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

Research output: Contribution to journalArticlepeer-review

4 Citations (SciVal)


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.

Original languageEnglish
Pages (from-to)18816-18823
Number of pages8
JournalPhysical Chemistry Chemical Physics
Issue number31
Early online date21 Jul 2022
Publication statusPublished - 21 Aug 2022

Bibliographical note

Funding Information:
C. F. gratefully thanks financial support from the Dipartimento di Ingegneria “Enzo Ferrari” (DIEF), UniMORE, FARD 2021 – linea di azione di tipo 3: “Materiali chirali per batterie al litio e celle a combustibile” and from the Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali (INSTM), fondi triennali: “INSTM21MOFONTANESI”.

ASJC Scopus subject areas

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry


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