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

Federica Solano; Paolo Inaudi; Ornella Abollino; Agnese Giacomino; Mario Chiesa; Enrico Salvadori; Gabriele Kociok-Kohn; Enrico da Como; Tommaso Salzillo; Claudio Fontanesi

doi:10.1039/D2CP01408D

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

Federica Solano,^a Paolo Inaudi,

*^a Ornella Abollino,

^a Agnese Giacomino,

^a Mario Chiesa,

^b Enrico Salvadori,

^b Gabriele Kociok-Kohn,^c Enrico da Como,

*^d Tommaso Salzillo

^e and Claudio Fontanesi

*^fg

Author affiliations

* Corresponding authors

^a Department of Drug Science and Technology, University of Torino, Via Giuria 9, Torino, Italy

^b Department of Chemistry, University of Torino, Via Giuria 5, Torino, Italy

^c Material and Chemical Characterization Facility (MC2), University of Bath, Claverton Down, Bath, UK

^d Department of Physics, University of Bath, UK

^e Department of Industrial Chemistry, “Toso Montanari”, University of Bologna, Viale del Risorgimento 4, Bologna, Italy

^f University of Modena and Reggio Emilia, DIEF, via Vivarelli 10, Modena, Italy
E-mail: claudio.fontanesi@unimore.it

^g National Interuniversity Consortium of Materials Science and Technology (INSTM), Via G. Giusti 9, Firenze, FI, Italy

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.

Physical Chemistry Chemical Physics

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

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

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