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Ferrocene and ferrocenium inclusion compounds with cucurbiturils: A study of metal atom dynamics probed by Mössbauer spectroscopy

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Title
Ferrocene and ferrocenium inclusion compounds with cucurbiturils: A study of metal atom dynamics probed by Mössbauer spectroscopy
Author(s)
Clara I. R. Magalha˜es; Ana C. Gomes; Andre´ D. Lopes; Isabel S. Gonçalves; Martyn Pillinger; Eunyoung Jin; Ikjin Kim; Young Ho Ko; Kimoon Kim; Israel Nowik; Rolfe H. Herber
Publication Date
2017-08
Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, v.19, no.32, pp.21548 - 21555
Publisher
ROYAL SOC CHEMISTRY
Abstract
Temperature-dependent 57Fe Mössbauer effect (ME) spectroscopic studies were carried out on ferrocene (Fc), 1,1′-dimethylferrocene (1,1′(CH3)2Fc) and ferrocenium hexafluorophosphate (FcPF6) guest species in cucurbit[n]uril (n = 7, 8) inclusion complexes. The solid inclusion complexes were isolated by freeze-drying of dilute aqueous solutions and/or microwave-assisted precipitation from concentrated mixtures. The presence of genuine 1:1 (host:guest) inclusion complexes in the isolated solids was supported by liquid-state 1H and solid-state 13C{1H} MAS NMR, elemental and thermogravimetric analyses, powder X-ray diffraction, FTIR spectroscopy, and diffuse reflectance UV-Vis spectroscopy. The ME spectra of the complexes CB7·Fc and CB7·1,1′(CH3)2Fc consist of well-resolved doublets with hyperfine parameters (isomer shift and quadrupole splitting at 90 K) and temperature-dependent recoil-free fraction data that are very similar to those for the neat parent compounds, Fc and 1,1′(CH3)2Fc, suggesting that the organometallic guest molecules do not interact significantly with the host environment over the experimental temperature range. The ME spectra for CB7·FcPF6 and CB8·FcPF6 consist of a major broad line resonance attributed to a paramagnetic FeIII site. From the temperature-dependence of the recoil-free fraction it is evident that the charged guest species in these systems interact with the host environment significantly more strongly than was observed in the case of the neutral guest species, Fc and 1,1′(CH3)2Fc. Moreover, the ME data indicate that the vibrational amplitude of the ferrocenium guest molecule is significantly larger in the CB8 host molecule than in the CB7 homologue, as expected on the basis of the different cavity sizes. © the Owner Societies 2017
URI
https://pr.ibs.re.kr/handle/8788114/3874
ISSN
1463-9076
Appears in Collections:
Center for Self-assembly and Complexity(복잡계 자기조립 연구단) > Journal Papers (저널논문)
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