Structure, stoichiometry, and charge transfer in cocrystals of perylene with TCNQ-Fx

Tommaso Salzillo, Matteo Masino, Gabriele Kociok-Kohn, Daniele Di Nuzzo, Elisabetta Venuti, Raffaele Guido Della Valle, Davide Vanossi, Claudio Fontanesi, Alberto Girlando, Aldo Brillante, Enrico Da Como

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Abstract

Semiconductor charge transfer (CT) cocrystals are an emerging class of molecular materials which combines the characteristics of the constituent molecules in order to tune physical properties. Cocrystals can exhibit polymorphism, but different stoichiometries of the donor-acceptor (DA) pair can also give different structures. In addition, the structures of the donor and acceptor as pristine compounds can influence the resulting cocrystal forms. We report a structural study on several CT cocrystals obtained by combining the polyaromatic hydrocarbon perylene with 7,7,8,8-tetracyanoquinodimethane (TCNQ) and its fluorinated derivatives having increasing electronegativity. This is achieved by varying the amount of fluorine substitution on the aromatic ring, with TCNQ-F2 and TCNQ-F4. We find structures with different stoichiometries. Namely, the system perylene:TCNQ-F0 is found with ratios 1:1 and 3:1, while the systems perylene:TCNQ-Fx (x = 2, 4) are found with ratios 1:1 and 3:2. We discuss the structures on the basis of the polymorphism of perylene as pure compound, and show that by a judicious choice of growth temperature the crystal structure can be in principle designed a priori. We also analyze the structural motifs taking into account the degree of charge transfer between the perylene donor and the TCNQ-Fx acceptors and the optical gap determined from infrared (IR) spectroscopy. This family of materials exhibits tunable optical gaps in the near-IR (NIR), promising applications in organic optoelectronics.

Original languageEnglish
Pages (from-to)3028-3036
Number of pages9
JournalCrystal Growth and Design
Volume16
Issue number5
Early online date14 Apr 2016
DOIs
Publication statusPublished - 4 May 2016

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Perylene
Stoichiometry
Charge transfer
stoichiometry
polymorphism
charge transfer
Polymorphism
Electronegativity
Growth temperature
Fluorine
Optoelectronic devices
fluorine
Infrared spectroscopy
emerging
Substitution reactions
Physical properties
hydrocarbons
physical properties
Crystal structure
Hydrocarbons

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Structure, stoichiometry, and charge transfer in cocrystals of perylene with TCNQ-Fx. / Salzillo, Tommaso; Masino, Matteo; Kociok-Kohn, Gabriele; Di Nuzzo, Daniele; Venuti, Elisabetta; Della Valle, Raffaele Guido; Vanossi, Davide; Fontanesi, Claudio; Girlando, Alberto; Brillante, Aldo; Da Como, Enrico.

In: Crystal Growth and Design, Vol. 16, No. 5, 04.05.2016, p. 3028-3036.

Research output: Contribution to journalArticle

Salzillo, T, Masino, M, Kociok-Kohn, G, Di Nuzzo, D, Venuti, E, Della Valle, RG, Vanossi, D, Fontanesi, C, Girlando, A, Brillante, A & Da Como, E 2016, 'Structure, stoichiometry, and charge transfer in cocrystals of perylene with TCNQ-Fx', Crystal Growth and Design, vol. 16, no. 5, pp. 3028-3036. https://doi.org/10.1021/acs.cgd.5b01663
Salzillo, Tommaso ; Masino, Matteo ; Kociok-Kohn, Gabriele ; Di Nuzzo, Daniele ; Venuti, Elisabetta ; Della Valle, Raffaele Guido ; Vanossi, Davide ; Fontanesi, Claudio ; Girlando, Alberto ; Brillante, Aldo ; Da Como, Enrico. / Structure, stoichiometry, and charge transfer in cocrystals of perylene with TCNQ-Fx. In: Crystal Growth and Design. 2016 ; Vol. 16, No. 5. pp. 3028-3036.
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AU - Di Nuzzo, Daniele

AU - Venuti, Elisabetta

AU - Della Valle, Raffaele Guido

AU - Vanossi, Davide

AU - Fontanesi, Claudio

AU - Girlando, Alberto

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