Synthesis, X-ray structure, magnetic resonance, and DFT analysis of a soluble copper(II) pPhthalocyanine lacking C-H bondsSynthesis, X-ray structure, magnetic resonance, and DFT analysis of a soluble copper(II) pPhthalocyanine lacking C-H bonds
Faculty of Sciences. Physics
Biophysics and Biomedical Physics
2010Easton, Pa, 2010
Inorganic chemistry / American Chemical Society. - Easton, Pa
49(2010):19, p. 8779-8789
University of Antwerp
The synthesis, crystal structure, and electronic properties of perfluoro-isopropyl-substituted perfluorophthalocyanine bearing a copper atom in the central cavity (F64PcCu) are reported. While most halogenated phthalocyanines do not exhibit long-term order sufficient to form large single crystals, this is not the case for F64PcCu. Its crystal structure was determined by X-ray analysis and linked to the electronic properties determined by electron paramagnetic resonance (EPR). The findings are corroborated by density functional theory (DFT) computations, which agree well with the experiment. X-band continuous-wave EPR spectra of undiluted F64PcCu powder, indicate the existence of isolated metal centers. The electron-withdrawing effect of the perfluoroalkyl (Rf) groups significantly enhances the complexes solubility in organic solvents like alcohols, including via their axial coordination. This coordination is confirmed by X-band 1H HYSCORE experiments and is also seen in the solid state via the X-ray structure. Detailed X-band CW-EPR, X-band Davies and Mims ENDOR, and W-band electron spin-echo-detected EPR studies of F64PcCu in ethanol allow the determination of the principal g values and the hyperfine couplings of the metal, nitrogen, and fluorine nuclei. Comparison of the g and metal hyperfine values of F64PcCu and other PcCu complexes in different matrices reveals a dominant effect of the matrix on these EPR parameters, while variations in the ring substituents have only a secondary effect. The relatively strong axial coordination occurs despite the diminished covalency of the C−N bonds and potentially weakening Jahn−Teller effects. Surprisingly, natural abundance 13C HYSCORE signals could be observed for a frozen ethanol solution of F64PcCu. The 13C nuclei contributing to the HYSCORE spectra could be identified as the pyrrole carbons by means of DFT. Finally, 19F ENDOR and easily observable paramagnetic NMR were found to relate well to the DFT computations, revealing negligible isotropic hyperfine (Fermi contact) contributions. The single-site isolation in solution and solid state and the relatively strong coordination of axial ligands, both attributed to the introduction of Rf groups, are features important for materials and catalyst design.