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首页> 外文期刊>Journal of the Chemical Society of Pakistan >Computational Study on the Effect of Axial Ligation Upon the Electronic Structure of Copper (II) Porphyrinate (CuTPPs = [5,10,15,20-tetrakis(N-methylpyridyl-4)porhinato]copper(II)tetratosylate)) - Electronic Structure with Different Axial Ligands
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Computational Study on the Effect of Axial Ligation Upon the Electronic Structure of Copper (II) Porphyrinate (CuTPPs = [5,10,15,20-tetrakis(N-methylpyridyl-4)porhinato]copper(II)tetratosylate)) - Electronic Structure with Different Axial Ligands

机译：轴向连接对卟啉铜（II）（CuTPPs = [5,10,15,20-四（N-甲基吡啶基-4）卟啉）铜（II）四甲苯磺酸盐）电子结构的影响的计算研究不同的轴向配体

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摘要

Copper porphyrins are generally known to show a less diverse reactivity as compared to their iron counterparts, both redox-wise and in terms of axial ligation. Reported here are density functional theory (DFT) results on models of copper (II)-porphyrins (models of [5,10,15,20-tetrakis(N-methylpyridyl-4)porhinato]copper(II)tetratosylate) with a set of axial ligands - nitrite (both the nitrogen-bound isomer and the oxygen-bound isomer, i.e., nitro and nitrito), imidazole, two forms of phenol (neutral and anionic), and water - related to an unexpected range of electronic structures detectable in electron paramagnetic resonance (EPR) spectra of a water-soluble copper porphyrin with water, nitrite, imidazole, dithionite, 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) (ABTS) and guaiacol. Computed spin densities and atomic charges reveal various degrees of influence of the axial ligands on the Cu-porphyrin electronic structure, which may be related to the notably different changes induced by each ligand (imidazole, nitrite, guaiacol and ABTS) on the EPR superhyperfine splitting, but with an unexpectedly strong dependence on choice of the computational methodology. Thus, at the B3LYP/6-31G** level the copper spin densities are predicted to range from 0.69 to 0.73 depending on the axial ligand, this contribution being located on the d(x2-y2) orbital in a range from 65% to 100%. BP86/DN** results tend to favor a distinctly larger spread of these values.
机译：铜卟啉与铁的对应物相比在氧化还原方式和轴向连接方面均表现出较低的反应性。此处报告的是对铜（II）-卟啉模型（[5,10,15,20-四（N-甲基吡啶基-4）卟啉]铜（II）四甲苯磺酸盐的模型）的密度泛函理论（DFT）结果轴向配体的亚硝酸盐（氮结合的异构体和氧结合的异构体，即硝基和亚硝基），咪唑，两种形式的苯酚（中性和阴离子）和水-与电子结构的意料不到的范围相关水，亚硝酸盐，咪唑，连二亚硫酸盐，2,2'-叠氮基双（3-乙基苯并噻唑啉-6-磺酸）（ABTS）和愈创木酚的水溶性铜卟啉的电子顺磁共振（EPR）光谱计算出的自旋密度和原子电荷揭示了轴向配体对Cu-卟啉电子结构的不同程度的影响，这可能与每种配体（咪唑，亚硝酸盐，愈创木酚和ABTS）在EPR超超细分裂中引起的显着不同变化有关。 ，但其对计算方法选择的依赖性出乎意料地强烈。因此，根据轴向配体，在B3LYP / 6-31G **水平上，铜自旋密度预计为0.69至0.73，该贡献位于d（x2-y2）轨道上，范围为65％至70％。 100％。 BP86 / DN **结果倾向于支持这些值的明显更大的分布。

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