Solvent controlled generation of spin active polarons in two-dimensional material under UV light irradiation

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Dátum

2024

Názov časopisu

ISSN časopisu

Názov zväzku

Vydavateľ

The American Chemical Society : Washington

ISBN

ISSN

0002-7863
1520-5126

Abstrakt

Polarons belong to a class of extensively studied quasiparticles that have found applications spanning diverse fields, including charge transport, colossal magnetoresistance, thermoelectricity, (multi)ferroism, optoelectronics, and photovoltaics. It is notable, though, that their interaction with the local environment has been overlooked so far. We report an unexpected phenomenon of the solvent-induced generation of polaronic spin active states in a two-dimensional (2D) material fluorographene under UV light. Furthermore, we present compelling evidence of the solvent-specific nature of this phenomenon. The generation of spin-active states is robust in acetone, moderate in benzene, and absent in cyclohexane. Continuous wave X-band electron paramagnetic resonance (EPR) spectroscopy experiments revealed a massive increase in the EPR signal for fluorographene dispersed in acetone under UV-light irradiation, while the system did not show any significant signal under dark conditions and without the solvent. The patterns appeared due to the generation of transient magnetic photoexcited states of polaronic character, which encompassed the net 1/2 spin moment detectable by EPR. Advanced ab initio calculations disclosed that polarons are plausibly formed at radical sites in fluorographene which interact strongly with acetone molecules in their vicinity. Additionally, we present a comprehensive scenario for multiplication of polaronic spin active species, highlighting the pivotal role of the photoinduced charge transfer from the solvent to the electrophilic radical centers in fluorographene. We believe that the solvent-tunable polaron formation with the use of UV light and an easily accessible 2D nanomaterial opens up a wide range of future applications, ranging from molecular sensing to magneto-optical devices.

Popis

In: Journal of the American Chemical Society. Washington : The American Chemical Society, 2024. ISSN 0002-7863. Vol. 146, no. 22 (2024), pp. 15010-15018.

Kľúčové slová

ultrafialové žiarenie, ožarovanie, ketóny, spektroskopia, spectroscopy

Výstup z projektu

GAČR GA22-33284S Horizon Europe - REA - HORIZONT-WIDERA-2021-ACCESS-03-01: 101079384 Single atom based nanohybrid photocatalyts for green fuels (SAN4Fuel) TAČR CZ.02.01.01/00/22_008/0004587 TECHSCALE: Technologie za hranicí nanosvěta Action CA21101 COST Confined molecular systems: From a new generation of materials to the stars (cosy) Ina CZ.10.03.01/00/22_003/0000048 REFRESH - Research Excellence For Region Sustainability and High-tech Industries Ministerstvo školstva, mládeže a telovýchovy ČR 90254 e-INFRA CZ

Citácia

Práva a licenčné podmienky

CC BY Creative Commons Attribution 4.0. International
info:eu-repo/semantics/openAccess