Effect of the Substitution Pattern (Peripheral vs Non-Peripheral) on the Spectroscopic, Electrochemical, and Magnetic Properties of Octahexylsulfanyl Copper Phthalocyanines Tulin Ateş Turkmen Lihan Zeng Yan Cui İsmail Fidan Fabienne Dumoulin Catherine Hirel Yunus Zorlu Vefa Ahsen Alexander A. Chernonosov Yurii Chumakov Karl M. Kadish Ayşe Gül Gürek Sibel Tokdemir Öztürk 10.1021/acs.inorgchem.8b00528.s001 https://acs.figshare.com/articles/journal_contribution/Effect_of_the_Substitution_Pattern_Peripheral_vs_Non-Peripheral_on_the_Spectroscopic_Electrochemical_and_Magnetic_Properties_of_Octahexylsulfanyl_Copper_Phthalocyanines/6275573 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 (<b>Cu-P</b>) and non-peripheral (<b>Cu-NP</b>) positions. <b>Cu-NP</b> showed a marked near-IR maximum absorption compared to <b>Cu-P</b> and, accordingly, a smaller HOMO–LUMO energy gap, calculated via the electrochemical results and simulations in the gas phase, as well as for <b>Cu-NP</b> from its crystallographic data. An electron-spin resonance (ESR) technique is used to extract the <i>g</i> values from the powder spectra that are taken at room temperature. The <i>g</i> values were determined to be <i>g</i><sub>∥</sub> = 2.160 and <i>g</i><sub>⊥</sub> = 2.045 for <b>Cu-P</b> and <i>g</i><sub>∥</sub> = 2.150 and <i>g</i><sub>⊥</sub> = 2.050 for <b>Cu-NP</b>. These values indicate that the paramagnetic copper center in both phthalocyanines has axial symmetry with a planar anisotropy (<i>g</i><sub>∥</sub> > <i>g</i><sub>⊥</sub>). The ESR spectra in solution could be obtained only for <b>Cu-P</b>. Curie law is used to fit the experimental data of the magnetic susceptibility versus temperature graphs, and the Curie constant (<i>C</i>) and diamagnetic/temperature-independent paramagnetic (α) contributions are deduced as 0.37598 (0.39576) cm<sup>3</sup>·K/mol and −23 × 10<sup>–5</sup> (25 × 10<sup>–5</sup>) cm<sup>3</sup>/mol respectively for <b>Cu-P</b> and <b>Cu-NP</b>. The room temperature magnetic moment value (1.70 μ<sub>B</sub>) is close to the spin-only value (1.73 μ<sub>B</sub>) for the peripheral complex, showing that there is no orbital contribution to μ<sub>eff</sub>. In contrast, at room temperature, the value of the magnetic moment (1.77 μ<sub>B</sub>) is above the spin-only value, showing an orbital contribution to the magnetic moment. <b>Cu-NP</b>’s room temperature magnetic moment value is larger than the value for <b>Cu-P</b>, 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 <b>Cu-P</b> and <b>Cu-NP</b> complexes have square-planar coordination. This result is consistent with the determined <i>g</i> values. The spin densities were determined experimentally, and the results suggest that the positions of the substituents affect these values (0.469 for <b>Cu-P</b> and 0.490 for <b>Cu-NP</b>). 2018-05-16 11:20:02 g values Cu-P Octahexylsulfanyl Copper Phthalocyanines Peripheral vs Non-Peripheral HOMO Cu-NP copper phthalocyanines substitution position effect ESR moment room temperature