Through-space hopping transport in an iodine-doped perylene-based metal-organic framework

abstract

Electrically conductive metal-organic frameworks (MOFs) have emerged in the past few years as promising materials towards applications in (opto)electronics, electrocatalysis and energy storage, among others. One of the most common strategies for the design of conductive MOFs is based on the use of electroactive organic ligands and their partial oxidation/reduction to increase the number of charge carriers. Although perylene salts were reported as the first molecular conductors, they have been scarcely explored as building blocks for the construction of conductive MOFs. Herein we report the electrical conductivity enhancement of a microporous perylene-based MOF upon partial ligand oxidation by using two-probe single-crystal devices. The origin of the conductivity enhancement is rationalised by means of spectroscopic studies and quantum-chemical calculations, supporting a through-space hopping transport along the herringbone perylene packing. This study opens the way for the design of conductive MOFs based on perylene building blocks.

keywords

ELECTRICAL-CONDUCTIVITY; THIN-FILMS; FLUORESCENCE; POLYIODIDE; CONVERSION; PENTACENE; RELEASE; MOFS

subject category

Chemistry; Engineering; Science & Technology - Other Topics; Materials Science

authors

Valente, G; Esteve-Rochina, M; Paracana, A; Rodriguez-Dieguez, A; Choquesillo-Lazarte, D; Orti, E; Calbo, J; Ilkaeva, M; Mafra, L; Hernandez-Rodriguez, MA; Rocha, J; Alves, H; Souto, M

Groups

G1 - Porous Materials and Nanosystems
G2 - Photonic, Electronic and Magnetic Materials
G3 - Electrochemical Materials, Interfaces and Coatings

Projects

CICECO - Aveiro Institute of Materials (UIDB/50011/2020)

CICECO - Aveiro Institute of Materials (UIDP/50011/2020)

Redox-active Metal-Organic Frameworks as Electrode Materials for Lithium-Ion Batteries (RedoxMOFs)

acknowledgements

This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, Grants UIDB/50011/2020 and UIDP/50011/2020, financed by national funds through the FCT/MEC and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement. We thank FCT for funding the project PTDC/QUI-ELT/2593/2021. We acknowledge Spanish government (PID2020-119748GA-I00, funded by MICIN/AEI/10.13039/501100011033, and the Maria de Maeztu CEX2019-000919-M grant) and Generalitat Valenciana (GV/2021/027, GVPROMETEO2020-077). G. V. is grateful to FCT for a PhD grant (2020.08520.BD). A. P. is grateful to FCT for a PhD grant (2020.06159.BD). FCT is also acknowledged by M. I. for a Junior Researcher Position (CEECIND/00546/2018). We thank Celeste Azevedo for TGA and Raman measurements. We thank Prof. Luis Carlos and Prof. Carlos Brites (Phantom-G) for the use and assistance with spectrofluorimeter and quantum yield equipment. We thank Prof. Nikolai Sobolev for EPR measurements.