Structure, Stoichiometry, and Charge Transfer in Cocrystals of Perylene with TCNQ-Fx

• DOI: 10.1021/acs.cgd.5b01663
• Publication Date: 2016-04-14T18:54:13Z
• Authors: Tommaso Salzillo; Matteo Masino; Gabriele Kociok-Köhn; Daniele Di Nuzzo; Elisabetta Venuti; Raffaele Guido De...; Davide Vanossi; Claudio Fontanesi; Alberto Girlando; Aldo Brillante; Enrico Da Como
• Keywords: Chemistry (all); Materials Science (all); Condensed Matter Physics; SOLID-STATE STRUCTURE; SINGLE-CRYSTALS; ORGANIC SEMICONDUCTORS; MOLECULAR-STRUCTURE; MICROSCOPIC PARAMETERS; TRANSFER COMPLEXES; PHASE-TRANSITION; OPTICAL-SPECTRA; RAMAN-SPECTRA; TRANSPORT; Ct crystals. Organic semiconductors; 02 engineering and technology; 540; 0210 nano-technology

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 ...