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Effect of the Substitution Pattern (Peripheral vs Non-Peripheral) on the Spectroscopic, Electrochemical, and Magnetic Properties of Octahexylsulfanyl Copper Phthalocyanines
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2018-05-16 00:00:00 , DOI: 10.1021/acs.inorgchem.8b00528 Tulin Ateş Turkmen , Lihan Zeng 1 , Yan Cui 1 , İsmail Fidan , Fabienne Dumoulin , Catherine Hirel , Yunus Zorlu , Vefa Ahsen , Alexander A. Chernonosov 2 , Yurii Chumakov 3 , Karl M. Kadish 1 , Ayşe Gül Gürek , Sibel Tokdemir Öztürk
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2018-05-16 00:00:00 , DOI: 10.1021/acs.inorgchem.8b00528 Tulin Ateş Turkmen , Lihan Zeng 1 , Yan Cui 1 , İsmail Fidan , Fabienne Dumoulin , Catherine Hirel , Yunus Zorlu , Vefa Ahsen , Alexander A. Chernonosov 2 , Yurii Chumakov 3 , Karl M. Kadish 1 , Ayşe Gül Gürek , Sibel Tokdemir Öztürk
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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 (α) contributions are deduced as 0.37598 (0.39576) cm3·K/mol and −23 × 10–5 (25 × 10–5) cm3/mol respectively for Cu-P and Cu-NP. The room temperature magnetic moment value (1.70 μB) is close to the spin-only value (1.73 μB) for the peripheral complex, showing that there is no orbital contribution to μeff. In contrast, at room temperature, the value of the magnetic moment (1.77 μB) 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).
中文翻译：
取代模式（外围与非外围）对八亚乙基硫烷基铜酞菁的光谱，电化学和磁性的影响
为了研究取代位置对铜酞菁的光谱，电化学和磁性能的影响，通过检查分别在外围（Cu-P）中被己基硫烷基链八取代的两个铜酞菁进行了详细的结构-性质分析。和非外围（Cu-NP）位置。Cu-NP与Cu-P相比显示出明显的近红外最大吸收，因此，通过气相中的电化学结果和模拟计算得出的HOMO-LUMO能隙以及从晶体学分析得出的Cu-NP的能隙更小数据。电子自旋共振（ESR）技术用于提取g在室温下从粉末光谱中获得的值。所述克测定值是克∥ = 2.160和克⊥ = 2.045对于Cu-P合金和克∥ = 2.150和克⊥为= 2.050的Cu-NP。这些值表明，在这两种酞菁顺磁性铜中心带有一个具有平面各向异性轴对称（克∥ >克⊥）。仅对于Cu-P可获得溶液中的ESR光谱。居里定律用于拟合磁化率与温度关系图的实验数据，以及居里常数（C）和抗磁/温度无关的顺磁（α）贡献分别推论为Cu-P和0.37598（0.39576）cm 3 ·K / mol和−23×10 –5（25×10 –5）cm 3 / mol铜-NP。室温磁矩值（1.70μ乙）接近的唯一自旋值（1.73μ乙用于外围复合物），这表明存在于μ没有轨道贡献EFF。与此相反，在室温下，磁矩（1.77μ的值乙）高于仅自旋值，表示对磁矩轨道贡献。铜NP的室温磁矩值大于Cu-P的值，表明轨道对磁矩的贡献取决于取代基的位置。有效磁矩值的大小也支持Cu-P和Cu-NP配合物都具有正方形-平面配位。该结果与确定的g值一致。实验确定了自旋密度，结果表明取代基的位置会影响这些值（Cu-P为0.469 ，Cu-NP为0.490 ）。
更新日期：2018-05-16
中文翻译：
取代模式（外围与非外围）对八亚乙基硫烷基铜酞菁的光谱，电化学和磁性的影响
为了研究取代位置对铜酞菁的光谱，电化学和磁性能的影响，通过检查分别在外围（Cu-P）中被己基硫烷基链八取代的两个铜酞菁进行了详细的结构-性质分析。和非外围（Cu-NP）位置。Cu-NP与Cu-P相比显示出明显的近红外最大吸收，因此，通过气相中的电化学结果和模拟计算得出的HOMO-LUMO能隙以及从晶体学分析得出的Cu-NP的能隙更小数据。电子自旋共振（ESR）技术用于提取g在室温下从粉末光谱中获得的值。所述克测定值是克∥ = 2.160和克⊥ = 2.045对于Cu-P合金和克∥ = 2.150和克⊥为= 2.050的Cu-NP。这些值表明，在这两种酞菁顺磁性铜中心带有一个具有平面各向异性轴对称（克∥ >克⊥）。仅对于Cu-P可获得溶液中的ESR光谱。居里定律用于拟合磁化率与温度关系图的实验数据，以及居里常数（C）和抗磁/温度无关的顺磁（α）贡献分别推论为Cu-P和0.37598（0.39576）cm 3 ·K / mol和−23×10 –5（25×10 –5）cm 3 / mol铜-NP。室温磁矩值（1.70μ乙）接近的唯一自旋值（1.73μ乙用于外围复合物），这表明存在于μ没有轨道贡献EFF。与此相反，在室温下，磁矩（1.77μ的值乙）高于仅自旋值，表示对磁矩轨道贡献。铜NP的室温磁矩值大于Cu-P的值，表明轨道对磁矩的贡献取决于取代基的位置。有效磁矩值的大小也支持Cu-P和Cu-NP配合物都具有正方形-平面配位。该结果与确定的g值一致。实验确定了自旋密度，结果表明取代基的位置会影响这些值（Cu-P为0.469 ，Cu-NP为0.490 ）。
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