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

Inorganic Chemistry
Tulin Ateş TurkmenSibel Tokdemir Öztürk

Abstract

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 g∥ = 2.160 and g⊥ = 2.045 for Cu-P and g∥ = 2.150 and g⊥ = 2.050 for Cu-NP. These values indicate that the paramagnetic copper center in both phthalocyanines has axial symmetry with a planar anisotropy ( g∥ > g⊥). 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 ...Continue Reading

References

Aug 26, 2003·Chemical Communications : Chem Comm·Paul M BurnhamDavid L Hughes
Jul 11, 2009·The Journal of Physical Chemistry. a·T KrollM Knupfer
Mar 29, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Sevinc Z TopalVefa Ahsen

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