Crystal Structures for the Electron Donor Dibenzotetrathiafulavalene, DBTTF, and Its Mixed-stack Charge-transfer Salts with the Electron Acceptors 7,7,8,8-tetracyano-<i>p</i>-quinodimethane, TCNQ, and 2,5-difluoro-7,7,8,8-tetracyano-<i>p</i>-quinodimethane, 2,5-TCNQF2

Emge, Thomas J.; Wiygul, F. Mitchell; Chappell, J.S.; Bloch, A. N.; Ferraris, John P.; Cowan, Dwaine O.; Kistenmacher, Thomas J.

doi:10.1080/00268948208083778

Cited by 82 publications

(21 citation statements)

References 53 publications

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“…The SAED results for the two DBTTF-TCNQ polymorphs are shown in Figure 2. The parameters for the α-polymorph (Figure 2a) are similar to the triclinic unit cell reported by Kobayashi, et al , where the space-group is P 1̄ [26,27] . Earlier SAED measurements on microrods of DBTTF-TCNQ exhibited a unit cell structure similar to the α-polymorph discussed here [33] .…”

Section: Resultssupporting

confidence: 79%

“…These form an excellent system for the study of the effect of D/A interactions on the optical properties and charge transport in CT complexes because the constituent molecules are exactly the same, but variations in their molecular packing result in different functionality. We will refer to the known, triclinic polymorph as the α-polymorph [25–27] . Crystals of this structure adopt a rectangular shape (Figure 1c), whereas the crystals of the new, previously-unreported polymorph (which we will call the β-polymorph), are elliptical in shape (Figure 1d).…”

Section: Introductionmentioning

confidence: 99%

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Polymorphism in the 1:1 Charge‐Transfer Complex DBTTF–TCNQ and Its Effects on Optical and Electronic Properties

Goetz

Tsutsumi

Pookpanratana

et al. 2016

Adv Elect Materials

106

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The organic charge-transfer (CT) complex dibenzotetrathiafulvalene – 7,7,8,8-tetracyanoquinodimethane (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 charge-transfer complexes.

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Section: Resultssupporting

confidence: 79%

Section: Introductionmentioning

confidence: 99%

Polymorphism in the 1:1 Charge‐Transfer Complex DBTTF–TCNQ and Its Effects on Optical and Electronic Properties

Goetz

Tsutsumi

Pookpanratana

et al. 2016

Adv Elect Materials

106

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“…5(c)). This distance is shorter than that in the case of DBTTF where no intermolecular interaction exists [3]. Intermolecular atomic distances less than vdW distance are seen at 0(3)-H(17B) (2.36 A:…”

Section: Atomscontrasting

confidence: 45%

Syntheses and Crystal Structures of DBTTF Derivatives Substituted Unsymmetrically by Electron Donating Groups: (MeO)₂(MDO) DBTTF, (EDO) (MDO) DBTTF and (MeO)₂(EDO) DBTTF

Inayoshi

Sato

Miyazaki

et al. 1998

Molecular Crystals and Liquid Crystals Science and Technology.

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Three novel unsymmetrically substituted DBTTF derivatives, (MeO)z (MDO) DBTTF, (EDO) (MDO) DBTTF, and (MeO)z (EDO) DBTTF, have been synthesized and their physicochemical properties are elucidated. Here, MeO, MDO, and E D 0 mean methoxy, methylenedioxy, and ethylenedioxy groups, respectively. Trimethylaluminum is found to be suitable for the syntheses of the above DBTTF derivatives using the non-coupling method. MDO is rather an effective substituent in reducing the difference between the first and the second redox potentials. The crystal structures of (MeO)z (MDO) D B m F and (Me0)2 (EDO) DBTTF were analyzed by an X-ray crystal structure analysis. In the crystal of (MeO)z (MDO) DBTTF, two molecules form a face-to-face pair, in which two molecules arrange so as to cancel their dipole moments to each other. The molecules of (Me0)z (EDO) DBTTF form a herringbone column structure in the crystal. Intermolecular short S . 4 atomic contacts are not found in the crystals of ( M e 0 )~ (MDO) DBTTF and (MeO)z ( E M ) DBTTF. However, intermolecular interactions through C-C and C -0 atomic contacts, and hydrogen bondings are recognized.

