Charge transfer, proton transfer and clathrate compounds of dihydrotetracyanodiphenoquinodimethane (H2TCNDQ) having highly acidic protonsElectronic supplementary information (ESI) available: elemental analysis results for H2TCNDQ complexes. See http://www.rsc.org/suppdata/jm/b1/b109503j/

Nishimura, Kazukuni; Khasanov, Salavat S.; Saito, Gunzi

doi:10.1039/b109503j

Cited by 11 publications

(10 citation statements)

References 43 publications

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“…For the sake of accuracy improvement in both the predicted geometries and the electron-donor strength, which are the main key factors of the materials we are interested in, different computational approaches were applied. From the results summarized in Table , the 6-31G(d,p) basis set is found to yield an improved accuracy on the 6-31G(d) with both the B3LYP and PBE0 functionals showing good agreement with available experimental data for bisethylenedioxy-tetrathiafulvalene (BO) in both the neutral and charged , forms. One can find, however, that for both BO and ET (whose results are not shown here), the PBE0/6-31G(d,p) yields the most accurate structures.…”

Section: Computational Strategymentioning

confidence: 66%

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Design of Tetrathiafulvalene-Based Phosphazenes Combining a Good Electron-Donor Capacity and Possible Inclusion Adduct Formation (Part II)

Gahungu

Zhang

2007

J. Phys. Chem. C

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Physical properties of intercalated porous material can be modulated by intercalation of small molecules, as this was demonstrated through the iodine (I2) intercalation into tris(o-phenylenedioxy)cyclotriphosphazene (TPP) crystals. This work describes in depth theoretical considerations of TPP derivatives. The core ring [(NP)3] substitution by [(CO)3], [(CNH)3], and [(CS)3], as well as the side group modification in size and composition (containing tetrathiafulvalene-like fragments), is well described from the most important aspects as their geometry optimization, their highest occupied molecular orbital (HOMO)−lowest unoccupied molecular orbital (LUMO) consideration together with ionization potentials (IP), and their charged forms. On the basis of PBE0/6-31G(d,p) calculations, the neutral forms of the [(CO)3], [(CNH)3], and [(CS)3] containing derivatives are predicted in a distorted caplike conformation. In the first two series, planar (or nearly planar) conformations are predicted upon oxidation, while IP and HOMO energy calculation revealed an electron-donor strength better or comparable to that of the known tetrathiafulvalene (TTF)-like superconductors. Within the [(NP)3] based derivatives, the results show that the geometry of the central part may be influenced by the structure of the side fragment. Among the most interesting results, a number of derivatives are predicted to show a good electron-donor strength compared to the commonly used TTF-like donors. More interestingly, a larger number of [(NP)3] containing derivatives, especially the O/“NH”-substituted series, are found to combine the good electron-donor capacity and the “paddle wheel” molecular shape, making them good candidates for organic superconductors with the ease of modulating their conducting properties by intercalation of suitable acceptors.

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Section: Computational Strategymentioning

confidence: 66%

“…b Average of the optimized BO and BO + structures. c Crystal data from ref . d Crystal data from ref .…”

Section: Introductionmentioning

confidence: 99%

Design of Tetrathiafulvalene-Based Phosphazenes Combining a Good Electron-Donor Capacity and Possible Inclusion Adduct Formation (Part II)

Gahungu

Zhang

2007

J. Phys. Chem. C

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“…The spectra in both frequency regions are comparable to those observed for addition of 2.5 mM TFA in which weak characteristic bands for HF4TCNQ − begin to emerge between 0 and −0.10 V and coexist with bands characteristic of F4TCNQ 2− at potentials negative of −0.20 V. These experiments also follow with the known pK a values of H 2 F4TCNQ in DMF which have been reported to be 4.01 and 7.2 or the first and second protons, respectively. 34,35 The results of this experiment show that even relatively weak acids such as water can result in the formation of HF4TCNQ − .…”

Section: ■ Experimental Sectionmentioning

confidence: 80%

“…The doubly protonated species, H 2 TCNQ and H 2 F4TCNQ, have been well-characterized spectroscopically in the solid state, as they have been used as stable starting materials for the generation of supramolecular systems. 1,4,7,29−33 These species are diprotic systems (pK a1 = 4.01, pK a2 = 7.2 in DMF 34,35 ). Thus, it would be useful to fully characterize the spectroscopy of the singly protonated monoanion forms HTCNQ − or HF4TCNQ − to fully understand the range of chemistry accessible through this route.…”

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confidence: 99%

FTIR Spectroelectrochemistry of F4TCNQ Reduction Products and Their Protonated Forms

et al. 2020

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The tetrafluorinated derivative of 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), is of interest for charge transfer complex formation and as a p-dopant in organic electronic materials. Fourier transform infrared (FTIR) spectroscopy is commonly employed to understand the redox properties of F4TCNQ in the matrix of interest; specifically, the ν(CN) region of the F4TCNQ spectrum is exquisitely sensitive to the nature of the charge transfer between F4TCNQ and its matrix. However, little work has been done to understand how these vibrational modes change in the presence of possible acid/base chemistry. Here, FTIR spectroelectrochemistry is coupled with density functional theory spectral simulation for study of the electrochemically generated F4TCNQ radical anion and dianion species and their protonation products with acids. Vibrational modes of HF4TCNQ–, formed by proton-coupled electron transfer, are identified, and we demonstrate that this species is readily formed by strong acids, such as trifluoroacetic acid, and to a lesser extent, by weak acids, such as water. The implications of this chemistry for use of F4TCNQ as a p-dopant in organic electronic materials is discussed.

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“…The partial CT state can be predicted and controlled by (I D À E A ) or ÁE(DA) for a specific DA system, and the complex exhibits a low lying CT band below 5 Â 10 3 cm À1 . 249 concerning the charge and proton-transfer interactions (Chart 7).…”

Section: Conductors Of Charge Transfer Typementioning

confidence: 99%

Development of Conductive Organic Molecular Assemblies: Organic Metals, Superconductors, and Exotic Functional Materials

Saito¹,

Yoshida²

2007

Bulletin of the Chemical Society of Japan

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370

127

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Charge transfer, proton transfer and clathrate compounds of dihydrotetracyanodiphenoquinodimethane (H2TCNDQ) having highly acidic protonsElectronic supplementary information (ESI) available: elemental analysis results for H2TCNDQ complexes. See http://www.rsc.org/suppdata/jm/b1/b109503j/

Cited by 11 publications

References 43 publications

Design of Tetrathiafulvalene-Based Phosphazenes Combining a Good Electron-Donor Capacity and Possible Inclusion Adduct Formation (Part II)

Design of Tetrathiafulvalene-Based Phosphazenes Combining a Good Electron-Donor Capacity and Possible Inclusion Adduct Formation (Part II)

FTIR Spectroelectrochemistry of F4TCNQ Reduction Products and Their Protonated Forms

Development of Conductive Organic Molecular Assemblies: Organic Metals, Superconductors, and Exotic Functional Materials

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