(19)F NMR Spectra and Structure of Halogenated Porphyrins

Article abstract of DOI:10.1021/ic00118a010

Fluorine-19 NMR spectra of a series of halogenated porphyrins have beenused to create a spectral library of different types of fluorine splitting patterns for tetrakis(pentafluorophenyl) porphyrins (TFPP) complexed with diamagnetic and paramagnetic metal ions. The paramagnetic shift, line broadening, and fine structure of the resonances from the peripheral pentafluorophenyl rings are dependent on the symmetry and core environment of the porphyrin macrocycles. In combination with crystal structuredata, (19)F NMR helps define the behavior of halogenated porphyrins in solution. Six new crystal structures for TFPP and octahalo-TFPP derivatives are reported: H2TFPP in rhombohedral space group R3-, a = 20.327(4) ?, c = 24.368(5) ?, V = 8720(3) ?**3, Z = 9; ZnTFPP in monoclinic space group P21/C, a = 12.653(4) ?, b = 11.883(5) ?, c = 15.261(2) ?, β = 103.87(2)°, V = 2227.6(13) ?**3, Z =2; CuTFPP in rhombohedral space group R3-, a = 20.358(5), c = 24.347(6)?, V = 8739(4) ?**3, Z = 9; H2TFPPCl8 in triclinic space group P1-, a = 11.066(1) ?, b = 14.641(3) ?, c = 14.678(2) ?, α = 88.97(1)°, β = 76.05(1)°, γ = 71.29(1)°, V = 2181.4(6) ?**3, Z = 2; ZnTFPPCl8 in tetragonal space groupP4-21C, a = 19.502(20), c = 10.916(8) ?, V = 4152(6) ?**3, Z = 2; H2TFPPBr8 in monoclinic space group C2, a = 27.634(6) ?, b = 6.926(2) ?, c = 14.844(3) ?, β = 109.64(2)°, V = 2675.8(11) ?**3, Z = 2.