Exploring the Luminescence, Redox, and Magnetic Properties in a Multivariate Metal-Organic Radical Framework

resumo

Persistent neutral organic radicals are excellent building blocks for the design of functional molecular materials due to their unique electronic, magnetic, and optical properties. Among them, triphenylmethyl radical derivatives have attracted a lot of interest as luminescent doublet emitters. Although neutral organic radicals have been underexplored as linkers for building metal-organic frameworks (MOFs), they hold great potential as organic elements that could introduce additional electronic properties within these frameworks. Herein, we report the synthesis and characterization of a novel multicomponent metal-organic radical framework (PTMTCR@NR-Zn MORF), which is constructed from the combination of luminescent perchlorotriphenylmethyl tricarboxylic acid radical (PTMTC (R)) and nonemissive nonradical (PTMTCNR) organic linkers and Zn(II) ions. The PTMTCR@NR-Zn MORF structure is layered with microporous one-dimensional channels embedded within these layers. Kelvin probe force microscopy further confirmed the presence of both organic nonradical and radical linkers in the framework. The luminescence properties of the PTMTC (R) ligand (first studied in solution and in the solid state) were maintained in the radical-containing PTMTCR@NR-Zn MORF at room temperature as fluorescence solid-state quenching is suppressed thanks to the isolation of the luminescent radical linkers. In addition, magnetic and electrochemical properties were introduced to the framework due to the incorporation of the paramagnetic organic radical ligands. This work paves the way for the design of stimuli-responsive hybrid materials with tunable luminescence, electrochemical, and magnetic properties by the proper combination of closed- and open-shell organic linkers within the same framework.

palavras-chave

PRESSURE-INDUCED CONDUCTIVITY; COORDINATION POLYMERS; DONOR; PERSISTENT

categoria

Chemistry; Materials Science

autores

Valente, G; Ferreira, P; Hernández-Rodríguez, MA; Brites, CDS; Amaral, JS; Zelenovskii, P; Paz, FAA; Guieu, S; Rocha, J; Souto, M

Grupos

G1 - Materiais Porosos e Nanossistemas
G2 - Materiais Fotónicos, Eletrónicos e Magnéticos
G3 - Materiais Eletroquímicos, Interfaces e Revestimentos

Projectos

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

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

Associated Laboratory CICECO-Aveiro Institute of Materials (LA/P/0006/2020)

Rede Nacional de Ressonância Magnética Nuclear (PTNMR)

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

Molecular logic devices and computing based on luminescent materials actuated by physical inputs (LogicALL)

Collaboratory for Emerging Technologies, CoLab (EMERGING TECHNOLOGIES)

agradecimentos

This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020, UIDP/50011/2020, and LA/P/0006/2020, financed by national funds through the FCT/MEC (PIDDAC) and LAQV-REQUIMTE, UIDB/50006/2020. The NMR spectrometers are part of the National NMR Network (PTNMR) and are partially supported by Infrastructure Project No. 022161 (co-financed by FEDER through COMPETE 2020 and POCI, PORL, and FCT through PIDDAC). We also thank FCT for funding the PTDC/QUI-ELT/2593/2021 and LogicALL (PTDC/CTM-CTM/0298/2020) projects. This work has also received funding from the European Research Council (ERC) under the European Union's Horizon Europe Framework Programme (ERC-2021-Starting Grant, grant agreement no. 101039748-ELECTROCOFS). G.V. and P.F. are grateful to FCT for their PhD grants (2020.08520.BD and UI/BD/151049/2021, respectively). This study was also funded by the PRR-Plano de Recuperacao e Resiliencia and by the NextGenerationEU funds at the University of Aveiro through the scope of the Agenda for Business Innovation "New Generation Storage" (project no. 58 with the application C644936001-00000045). This work has received financial support from the Xunta de Galicia (Centro singular de investigacion de Galicia accreditation 2019-2022, ED431G 2019/03), the Oportunius program (Gain) and the European Union (European Regional Development Fund - ERDF).