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“…Electronic-structure calculations on both pentacene (V polymorph with interlayer spacing of 14.1Å) [11] and DBTTF-TCNQ [12] have been performed on the basis of their experimental crystal structures. The impact of the %HF exchange has been investigated by using the αPerdew-Burke-Ernzerhof (αPBE) functional, based on the original PBE functional [13,14], following the simple hybrid scheme proposed by Adamo and Barone [15]:…”

Section: Computational Methodologymentioning

confidence: 99%

Impact of exact exchange in the description of the electronic structure of organic charge-transfer molecular crystals

et al. 2014

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We evaluate the impact that the amount of nonlocal Hartree-Fock (%HF) exchange included in a hybrid density functional has on the microscopic parameters (transfer integrals, band gaps, bandwidths, and effective masses) describing charge transport in high-mobility organic crystals. We consider both crystals based on a single molecule, such as pentacene, and crystals based on mixed-stack charge-transfer systems, such as dibenzo-TTF-TCNQ. In the pentacene crystal, the band gap decreases and the effective masses increase linearly with an increase in the amount of %HF exchange. In contrast, in the charge-transfer crystals, while the band gap increases linearly, the effective masses vary only slightly with an increase in %HF exchange. We show that the superexchange nature of the electronic couplings in charge-transfer systems is responsible for this peculiar evolution of the effective masses. We compare the density functional theory results with results obtained within the G 0 W 0 approximation as a way of benchmarking the optimal amount of %HF exchange needed in a given functional.

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Crystal Structures for the Electron Donor Dibenzotetrathiafulavalene, DBTTF, and Its Mixed-stack Charge-transfer Salts with the Electron Acceptors 7,7,8,8-tetracyano-p-quinodimethane, TCNQ, and 2,5-difluoro-7,7,8,8-tetracyano-p-quinodimethane, 2,5-TCNQF2

Cited by 82 publications

References 53 publications

Polymorphism in the 1:1 Charge‐Transfer Complex DBTTF–TCNQ and Its Effects on Optical and Electronic Properties

Polymorphism in the 1:1 Charge‐Transfer Complex DBTTF–TCNQ and Its Effects on Optical and Electronic Properties

Syntheses and Crystal Structures of DBTTF Derivatives Substituted Unsymmetrically by Electron Donating Groups: (MeO)₂(MDO) DBTTF, (EDO) (MDO) DBTTF and (MeO)₂(EDO) DBTTF

Impact of exact exchange in the description of the electronic structure of organic charge-transfer molecular crystals

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Crystal Structures for the Electron Donor Dibenzotetrathiafulavalene, DBTTF, and Its Mixed-stack Charge-transfer Salts with the Electron Acceptors 7,7,8,8-tetracyano-p-quinodimethane, TCNQ, and 2,5-difluoro-7,7,8,8-tetracyano-p-quinodimethane, 2,5-TCNQF2

Cited by 82 publications

References 53 publications

Polymorphism in the 1:1 Charge‐Transfer Complex DBTTF–TCNQ and Its Effects on Optical and Electronic Properties

Polymorphism in the 1:1 Charge‐Transfer Complex DBTTF–TCNQ and Its Effects on Optical and Electronic Properties

Syntheses and Crystal Structures of DBTTF Derivatives Substituted Unsymmetrically by Electron Donating Groups: (MeO)2(MDO) DBTTF, (EDO) (MDO) DBTTF and (MeO)2(EDO) DBTTF

Impact of exact exchange in the description of the electronic structure of organic charge-transfer molecular crystals

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Syntheses and Crystal Structures of DBTTF Derivatives Substituted Unsymmetrically by Electron Donating Groups: (MeO)₂(MDO) DBTTF, (EDO) (MDO) DBTTF and (MeO)₂(EDO) DBTTF