Valence Electronic Structure and Charge Transfer in Tetrathiofulvalinium Tetracyanoquinodimethane (TTF-TCNQ) from Photoemission Spectroscopy

Grobman, W. D.; Pollak, R. A.; East̀man, D. E.; Maas, E.T.; Scott, B. A.

doi:10.1103/physrevlett.32.534

Cited by 156 publications

(52 citation statements)

References 10 publications

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“…4 shows N 1s spectra of the TMP-TCNQ complex and the corresponding spectrum of pure TCNQ (c). The latter spectrum is well-known [9,13,14,20], our spectrum agrees perfectly with the literature spectra. It shows a strong main peak E (width 0.95 eV FWHM) and a weaker signal F located 2.6 eV at higher binding energy.…”

Section: Spectra Of Solution-grown Co-crystalssupporting

confidence: 91%

Charge transfer in the novel donor–acceptor complexes tetra- and hexamethoxypyrene with tetracyanoquinodimethane studied by HAXPES

Medjanik

Gloskovskii

Kutnyakhov

et al. 2012

Journal of Electron Spectroscopy and Related Phenomena

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This article appeared in a journal published by Elsevier. The attached copy is furnished to the author for internal non-commercial research and education use, including for instruction at the authors institution and sharing with colleagues.Other uses, including reproduction and distribution, or selling or licensing copies, or posting to personal, institutional or third party websites are prohibited. The effect of charge transfer (CT) in complexes of the donors tetra-and hexamethoxyprene (TMP and HMP) with the classical acceptor tetracyanoquinodimethane (TCNQ) was studied using hard X-ray photoemission (HAXPES). Microcrystals of the complex were grown via vapour diffusion from donor-acceptor mixtures. The bulk sensitivity of HAXPES at a photon energy of 6 keV completely eliminates the problem of surface contamination for such delicate organic materials grown from solution. The donor molecules were produced using a novel synthesis route functionalizing polycyclic aromatic hydrocarbons at their periphery. For comparison, spectra were also taken from thin-film samples of the same compounds produced via co-deposition in UHV. Upon complex formation, the oxygen 1s core-level spectra (being a fingerprint of the methoxy-group of the donors) change from the single-line spectrum of pure HMP (TMP) to a spectrum with two distinct lines shifted by 1.4 (0.9) eV and 2.6 (2.3) eV with respect to the position of the oxygen 1s line of the pure donors. The nitrogen 1s spectra (being a fingerprint of the cyano-group in the acceptor) show two peaks as well with a corresponding shift of 0.9 eV and 2.0 eV in comparison with the leading line of pure TCNQ in opposite direction to the oxygen 1s spectra. These values are substantially larger than shifts in near edge X-ray absorption fine structure (NEXAFS) and ultraviolet photoelectron spectroscopy (UPS) spectra of the same complexes. The changes in the spectra are discussed in terms of the CT in the complexes. Residues of pure donor and acceptor materials in the microcrystal fractions of the complexes are evident from the presence of non-shifted lines. Peak-area analysis reveals that charge is transferred to a fraction of 60% of the molecules in the complexes.

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Section: Spectra Of Solution-grown Co-crystalssupporting

confidence: 91%

Charge transfer in the novel donor–acceptor complexes tetra- and hexamethoxypyrene with tetracyanoquinodimethane studied by HAXPES

Medjanik

Gloskovskii

Kutnyakhov

et al. 2012

Journal of Electron Spectroscopy and Related Phenomena

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“…In Table 6 we compare the average bond lengths and angles (mmm molecular symmetry) for the TCNQ species in (TMTTF)F3(TCNQ)2 and TTF-TCNQ with those compiled by Herbstein (1971) for TCNQ -1 and TCNQ -°'5. Whereas for TTF-TCNQ these dimensions suggest a charge between -0.5 and -1.0, consistent with photoemission studies (Butler, Ferraris, Bloch & Cowan, 1974;Grobman, Pollak, Eastman, Maas & Scott, 1974), it is clear that for the 1.3:2 TMTTF salt the geometry of TCNQ is in this context anomalous. In particular, the endocyclic carbon-carbon bond length of 1.393 (10) A is about 0.04 A longer, and the exocyclic carbon-carbon bond at least 0.01 A shorter, than in any of the other cases.…”

Section: Discussion Of the Crystal Structure (A) Molecular Geometry Osupporting

confidence: 57%

Crystal structure and diffuse X-ray scattering of the 1.3:2 salt of 4,4',5,5'-tetramethyl-Δ^2,2-bis-1,3-dithiole [TMTTF] and 7,7,8,8-tetracyano-p-quinodimethane [TCNQ], a nonstoichiometric quasi one-dimensional organic conductor

