ic4001208_si_001.pdf (2.14 MB)
Geometry and Temperature Dependence of meso-Aryl Rotation in Strained Metalloporphyrins: Adjustable Turnstile Molecules
journal contribution
posted on 2016-02-18, 21:45 authored by Zaichun Zhou, Xi Zhang, Qiuhua Liu, Ziqiang Yan, Chengjin Lv, Ge LongThe
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.