Geometry and Temperature Dependence of meso-Aryl Rotation in Strained Metalloporphyrins: Adjustable Turnstile Molecules

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• 作者：Zaichun Zhou ; Xi Zhang ; Qiuhua Liu ; Ziqiang Yan ; Chengjin Lv ; Ge Long
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：September 16, 2013
• 年：2013
• 卷：52
• 期：18
• 页码：10258-10263
• 全文大小：355K
• 年卷期：v.52,no.18(September 16, 2013)
• ISSN：1520-510X

文摘

The rotation of meso-aryl groups in porphyrins depends on the degree of macrocyclic distortion and is also influenced by the surrounding temperature. Dynamic NMR methods and crystal structures of series of nonplanar metalloporphyrins reveal that macrocyclic distortion lowers the rotational barrier by weakening the nonbinding interactions of neighboring groups, while increased temperature allows the rotational barrier to be overcome more readily. Two empirical methods are developed to acquire the rotational barrier. This type of strained molecule can act as an adjustable molecular turnstile through adjusting the degree of macrocyclic distortion and changing the surrounding temperature.