The Stoichiometry of TCNQ-Based Organic Charge-Transfer Cocrystals (original) (raw)
Related papers
Journal of Solid State Chemistry, 2019
Two luminescent Charge Transfer (CT) cocrystals involving planar phenanthrene derivatives namely, formyl phenanthrene (FP) and acetyl phenanthrene (AP) as donors (D) and 1,2,4,5tetracyanobenzene (TCNB) as an acceptor (A) building block, are formed by molecular selfassembly. Detailed structural and spectroscopic measurements elucidated the mixed stack sequence DADAD in the CT cocrystals. The solid supramolecular architecture for both the cocrystals forms 2D sheet, supported by the extended network of C-H•••O, and C-H•••N hydrogen bonds as evidenced by the crystallographic observation. Interestingly, the two cocrystals display tunable emissions compared to the blue emissions of donor compounds, which correlate with the formation of excited CT state between the donor and acceptor motifs as a result of mixed stack orientation. The nature of the CT interactions in the two cocrystals was further explored by applying density functional theoretical (DFT) studies. Such a supramolecular cocrystal approach provides a facile platform towards the design of new luminescent two component CT complexes with desired functionalities. Table of content Two luminescent CT complexes have been fabricated based on the phenathrene derivative that showed tunable photophysical properties due to mixed sandwich motifs.
Structure, Stoichiometry, and Charge Transfer in Cocrystals of Perylene with TCNQ-Fx
Crystal Growth & Design, 2016
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-F 2 and TCNQ-F 4. We find structures with different stoichiometries. Namely, the system perylene:TCNQ-F 0 is found with ratios 1:1 and 3:1, while the systems perylene:TCNQ-F x (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 analyse the structural motifs taking into account the degree of charge transfer between the perylene donor and the TCNQ-F x acceptors and the optical gap determined
Structure and Transport Properties of the Charge-Transfer Salt Coronene−TCNQ
Chemistry of Materials
Coronene is a highly symmetric organic molecule whose molecular structure resembles a fragment of graphite. We have crystallized a charge-transfer complex based on coronene and TCNQ, and present crystal structure and transport properties. The complex adopts alternate stacking between coronene and TCNQ, and the charge-transfer was estimated to be of the order of 0.3 by the structure and IR analysis of TCNQ. This degree of chargetransfer is larger than those of other hydrocarbon based charge-transfer complexes reported. We find semiconductor behavior with an optical gap of 1.55 eV and a transport gap of 0.49 eV. The Child's law mobility is estimated to be 0.3 cm 2 /Vssthis along with the small transport gap suggests this compound might be attractive for device applications.
Advanced Electronic Materials, 2016
The organic charge-transfer (CT) complex dibenzotetrathiafulvalene-7,7,8,8tetracyanoquinodimethane (DBTTF-TCNQ) is found to crystallize in two polymorphs when grown by physical vapor transport: the known α-polymorph and a new structure, the β-polymorph. Structural and elemental analysis via selected area electron diffraction (SAED), X-ray photoelectron spectroscopy (XPS), and polarized IR spectroscopy reveal that the complexes have the same stoichiometry with a 1:1 donor:acceptor ratio, but exhibit unique unit cells. The structural variations result in significant differences in the optoelectronic properties of the crystals, as observed in our experiments and electronic-structure calculations. Raman spectroscopy shows that the α-polymorph has a degree of charge transfer of about 0.5e, while the β-polymorph is nearly neutral. Organic field-effect transistors fabricated on these crystals reveal that in the same device structure both polymorphs show ambipolar charge transport, but the α-polymorph exhibits electron-dominant transport while the β-polymorph is hole-dominant. Together, these measurements imply that the transport features result from differing donor-acceptor overlap and consequential varying in frontier molecular orbital mixing, as suggested theoretically for chargetransfer complexes.
