Effect of the Substitution Pattern (Peripheral vs Non-Peripheral) on the Spectroscopic, Electrochemical, and Magnetic Properties of Octahexylsulfanyl Copper Phthalocyanines

Turkmen T. A. , Zeng L., Cui Y., Fidan I., DUMOULIN F. , Hirel C., ...Daha Fazla

INORGANIC CHEMISTRY, cilt.57, ss.6456-6465, 2018 (SCI İndekslerine Giren Dergi) identifier identifier identifier

  • Cilt numarası: 57 Konu: 11
  • Basım Tarihi: 2018
  • Doi Numarası: 10.1021/acs.inorgchem.8b00528
  • Sayfa Sayıları: ss.6456-6465


In order to investigate the substitution position effect on the spectroscopic, electrochemical, and magnetic properties of copper phthalocyanines, a detailed structure property analysis has been performed by examining two copper phthalocyanines that are octasubstituted by hexylsulfanyl chains respectively in the peripheral (Cu-P) and non-peripheral (Cu NP) positions. Cu-NP showed a marked near-IR maximum absorption compared to Cu-P and, accordingly, a smaller HOMO LUMO energy gap, calculated via the electrochemical results and simulations in the gas phase, as well as for Cu-NP from its crystallographic data. An electron-spin resonance (ESR) technique is used to extract the g values from the powder spectra that are taken at room temperature. The g values were determined to be gil = 2.160 and gi = 2.045 for Cu-P and g(perpendicular to) = 2.150 and g(i) = 2.050 for Cu-NP. These values indicate that the paramagnetic copper center in both phthalocyanines has axial symmetry with a planar anisotropy (gii > &D. The ESR spectra in solution could be obtained only for Cu-P. Curie law is used to fit the experimental data of the magnetic susceptibility versus temperature graphs, and the Curie constant (C) and diamagnetic/temperature-independent paramagnetic (a) contributions are deduced as 0.37598 (0.39576) cm(3).K/mol and 23 X 10(-3) (25 X 10(-3)) cm(3)/mol respectively for Cu-P and Cu-NP. The room temperature magnetic moment value (1.70 /4) is close to the spin-only value (1.73 /413) for the peripheral complex, showing that there is no orbital contribution to yeff. In contrast, at room temperature, the value of the magnetic moment (1.77 peB) is above the spin-only value, showing an orbital contribution to the magnetic moment. Cu-NP's room temperature magnetic moment value is larger than the value for Cu-P, demonstrating that the orbital contribution to the magnetic moment depends upon the substituent position. The magnitudes of the effective magnetic moment values also support that both Cu-P and Cu-NP complexes have square-planar coordination. This result is consistent with the determined g values. The spin densities were determined experimentally, and the results suggest that the positions of the substituents affect these values (0.469 for Cu-P and 0.490 for Cu-NP).