c = 13.8403(10) A, alpha = 90.854(1) degrees, beta = 103.417(1) degrees, gamma = 97.049(1)E degrees, V = 1535.61(19) A(3), T = 153 K, Z = 1. The extended structure of [H(2)(pc)][IBr(2)] comprises slipped columns of pc rings stacked along the a axis in adjacent columns at approximately 70 degrees to one another. IBr(2-) ions occupy the interstitial columns. The extended structure of [H(2)(pc)](2)[IBr(2)]Br.C(10)H(7)Br comprises slant stacks of pc rings along the crystallographic a axis with IBr(2-) ions, Br(-) ions, and disordered 1-bromonaphthalene molecules in the adjacent, parallel columns. The overall reaction for the formation of 1 is 2H(2)(pc) + 4IBr --> 2[H(2)(pc)][IBr(2)] + I(2), and the overall reaction for the formation of 2 (not including solvent) is 2H(2)(pc) + 3IBr --> [H(2)(pc)](2)Br[IBr(2)] + I(2).