Möbius Aromatic [28]Hexaphyrin Germanium(IV) and Tin(IV) Complexes: Efficient Formation of Triplet Excited States,Angewandte Chemie International Edition

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Möbius Aromatic [28]Hexaphyrin Germanium(IV) and Tin(IV) Complexes: Efficient Formation of Triplet Excited States
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2017-02-28 , DOI: 10.1002/anie.201700063
Mondo Izawa ₁ , Taeyeon Kim ₂ , Shin-ichiro Ishida ₁ , Takayuki Tanaka ₁ , Tadashi Mori ₃ , Dongho Kim ₂ , Atsuhiro Osuka ₁

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[28]Hexaphyrin Ge^IV and Sn^IV complexes were synthesized in high yields by reactions of [28]hexaphyrin with GeCl₄ or SnCl₄ in the presence of triethylamine. Both complexes display distinct 28π Möbius aromatic character and possess a trigonal bipyramidal geometry at the central Ge^IV or Sn^IV atom. The equatorial hydroxy group of the Ge^IV complex was smoothly exchanged with neutral nucleophiles, such as phenol derivatives and thiophenol, with retention of configuration. In the Sn^IV complex, intersystem crossing to the T₁ state is remarkably enhanced owing to the effective heavy‐atom effect, thus allowing the formation of the T₁ state in high yield. The T₁ states of the Ge^IV and Sn^VI complexes were found to be antiaromatic on the basis of the transient absorption features in line with the Baird rule.

中文翻译：

莫比乌斯族芳香族化合物[28]卟啉锗（IV）和锡（IV）配合物：三重态激发态的有效形成

[28]六氢卟啉Ge ^IV和Sn ^IV配合物是在三乙胺存在下，通过[28]六氢卟啉与GeCl ₄或SnCl ₄的反应高产率合成的。两种络合物均显示出独特的28πMöbius芳族特征，并在中心Ge ^IV或Sn ^IV原子处具有三角双锥体几何形状。Ge ^IV络合物的赤道羟基与中性亲核试剂（如苯酚衍生物和苯硫酚）平稳交换，并保留了构型。在Sn ^IV复合物中，系统间穿越到T ₁ 有效的重原子效应显着增强了铁基态，从而可以高收率形成T ₁态。根据符合Baird法则的瞬态吸收特征，发现 Ge ^IV和Sn ^VI配合物的T ₁状态是抗芳族的。

更新日期：2017-02-28

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