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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >DFT/TDDFT study of Lanthanide(III) mono- and bisporphyrin complexes
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DFT/TDDFT study of Lanthanide(III) mono- and bisporphyrin complexes

机译：DFT / TDDFT研究镧系元素（III）单和双卟啉配合物

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摘要

The electronic structure, molecular structure, and electronic spectra of lanthanide(III) mono- and bisporphyrin complexes are investigated using a DFT/TDDFT method. These complexes include YbP( acac), YbP2, [ YbP2](+), YbHP2, and [ YbP2](-) ( where P) porphine and acac) acetylacetonate). To shed some light on the origin of the out-of-plane displacement of Yb in YbP( acac), unligated model systems, namely, planar D-4h and distorted C-4v YbP, were calculated. For comparison, the calculations were also extended to include the (CeP2)-P-IV and [ (CeP2)-P-IV](+) systems. Even without an axial ligand, the lanthanide atom lies considerably above the porphyrin plane; the distortion of the YbP molecular structure from a planar D-4h to the nonplanar C-4v symmetry leads to a considerable energy lowering. The axial ligand makes the metal out-of-plane displacement even larger, and it also changes the redox properties of the lanthanide monoporphyrin. The ground-state configurations of YbP2 and YbHP2 were determined by considering several possible low-lying states. YbP2 is confirmed to be a single-hole radical. The special redox properties of the bisporphyrin complexes can well be accounted for by the calculated ionization potentials and electron affinities. The TDDFT results provide a clear description of the UV-vis and near-IR absorption spectra of the various lanthanide porphyrins.
机译：使用DFT / TDDFT方法研究了镧系元素（III）单和双卟啉配合物的电子结构，分子结构和电子光谱。这些络合物包括YbP（acac），YbP2，[YbP2]（+），YbHP2和[YbP2]（-）（其中P为吗啡和acac）乙酰丙酮酸盐。为了阐明YbP（acac）中Yb的平面外位移的起源，计算了未绑定的模型系统，即平面D-4h和扭曲的C-4v YbP。为了比较，计算也扩展到包括（CeP2）-P-IV和[（CeP2）-P-IV]（+）系统。即使没有轴向配体，镧系元素原子也位于卟啉平面的上方。 YbP分子结构从平面D-4h到非平面C-4v对称的扭曲导致能量显着降低。轴向配体使金属的面外位移更大，并且还改变了镧系单卟啉的氧化还原性质。 YbP2和YbHP2的基态配置是通过考虑几种可能的低洼状态确定的。确认YbP2为单孔自由基。双卟啉配合物的特殊氧化还原特性可以通过计算出的电离势和电子亲和力很好地解释。 TDDFT结果清楚地描述了各种镧系卟啉的紫外可见光谱和近红外吸收光谱。

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