Reversibly Switchable Fluorescent Molecular Systems Based on Metallacarborane-Perylenediimide Conjugates
Parejo Bruque, Laura (Universitat Autònoma de Barcelona. Departament de Química)
Chaari, Mahdi (Institut de Ciència de Materials de Barcelona)
Santiago, Sara (Universitat Autònoma de Barcelona. Departament de Química)
Guirado López, Gonzalo (Universitat Autònoma de Barcelona. Departament de Química)
Teixidor, Francesc (Institut de Ciència de Materials de Barcelona)
Núñez, Rosario (Institut de Ciència de Materials de Barcelona)
Hernando Campos, Jordi (Universitat Autònoma de Barcelona. Departament de Química)

Additional title:	Novel reversibly switchable fluorescent molecular systems based on metallacarborane-perylenediimide conjugates
Date:	2021
Abstract:	Icosahedral metallacarboranes are θ-shaped anionic molecules in which two icosahedra share one vertex that is a metal center. The most remarkable of these compounds is the anionic cobalt-based metallacarborane [Co(CBH)], whose oxidation-reduction processes occur via an outer sphere electron process. This, along with its low density negative charge, makes [Co(CBH)] very appealing to participate in electron-transfer processes. In this work, [Co(CBH)] is tethered to a perylenediimide dye to produce the first examples of switchable luminescent molecules and materials based on metallacarboranes. In particular, the electronic communication of [Co(CBH)] with the appended chromophore unit in these compounds can be regulated upon application of redox stimuli, which allows the reversible modulation of the emitted fluorescence. As such, they behave as electrochemically-controlled fluorescent molecular switches in solution, which surpass the performance of previous systems based on conjugates of perylendiimides with ferrocene. Remarkably, they can form gels by treatment with appropriate mixtures of organic solvents, which result from the self-assembly of the cobaltabisdicarbollide-perylendiimide conjugates into 1D nanostructures. The interplay between dye π-stacking and metallacarborane electronic and steric interactions ultimately governs the supramolecular arrangement in these materials, which for one of the compounds prepared allows preserving the luminescent behavior in the gel state.
Grants:	Agencia Estatal de Investigación PID2019-106171RB-I00 Agencia Estatal de Investigación PID2019-106832RB-I00 Agència de Gestió d'Ajuts Universitaris i de Recerca 2017/SGR-465 Agència de Gestió d'Ajuts Universitaris i de Recerca 2017/SGR-1720 Agencia Estatal de Investigación CEX2019-000917-S
Note:	Altres ajuts: Universitat Autònoma de Barcelona predoctoral PIF fellowship
Rights:	Tots els drets reservats.
Language:	Anglès
Document:	Article ; recerca ; Versió acceptada per publicar
Published in:	Chemistry, Vol. 27, Issue 1 (January 2021) , p. 270-280, ISSN 1521-3765

DOI: 10.1002/chem.202002419
PMID: 32648595

Postprint 61 p, 3.4 MB

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Research literature > UAB research groups literature > Research Centres and Groups (research output) > Experimental sciences > Group in Electrochemistry, Photochemistry and Organic Reactivity (GEFRO)
Articles > Research articles
Articles > Published articles