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Published on: March 24, 2019
Geometry and temperature dependence of meso-aryl rotation in strained metalloporphyrins: adjustable turnstile
Zaichun Zhou1, Xi Zhang, Qiuhua Liu
1School of Chemistry and Chemical Engineering, Key Laboratory of Theoretical Chemistry and Molecular Simulation of Ministry of Education, and Hunan Provincial University Key Laboratory of QSAR/QSPR, Hunan University of Science and Technology , Xiangtan 411201, China.
Abstract:
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.
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