Kistenmacher¹,

Phillips²,

Cowan³

et al. 1976

Acta Crystallogr Sect B

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The diffraction properties of an unusual radical cation-radical anion salt of composition (TMTTF)I.a(TCNQ)2 [(CIoHI2S4)l.a(C12H4N4)2] have been studied by single-crystal X-ray methods.The diffraction patterns show a strong subcell of monoclinic symmetry, space group P2~/n, with a= 3-819(1), b= 13.021 (6), c= 34.827 (14)/~, fl= 91"68 (3) °, V= 1731.1 ,~a, Z= 2 (for the empirical formula 1.3:2), Dm = 1"43 (1), De= 1"433 g cm -3. Intensities for 2731 reflections with l>a(I)were collected by counter methods in this subcell. The structure was solved by conventional heavy-atom Patterson and Fourier methods and has been refined by full-matrix least-squares calculations to a final R value of 0.127. The final weighted R value and goodness-of-fit are 0.114 and 2.5, respectively. The subcell structure is dominated by homologous columns of cations and anions running parallel to the short a axis. The interplanar spacing in the TCNQ columns is small, 3.24 /~, while the spacing in the TMTTF columns is 3.59/~ and corresponds to about the expected van der Waals separation. Among the columns of molecular cations and anions are channels of TMTTF residues (0.6 per subcell). The end-to-end alignment of the TMTTF residues in these channels approximately parallels the a axis and the stacks of cations and anions. Oscillation photographs about the a axis show a set of diffuse layer lines with a period corresponding to 10/3a. These are interpreted as arising from an incipient Peierls distortion of the columns, the first observed in an organic system. The material is a semiconductor with a room temperature conductivity of order 10 .Q-~ cm-~

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“…On peut citer la spectroscopic optique (Torrance. Scott & Kaufman, 1975), I'ESCA (Grobman, Pollak, Eastman, Maas & Scott, 1974: Epstein. Lipari, Nielsen & Sandman, 1975, la diffusion des rayons X (Denoyer, Com+s, Garito & Heeger, 1975: Kagoshima.…”

Section: Lntroduetionunclassified

Longueurs de liaison et transfert de charge dans les sels du tétracyanoquinodiméthane (TCNQ)

Flandrois¹,

Chasseau²

1977

Acta Crystallogr B Struct Sci

197

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An examination of most of the known crystal structures of TCNQ salts is made in connexion with deter mining the amount of charge transfer. A method based on the bond lengths is shown to provide a sensitive test for determining this important quantity'. The charge distribution between different TCNQ molecules of the same compound can also be deduced. The results obtained are used to correlate the degree of charge with the occurrence of a hydrogen bond. the rotation of C(CN)z groups and the experimental values of dipolar splittings D and E.

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Valence Electronic Structure and Charge Transfer in Tetrathiofulvalinium Tetracyanoquinodimethane (TTF-TCNQ) from Photoemission Spectroscopy

Cited by 156 publications

References 10 publications

Charge transfer in the novel donor–acceptor complexes tetra- and hexamethoxypyrene with tetracyanoquinodimethane studied by HAXPES

Charge transfer in the novel donor–acceptor complexes tetra- and hexamethoxypyrene with tetracyanoquinodimethane studied by HAXPES

Crystal structure and diffuse X-ray scattering of the 1.3:2 salt of 4,4',5,5'-tetramethyl-Δ^2,2-bis-1,3-dithiole [TMTTF] and 7,7,8,8-tetracyano-p-quinodimethane [TCNQ], a nonstoichiometric quasi one-dimensional organic conductor

Longueurs de liaison et transfert de charge dans les sels du tétracyanoquinodiméthane (TCNQ)

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Valence Electronic Structure and Charge Transfer in Tetrathiofulvalinium Tetracyanoquinodimethane (TTF-TCNQ) from Photoemission Spectroscopy

Cited by 156 publications

References 10 publications

Charge transfer in the novel donor–acceptor complexes tetra- and hexamethoxypyrene with tetracyanoquinodimethane studied by HAXPES

Charge transfer in the novel donor–acceptor complexes tetra- and hexamethoxypyrene with tetracyanoquinodimethane studied by HAXPES

Crystal structure and diffuse X-ray scattering of the 1.3:2 salt of 4,4',5,5'-tetramethyl-Δ2,2-bis-1,3-dithiole [TMTTF] and 7,7,8,8-tetracyano-p-quinodimethane [TCNQ], a nonstoichiometric quasi one-dimensional organic conductor

Longueurs de liaison et transfert de charge dans les sels du tétracyanoquinodiméthane (TCNQ)

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Crystal structure and diffuse X-ray scattering of the 1.3:2 salt of 4,4',5,5'-tetramethyl-Δ^2,2-bis-1,3-dithiole [TMTTF] and 7,7,8,8-tetracyano-p-quinodimethane [TCNQ], a nonstoichiometric quasi one-dimensional organic conductor