The design of metal-organic frameworks (MOFs) incorporating electroactive guest molecules in the pores has become a subject of great interest in order to obtain additional electrical functionalities within the framework while maintaining porosity. Understanding the charge-transfer (CT) process between the framework and the guest molecules is a crucial step towards the design of new electroactive MOFs. Herein, we present the encapsulation of fullerenes (C60) in a mesoporous tetrathiafulvalene (TTF)-based MOF. The CT process between the electron-acceptor C60 guest and the electron-donor TTF ligand is studied in detail by means of different spectroscopic techniques and density functional theory (DFT) calculations. Importantly, gas sorption measurements demonstrate that sorption capacity is maintained after encapsulation of fullerenes, whereas the electrical conductivity is increased by two orders of magnitude due to the CT interactions between C60 and the TTF-based framework.
Bibliographical noteFunding Information:
This work has been supported by the European Union (ERC-2016-CoG 724681-S-CAGE) and the Spanish MICINN (CTQ2017-89528-P). G.M.E. and M.S. thank MICINN for a Ramón y Cajal and a Juan de la Cierva-Formación fellowships, respectively. J.C. acknowledges the Generalitat Valenciana for the postdoctoral APOSTD/2017/081 fellowship. Via our membership of the UK's HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202), this work used the ARCHER UK National Supercomputing Service (http:// www.archer.ac.uk).
All Science Journal Classification (ASJC) codes
- Materials Science(all)
- Physics and Astronomy(all)
- Electrical and Electronic Engineering