A1 Journal article (refereed)
A conformationally adaptive macrocycle : conformational complexity and host–guest chemistry of zorb[4]arene (2018)

Yang, L.-P., Lu, S.-B., Valkonen, A., Pan, F., Rissanen, K., & Jiang, W. (2018). A conformationally adaptive macrocycle : conformational complexity and host–guest chemistry of zorb[4]arene. Beilstein Journal of Organic Chemistry, 14(2018), 1570-1577. https://doi.org/10.3762/bjoc.14.134

JYU authors or editors

Valkonen, Arto
Rissanen, Kari

Publication details

All authors or editors: Yang, Liu-Pan; Lu, Song-Bo; Valkonen, Arto; Pan, Fangfang; Rissanen, Kari; Jiang, Wei

Journal or series: Beilstein Journal of Organic Chemistry

ISSN: 2195-951X

eISSN: 1860-5397

Publication year: 2018

Volume: 14

Issue number: 2018

Pages range: 1570-1577

Publisher: Beilstein-Institut zur Foerderung der Chemischen Wissenschaften

Publication country: Germany

Publication language: English

DOI: https://doi.org/10.3762/bjoc.14.134

Publication open access: Openly available

Publication channel open access: Open Access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/58829

Abstract

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-O-ethoxyzorb[4]arene (ZB4). Similar to per-O-ethoxyoxatub[4]arene, ZB4 is capable of accommodating a wide range of organic cations. However, ZB4 does not show large amplitude conformational responses to the electronic substituents on the guests. Instead of a linear free-energy relationship, ZB4 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 (ΔCp) 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 ZB4 and lays the basis for the construction of stimuli-responsive materials with ZB4 as a major component.

Keywords: supramolecular chemistry

Free keywords: conformations; host-guest chemistry; macrocycles; zorb[4]arene

Fields of science: