A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
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-tekijät tai -toimittajat

Valkonen, Arto
Rissanen, Kari

Julkaisun tiedot

Julkaisun kaikki tekijät tai toimittajat: Yang, Liu-Pan; Lu, Song-Bo; Valkonen, Arto; Pan, Fangfang; Rissanen, Kari; Jiang, Wei

Lehti tai sarja: Beilstein Journal of Organic Chemistry

ISSN: 2195-951X

eISSN: 1860-5397

Julkaisuvuosi: 2018

Volyymi: 14

Lehden numero: 2018

Artikkelin sivunumerot: 1570-1577

Kustantaja: Beilstein-Institut zur Foerderung der Chemischen Wissenschaften

Julkaisumaa: Saksa

Julkaisun kieli: englanti

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

Julkaisun avoin saatavuus: Avoimesti saatavilla

Julkaisukanavan avoin saatavuus: Kokonaan avoin julkaisukanava

Julkaisu on rinnakkaistallennettu (JYX): https://jyx.jyu.fi/handle/123456789/58829

Tiivistelmä

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.

YSO-asiasanat: supramolekulaarinen kemia

Vapaat asiasanat: conformations; host-guest chemistry; macrocycles; zorb[4]arene

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