A conformationally adaptive macrocycle: conformational complexity and host-guest chemistry of zorb[4]arene

• Published in: Beilstein journal of organic chemistry 2018-06, Vol.14 (1), p.1570-1577
• Main Authors: Yang, Liu-Pan, Lu, Song-Bo, Valkonen, Arto, Pan, Fangfang, Rissanen, Kari, Jiang, Wei
• Format: Article
• Language: English
• Subjects: Allosteric properties; Cations; Chemistry; conformations; Entropy; Free energy; Full Research Paper; Heat; host–guest chemistry; Hydrogen bonding; macrocycles; Signal transduction; Solvents; supramolecular chemistry; zorbarene
• ISSN: 1860-5397; 2195-951X; 1860-5397
• DOI: 10.3762/bjoc.14.134

Large amplitude conformational change is one of the features of biomolecular recognition and is also the basis for allosteric effects and signal transduction in functional biological systems. However, synthetic receptors with controllable conformational changes are rare. In this article, we present a thorough study on the host-guest chemistry of a conformationally adaptive macrocycle, namely per- -ethoxyzorb[4]arene ( ). Similar to per- -ethoxyoxatub[4]arene, is capable of accommodating a wide range of organic cations. However, does not show large amplitude conformational responses to the electronic substituents on the guests. Instead of a linear free-energy relationship, follows a parabolic free-energy relationship. This is explained by invoking the influence of secondary C-H···O hydrogen bonds on the primary cation···π interactions based on the information obtained from four representative crystal structures. In addition, heat capacity changes (Δ ) and enthalpy-entropy compensation phenomena both indicate that solvent reorganization is also involved during the binding. This research further deepens our understanding on the binding behavior of and lays the basis for the construction of stimuli-responsive materials with as a major component.