The electronic properties of a charge-transfer (donor-acceptor) semiconducting organic co-crystal, Perylene:F4-TCNQ (PE:F4) (the donor, D, is PE and the acceptor, A, is 2,3,5,6-tetrafluoro-7,7,8,8 tetracyanoquinodimethane (F4)) in its 3 : 2 stoichiometry, are experimentally and theoretically studied. This is performed by means of electron paramagnetic resonance (EPR) and solid state electrochemical techniques, such as cyclic voltammetry (CV) measurements on single crystals. In particular, solid state electrochemistry proves to be an effective tool to probe, on a macroscopic scale, the electronic characteristics of the co-crystal. However, EPR highlights the presence of spin ½ radicals localized on F4 molecules, possibly linked to defects. The experimental findings are discussed on the basis of density functional theory (DFT) based calculations, carried out using both the projector augmented wave (PAW), with “periodic boundary conditions” (pbc), method and the localized orbitals, molecular cluster, approach. In particular, a satisfying agreement is found between the experimental, 0.336 eV (electrochemical), and theoretical, 0.303 eV (PAW), band gaps. Differences with the reported optical bandgap are discussed considering excitonic effects.

Charge transfer modulation in charge transfer co-crystals driven by crystal structure morphology / Solano, F.; Inaudi, P.; Abollino, O.; Giacomino, A.; Chiesa, M.; Salvadori, E.; Kociok-Kohn, G.; da Como, E.; Salzillo, T.; Fontanesi, C.. - In: PHYSICAL CHEMISTRY CHEMICAL PHYSICS. - ISSN 1463-9076. - 24:31(2022), pp. 18816-18823. [10.1039/d2cp01408d]

Charge transfer modulation in charge transfer co-crystals driven by crystal structure morphology

Fontanesi C.
2022

Abstract

The electronic properties of a charge-transfer (donor-acceptor) semiconducting organic co-crystal, Perylene:F4-TCNQ (PE:F4) (the donor, D, is PE and the acceptor, A, is 2,3,5,6-tetrafluoro-7,7,8,8 tetracyanoquinodimethane (F4)) in its 3 : 2 stoichiometry, are experimentally and theoretically studied. This is performed by means of electron paramagnetic resonance (EPR) and solid state electrochemical techniques, such as cyclic voltammetry (CV) measurements on single crystals. In particular, solid state electrochemistry proves to be an effective tool to probe, on a macroscopic scale, the electronic characteristics of the co-crystal. However, EPR highlights the presence of spin ½ radicals localized on F4 molecules, possibly linked to defects. The experimental findings are discussed on the basis of density functional theory (DFT) based calculations, carried out using both the projector augmented wave (PAW), with “periodic boundary conditions” (pbc), method and the localized orbitals, molecular cluster, approach. In particular, a satisfying agreement is found between the experimental, 0.336 eV (electrochemical), and theoretical, 0.303 eV (PAW), band gaps. Differences with the reported optical bandgap are discussed considering excitonic effects.
24
31
18816
18823
Charge transfer modulation in charge transfer co-crystals driven by crystal structure morphology / Solano, F.; Inaudi, P.; Abollino, O.; Giacomino, A.; Chiesa, M.; Salvadori, E.; Kociok-Kohn, G.; da Como, E.; Salzillo, T.; Fontanesi, C.. - In: PHYSICAL CHEMISTRY CHEMICAL PHYSICS. - ISSN 1463-9076. - 24:31(2022), pp. 18816-18823. [10.1039/d2cp01408d]
Solano, F.; Inaudi, P.; Abollino, O.; Giacomino, A.; Chiesa, M.; Salvadori, E.; Kociok-Kohn, G.; da Como, E.; Salzillo, T.; Fontanesi, C.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11380/1286007
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