Solid-state study of the structure and host-guest chemistry of cucurbituril-ferrocene inclusion complexes

abstract

Inclusion complexes of ferrocene (Fc) with cucurbit[n]urils (n = 7, 8) have been prepared via a rapid microwave-assisted hydrothermal approach. Solids were isolated and characterised by elemental analysis, powder X-ray diffraction (PXRD), spectroscopic, and thermoanalytical methods. The UV-Vis spectra support the presence of Fc in Fc@CB7 and a mixture of Fc and ferrocenium ions in Fc@CB8. Partial oxidation of Fc to Fc(+) takes place in situ mainly due to the presence of acid of crystallisation in CB8. On the basis of PXRD, the complex Fc@CB8 is classified into an isostructural series that is formed by several CB8-containing compounds that crystallise in the space group /4(1)/a and have similar unit cell dimensions and CB8 packing motifs. The FT-IR and Raman spectra of Fc@CB7 are compared with those of the CB7 host and the Fc guest starting materials, revealing significant frequency shifts of some Fc-centered vibrational modes upon complexation. Blueshifts of the Fe-Cp stretching and ring tilt bands are attributed to encapsulation of Fc monomers in a constrained environment, leading to restricted motion effects and/or a change in the Fc conformation from staggered to eclipsed. The absence of comparable shifts for Fc@CB8 point to a weaker host-guest interaction as a consequence of the larger cavity size. The different host-guest interactions are also evident through a comparison of the C-13{H-1} CP MAS NMR spectra. Thermogravimetric analysis for the inclusion compounds reveals that sublimation of Fc is inhibited by molecular encapsulation to the extent that oxidative decomposition of the organoiron species takes place concurrently with cucurbituril decomposition, leading to the formation of hematite, alpha-Fe2O3.

keywords

MOLYBDENOCENE DICHLORIDE CP2MOCL2; ELECTRON-TRANSFER REACTIONS; BETA-CYCLODEXTRIN; METAL-COMPLEXES; ELECTROCHEMICAL PROPERTIES; ORGANOMETALLIC COMPLEXES; 2ND-SPHERE COORDINATION; POLYPYRIDYL COMPLEX; GAMMA-CYCLODEXTRIN; ACYLATION RATES

subject category

Chemistry

authors

Gomes, AC; Magalhaes, CIR; Oliveira, TSM; Lopes, AD; Goncalves, IS; Pillinger, M

our authors

acknowledgements

This work was developed in the scope of the project CICECO-Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 [FCT (Fundacao para a Ciencia e a Tecnologia) ref. UID/CTM/50011/2013], financed by national funds through the FCT/MEC and when applicable co-financed by FEDER (Fundo Europeu de Desenvolvimento Regional) under the PT2020 Partnership Agreement. The FCT and the European Union are acknowledged for a post-doctoral grant to A. C. G. (SFRH/BPD/108541/2015) co-funded by MCTES and the European Social Fund through the program POPH of QREN.

Share this project:

Related Publications

We use cookies for marketing activities and to offer you a better experience. By clicking “Accept Cookies” you agree with our cookie policy. Read about how we use cookies by clicking "Privacy and Cookie Policy".