Synthesis and structural characterization of integrally oxidized, metal-free phthalocyanine compounds:: [H2(pc)][IBr2] and [H2(pc)]2[IBr2]Br•C10H7Br

The first integrally oxidized metal-free phthalocyanine compounds have been synthesized by chemical oxidation. Phthalocyanine (H-2(pc) = phthalocyaninato) was oxidized with IBr to afford the compounds [H-2(pc)][IBr2] (1) and [H-2(pc)](2)[IBr2]BrAC(10)H(7)Br (2), whose structures were determined by means of single-crystal X-ray diffraction methods: [H-2(pc)][IBr2], P2(1)/c, a = 8.0272(9) Angstrom, b = 21,258(2) Angstrom, c = 18.1439(2) Angstrom, beta = 113.975(2)(.), V = 2828.8(5) Angstrom(3), T = 153 K, Z = 4; [H-2(pc)](2)[IBr2]Br.C10H7Br, P (1) over bar, a = 8.4724(6) Angstrom, b = 13,5794(10) Angstrom, c = 13.8403(10) Angstrom, alpha = 90.854(1)degrees, beta = 103.417(1)degrees, gamma = 97,049(1)Edegrees, V = 1535.61(19) Angstrom(3), T = 153 K, Z = 1. The extended structure of [H-2(pc)][IBr2] comprises slipped columns of pc rings stacked along the a axis in adjacent columns at similar to70degrees to one another. IBr2- ions occupy the interstitial columns. The extended structure of [H-2(pc)](2)[IBr2]Br.C10H7Br comprises slant stacks of pc rings along the crystallographic a axis with IBr2- 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)][IBr2] + I-2, and the overall reaction for the formation of 2 (not including solvent) is 2H(2)(pc) + 3IBr --> [H-2(pc)](2)Br[IBr2] + I-2.