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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Time-dependent density functional molecular orbital and excited state calculations on bis(porphyrinyl)butadiynes in the monocationic, neutral, monoanionic, and dianionic oxidation states
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Time-dependent density functional molecular orbital and excited state calculations on bis(porphyrinyl)butadiynes in the monocationic, neutral, monoanionic, and dianionic oxidation states

机译：双（卟啉基）丁二炔在单阳离子，中性，单阴离子和双阴离子氧化态下随时间变化的密度泛函分子轨道和激发态计算

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摘要

We report a theoretical study of the multiple oxidation states (1+, 0, 1-, and 2-) of a meso,meso-linked diporphyrin, namely bis[10,15,20-triphenylporphyrinatozinc(II)-5-yl]butadiyne (4), using Time-Dependent Density Functional Theory (TDDFT). The origin of electronic transitions of singlet excited states is discussed in comparison to experimental spectra for the corresponding oxidation states of the close analogue bis{10,15,20-tris[3',5'-di-tert-butylphenyl]porphyrinatozinc(II)-5-yl}butadiyne (3). The latter were measured in previous work under in situ spectroelectrochemical conditions. Excitation energies and orbital compositions of the excited states were obtained for these large delocalized aromatic radicals, which are unique examples of organic mixed-valence systems. The radical cations and anions of butadiyne-bridged diporphyrins such as 3 display characteristic electronic absorption bands in the near-IR region, which have been successfully predicted with use of these computational methods. The radicals are clearly of the "fully delocalized" or Class III type. The key spectral features of the neutral and dianionic states were also reproduced, although due to the large size of these molecules, quantitative agreement of energies with observations is not as good in the blue end of the visible region. The TDDFT calculations are largely in accord with a previous empirical model for the spectra, which was based simplistically on one-electron transitions among the eight key frontier orbitals of the C-4 (1,4-butadiyne) linked diporphyrins.
机译：我们报告了一个介观，中观联系的双卟啉，即双[10,15,20-triphenylporphyrinatozinc（II）-5-yl]的多个氧化态（1 +，0、1-和2-）的理论研究。丁二炔（4），使用时变密度泛函理论（TDDFT）。对比了类似的双{10,15,20-三[3'，5'-二叔丁基苯基]卟啉邻苯二酚（II）的相应氧化态的实验光谱，讨论了单线态激发态电子跃迁的起源）-5-基}丁二炔（3）。后者是在以前的工作中在原位光谱电化学条件下测量的。对于这些大的离域芳香族自由基，获得了激发态的激发能和轨道组成，这是有机混合价体系的独特实例。丁二炔桥联的双卟啉的自由基阳离子和阴离子（例如3个）在近红外区域显示了特征性的电子吸收带，已使用这些计算方法成功预测了这些吸收带。自由基显然是“完全离域”或III类的。还重现了中性和双阴离子状态的关键光谱特征，尽管由于这些分子的尺寸较大，在可见光区域的蓝色端，能量与观测值的定量吻合性不佳。 TDDFT计算在很大程度上与先前的光谱经验模型相符，该模型简单地基于C-4（1,4-丁二炔）连接的双卟啉的八个关键前沿轨道之间的单电子跃迁。

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