Crystals
The 3:2 Charge Transfer (CT) co-crystal (Perylene)3(TCNQF1)2 is grown by the Physical Vapor Transport (PVT) method, and characterized structurally and spectroscopically. Infrared analysis of the charge sensitive modes reveals a low degree of charge transfer (less than 0.1) between donor and acceptor molecules. The crystal is isostructural to the other 3:2 CT crystals formed by Perylene with TCNQF2 and TCNQF4, whereas such stoichiometry and packing is not known for the CT crystals with non-fluorinated TCNQ. The analysis of the isostructural family of 3:2 Perylene–TCNQFx (x = 1,2,4) co-crystal put in evidence the role of weak F…HC bonding in stabilizing this type of structure
Crystal Growth & Design, 2019
A lightweight organic material, trans-4'-dimethylamino-4-nitro-α-cyanostilbene, exhibits notable charge carrier mobility (~10-4 cm 2 V-1 s-1). The non-centrosymmetric material also displays moderate second harmonic generation activity. This is one of the rarest examples of small organic materials displaying semiconductor characteristics. The charge-transfer pathway as elucidated via high-resolution single-crystal X-ray diffraction data based 'energy frameworks' and 'experimental charge density' analyses is assessed by measuring the charge carrier mobility using the space charge limited current technique on pure single-crystal diode devices. These advanced structural analyses clearly demonstrate that charge transport in organic crystals is purely governed by its molecular packing, especially the π-π stacking geometry. The balanced ambipolar charge transport behavior makes this highly soluble and thermally stable organic crystal promising for applications in optoelectronic devices. Moreover, this report introduces the crucial role of energy frameworks and charge density analyses for fundamental understanding of structure-property relationship in organic semiconductors.
Room-Temperature Ferroelectricity in an Organic Cocrystal
Angewandte Chemie (International ed. in English), 2018
Ferroelectric materials exhibit switchable remanent polarization due to reversible symmetry breaking under an applied electric field. Previous research has leveraged temperature-induced neutral-ionic transitions in charge-transfer (CT) cocrystals to access ferroelectrics that operate through displacement of molecules under an applied field. However, displacive ferroelectric behavior is rare in organic CT cocrystals and achieving a Curie temperature (T ) above ambient has been elusive. Here a cocrystal between acenaphthene and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane is presented that shows switchable remanent polarization at room temperature (T =68 °C). Raman spectroscopy, X-ray diffraction, and solid-state NMR spectroscopy indicate the ferroelectric behavior is facilitated by acenaphthene (AN) rotation, deviating from conventional design strategies for CT ferroelectrics. These findings highlight the relevance of non-CT interactions in the design of displacive ferroelect...
Advanced Materials, 2009
Organic conjugated compounds are envisaged as functional materials for fabricating devices able to drive low-cost, lowperformance consumer electronics. To reach this goal, however, a better understanding of their electrical behavior is needed. In this view, organic single crystals offer the interesting and unique opportunity to investigate the intrinsic electrical behavior of organic materials, excluding hopping phenomena due to grain boundaries and structural imperfections. Their structural asymmetry also allows the investigation of the correlation between their 3D order and their charge-transport characteristics. One useful investigation tool in this sense may be found in organic field-effect transistors (OFETs), which can provide precious information on the nature of the chargetransport phenomena in organic materials. Indeed, single-crystal organic transistors, where the active channel is a single crystal, exhibited up to now the best performances in terms of charge-carriers mobility, reaching time-of-flight (TOF)-measured values as high as 400 cm 2 V À1 s À1 , and FET-measured mobilities of several units, up to tens of cm 2 V À1 s À1 . In this light, macroscopic (millimeter-sized) self-standing crystals suitable for being manipulated and selectively deposited on any surface and in any position with respect to existing electrodes are very useful, and recent studies showed that macroscopic crystals of rubrene present 2D electrical anisotropy. For obtaining crystals suited for these investigations, vacuumbased methods are up to now the most exploited strategy. However, macroscopic organic crystals may be easily grown also from solution, permitting a considerable degree of control over the final crystal characteristics in terms of dimensions and of the developed crystallographic phase. The suitability of solution grown (SG) organic crystals for electronic studies has been recently confirmed by a report on dicyclohexyl-a-quaterthiophene single crystals. The crystals were grown from solution and used as active materials in FETs, demonstrating 2D electrical anisotropy even though in this case the studied crystals had dimensions in the micrometers domain, and an investigation of their electrical behavior in the third dimension was not presented.