Zhang Yuexing, Cai Xue, Yao Ping, Xu Hui, Bian Yongzhong, Jiang Jianzhuang
Key Lab for Colloid and Interface Chemistry of Education Ministry, Department of Chemistry, Shandong University, Jinan 250100, PR China.
Chemistry. 2007;13(34):9503-14. doi: 10.1002/chem.200700132.
The location of the hole and acid proton in neutral nonprotonated and protonated mixed (phthalocyaninato)(porphyrinato) yttrium double-decker complexes, respectively, is studied on the basis of density functional theory (DFT) calculations on the molecular structures, molecular orbitals, atomic charges, and electronic absorption and infrared spectra of the neutral, reduced, and two possible protonated species of a mixed (phthalocyaninato)(porphyrinato) yttrium compound: [(Pc)Y(Por)], [(Pc)Y(Por)]-, [(HPc)Y(Por)], and [(Pc)Y(HPor)], respectively. When the neutral [(Pc)Y(Por)] is reduced to [(Pc)Y(Por)]-, the calculated results on the molecular structure, atomic charge, and electronic absorption and infrared spectra show that the added electron has more influence on the Pc ring than on its Por counterpart, suggesting that the location of the hole is on the Pc ring in neutral [(Pc)Y(Por)]. Nevertheless, comparison of the calculation results on the structure, orbital composition, charge distribution, and electronic absorption and infrared spectra between [(HPc)Y(Por)] and [(Pc)Y(HPor)] leads to the conclusion that the acid proton in the protonated mixed (phthalocyaninato)(porphyrinato) yttrium compound should be localized on the Por ring rather than the Pc ring, despite the localization of the hole on the Pc ring in [(Pc)Y(Por)]. This result is in line with the trend revealed by comparative studies of the X-ray single-crystal molecular structures between [MIII{Pc(alpha-OC5H11)4}(TClPP)] and [M(III)H{Pc(alpha-OC5H11)4}(TClPP)] (H2TClPP=5,10,15,20-tetrakis(4-chlorophenyl)porphyrin; M=Sm, Eu). The present work not only represents the first systemic DFT study on the structures and properties of mixed (phthalocyaninato)(porphyrinato) yttrium double-decker complexes, but more importantly sheds further light on the nature of protonated bis(tetrapyrrole) rare-earth complexes.
基于对混合（酞菁基）（卟啉基）钇化合物的中性、还原态以及两种可能的质子化物种：[(Pc)Y(Por)]、[(Pc)Y(Por)]⁻、[(HPc)Y(Por)]和[(Pc)Y(HPor)]的分子结构、分子轨道、原子电荷以及电子吸收光谱和红外光谱的密度泛函理论（DFT）计算，分别研究了中性非质子化和质子化混合（酞菁基）（卟啉基）钇双层配合物中孔洞和酸性质子的位置。当中性的[(Pc)Y(Por)]还原为[(Pc)Y(Por)]⁻时，分子结构、原子电荷以及电子吸收光谱和红外光谱的计算结果表明，添加的电子对酞菁环的影响比对卟啉环的影响更大，这表明中性[(Pc)Y(Por)]中孔洞的位置在酞菁环上。然而，[(HPc)Y(Por)]和[(Pc)Y(HPor)]在结构、轨道组成、电荷分布以及电子吸收光谱和红外光谱方面的计算结果比较得出结论，质子化混合（酞菁基）（卟啉基）钇化合物中的酸性质子应定域在卟啉环上而非酞菁环上，尽管[(Pc)Y(Por)]中孔洞定域在酞菁环上。这一结果与[MIII{Pc(α - OC5H11)4}(TClPP)]和[M(III)H{Pc(α - OC5H11)4}(TClPP)]（H2TClPP = 5,10,15,20 - 四（4 - 氯苯基）卟啉；M = Sm, Eu）的X射线单晶分子结构比较研究揭示的趋势一致。本工作不仅是对混合（酞菁基）（卟啉基）钇双层配合物的结构和性质的首次系统性DFT研究，更重要的是进一步阐明了质子化双（四吡咯）稀土配合物的本质。
