A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
Chiral hemicucurbit[8]uril as an anion receptor: selectivity to size, shape and charge distribution (2017)

Kaabel, S., Adamson, J., Topic, F., Kiesilä, A., Kalenius, E., Öeren, M., Reimund, M., Prigorchenko, E., Lõokene, A., Reich, H. J., Rissanen, K., & Aav, R. (2017). Chiral hemicucurbit[8]uril as an anion receptor: selectivity to size, shape and charge distribution. Chemical Science, 8(3), 2184-2190. https://doi.org/10.1039/C6SC05058A

JYU-tekijät tai -toimittajat

Topic, Filip
Kalenius, Elina
Kiesilä, Anniina
Rissanen, Kari

Julkaisun tiedot

Julkaisun kaikki tekijät tai toimittajat: Kaabel, Sandra; Adamson, Jasper; Topic, Filip; Kiesilä, Anniina; Kalenius, Elina; Öeren, Mario; Reimund, Mart; Prigorchenko, Elena; Lõokene, Aivar; Reich, Hans J.; et al.

Lehti tai sarja: Chemical Science

ISSN: 2041-6520

eISSN: 2041-6539

Julkaisuvuosi: 2017

Volyymi: 8

Lehden numero: 3

Artikkelin sivunumerot: 2184-2190

Kustantaja: Royal Society of Chemistry

Julkaisumaa: Britannia

Julkaisun kieli: englanti

DOI: https://doi.org/10.1039/C6SC05058A

Julkaisun avoin saatavuus: Avoimesti saatavilla

Julkaisukanavan avoin saatavuus: Kokonaan avoin julkaisukanava

Julkaisu on rinnakkaistallennettu (JYX): https://jyx.jyu.fi/handle/123456789/66509

Tiivistelmä

A novel eight-membered macrocycle of the hemicucurbit[n]uril family, chiral (all-R)-cyclohexanohemicucurbit[8]uril (cycHC[8]) binds anions in a purely protic solvent with remarkable selectivity. The cycHC[8] portals open and close to fully encapsulate anions in a 1 : 1 ratio, resembling a molecular Pac-Man™. Comprehensive gas, solution and solid phase studies prove that the binding is governed by the size, shape and charge distribution of the bound anion. Gas phase studies show an order of SbF6− ≈ PF6− > ReO4− > ClO4− > SCN− > BF4− > HSO4− > CF3SO3− for anion complexation strength. An extensive crystallographic study reveals the preferred orientations of the anions within the octahedral cavity of cycHC[8] and highlights the importance of the size- and shape-matching between the anion and the receptor cavity. The solution studies show the strongest binding of the ideally fitting SbF6− anion, with an association constant of 2.5 × 105 M−1 in pure methanol. The symmetric, receptor cavity-matching charge distribution of the anions results in drastically stronger binding than in the case of anions with asymmetric charge distribution. Isothermal titration calorimetry (ITC) reveals the complexation to be exothermic and enthalpy-driven. The DFT calculations and VT-NMR studies confirmed that the complexation proceeds through a pre-complex formation while the exchange of methanol solvent with the anion is the rate-limiting step. The octameric cycHC[8] offers a unique example of template-controlled design of an electroneutral host for binding large anions in a competitive polar solvent.

YSO-asiasanat: valikoivuus

Vapaat asiasanat: macrocycles; hemicucurbituril; anion receptors

Liittyvät organisaatiot

Hankkeet, joissa julkaisu on tehty

OKM-raportointi: Kyllä

Raportointivuosi: 2017

JUFO-taso: 3