EPR AND ENDOR STUDY OF SELECTED PORPHYRIN-COPPER AND PHTHALOCYANINE-COPPER COMPLEXES
EPR AND ENDOR STUDY OF SELECTED PORPHYRIN-COPPER AND PHTHALOCYANINE-COPPER COMPLEXES
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DOI：
10.1021/j100202a012
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发表时间：
1992-11-12
影响因子：
--
通讯作者：
KREILICK, RW
中科院分区：
文献类型：
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作者：
GREINER, SP;ROWLANDS, DL;KREILICK, RW
本文报道了四苯基卟啉、meso-四（2-甲基吡啶-N-基）卟啉（邻位）、meso-四（4-甲基吡啶-N-基）卟啉（帕拉）和酞菁铜配合物在4K左右的电子顺磁共振谱和氮ENDOR粉末谱。所有四个样本均显示轴对称。这三种卟啉的g（x）和g（y）值几乎相同（2.054，2.055），但它们的g1值不同（2.186，2.209，2.212）。酞菁铜具有等于2.060的轴向分量和2.179的z分量。CuTPP具有最大的轴向分量的铜超精细张量，98.6 MHz的值相比，从其他三个样品的80 MHz。铜超精细张量的z分量在CuTPP和铜酞菁的量值上更接近（631和637 MHz），而对于甲基吡啶类，其值为593 MHz（邻位）和598 MHz（帕拉）。通过分析这些数据，有助于每个ENDOR光谱的分子的取向很容易计算。氮超精细和四极张量的幅度通过分析的角度选择ENDOR光谱确定。氮超精细张量的最大组成部分被发现躺在沿着Cu-N键轴在每种情况下。
Electron paramagnetic resonance spectra and nitrogen ENDOR powder spectra have been obtained from copper complexes of tetraphenylporphyrin, meso-tetrakis(2-methylpyridinium-N-yl)porphyrin (ortho), meso-tetrakis(4-methylpyridinium-N-yl)porphyrin (para), and phthalocyanine at approximately 4 K. All four samples display axial symmetry. The three porphyrins have nearly identical g(x) and g(y) values (2.054, 2.055) but differ in their g, values (2.186, 2.209, 2.212). The copper phthalocyanine has axial components equal to 2.060 and a z component of 2.179. CuTPP has the largest axial component of the copper hyperfine tensor, 98.6 MHz compared with values from the other three samples of 80 MHz. The z component of the copper hyperfine tensor is closer in magnitude for CuTPP and copper phthalocyanine (631 and 637 MHz), while for the methylpyridyl species its value is 593 MHz (ortho) and 598 MHz (para). Through analysis of these data, the orientations of molecules contributing to each ENDOR spectrum are readily calculated. The magnitudes of the nitrogen hyperfine and quadrupolar tensors were determined through analysis of the angle-selected ENDOR spectra. The largest component of the nitrogen hyperfine tensor was found to lie along the Cu-N bond axis in each case.