The UV spectra and their calculation of TCNQ and its mono- and di-valent anion

Jonkman, Harry T.; Kommandeur, Jan

doi:10.1016/0009-2614(72)80357-9

Cited by 145 publications

(86 citation statements)

References 12 publications

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“…For comparison purposes the gross charges found in the π-electron calculations of ref. [1] are included. Finally, table 5 shows the spin densities calculated for TCNQ -, i.e., the gross atomic populations corresponding to the open shell 3b 2g orbital.…”

Section: Resultsmentioning

confidence: 99%

“…To this end a number of ab initio closed and open shell restricted SCF calculations [4] were performed on the ground states and a variety of excited states of TCNQ + , TCNQ, TCNQ -and TCNQ 2-using the same structural parameters as in ref. [1](see also fig. 1).…”

Section: Introductionmentioning

confidence: 99%

“…1) and its mono-and divalent anions [1] by means of an SCF MO CI treatment of the π-electron system using the approximations proposed by Pariser, Parr and Pople (PPP) [2]. Since the physical properties of TCNQ in salts, particularly its electrical conductivity [3] continue to be of interest we decided to carry out a more detailed and less approximate theoretical investigation of the electronic wavefunctions.…”

Section: Introductionmentioning

confidence: 99%

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Ab initio SCF MO calculation of ionisation energies and charge distributions of TCNQ and its mono- and divalent anions

Jonkman

Velde

Nieuwpoort

1974

Chemical Physics Letters

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Ab initio SCF MO calculations using a contracted double zeta basis set of 168 gaussian type functions were performed on TCNQ + , TCNQ, TCNQ -and TCNQ 2-. The ionisation potentials obtained from total energy differences are generally 0.25-0.50 eV higher than the corresponding negative orbital energies from the TCNQ calculation and in satisfactory agreement with experimental results. The energy of the disproportionation reaction 2TCNQ -→ TCNQ + TCNQ 2-is calculated to be 4.62 eV. The charge distributions as measured by the gross atomic populations generally deviate from those obtained in earlier π-electron calculations as a consequence of taking the σ-electron distribution into account. The atomic charges are in good agreement with the limited experimental data available.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ab initio SCF MO calculation of ionisation energies and charge distributions of TCNQ and its mono- and divalent anions

Jonkman

Velde

Nieuwpoort

1974

Chemical Physics Letters

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“…In all four of the product spectra the neutral F4TCNQ absorption at 390 nm is absent, indicating that the reactions proceed in quantitative yield. The primary and secondary amines all show show similar product absorption peaks at about 3.7 eV (340 nm), while the tertiary amine (TEA) shows absorption bands corresponding to the radical anion, 40 indicative of the reaction shown in Figure 2e. Salts of tertiary amines including TEA:TCNQ have been studied extensively 41,42 and have not been observed to involve covalent bonds between the amine and TCNQ, consistent with our observations in TEA:F4TCNQ.…”

Section: ■ Experimental Sectionmentioning

confidence: 98%

Quantitative Dedoping of Conductive Polymers

Jacobs¹,

Wang²,

Hafezi³

et al. 2017

Chem. Mater.

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Although doping is a cornerstone of the inorganic semiconductor industry, most devices using organic semiconductors (OSCs) make use of intrinsic (undoped) materials. Recent work on OSC doping has focused on the use of dopants to modify a material’s physical properties, such as solubility, in addition to electronic and optical properties. However, if these effects are to be exploited in device manufacturing, a method for dedoping organic semiconductors is required. Here, we outline two chemical strategies for dedoping OSC films. In the first strategy, we use an electron donor (a tertiary amine) to act as competitive donor. This process is based on a thermodynamic equilibrium between ionization of the donor and OSC and results in only partial dedoping. In the second strategy, we use an electron donor that subsequently reacts with the p-type dopant to create a nondoping product molecule. Primary and secondary amines undergo a rapid addition reaction with the dopant molecule 2,3,5,6-tetrafluoro-7,7,8,8,-tetracyanoquinodimethane (F4TCNQ), with primary amines undergoing a further reaction eliminating HCN. Under optimized conditions, films of semiconducting polymer poly(3-hexylthiophene) (P3HT) dedoped with 1-propylamine (PA) reach as-cast fluorescence intensities within 5 s of exposure to the amine, eventually reaching 140% of the as-cast values. Field-effect mobilities similarly recover after dedoping. Quantitative fluorescence recovery is possible even in highly fluorescent polymers such as PFB, which are expected to be much more sensitive to residual dopants. Interestingly, treatment of undoped films with PA also yields increased fluorescence intensity and a reduction in conductivity of at least 2 orders of magnitude. These results indicate that the process quantitatively removes not only F4TCNQ but also intrinsic p-type impurities present in as-cast films. The dedoping strategies outlined in this article are generally applicable to other p- and n-type molecular dopants in OSC films.

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“…According to the literature (Hoekstra, Spoelder & Vos, 1972;Jonkman & Kommandeur, 1972) there is a relation between the bond lengths in a TCNQ group and its charge. By use of the method of Flandrois & Chasseau (1977) charges of-0.8 e and 0.0 e are calculated for nc and c respectively.…”

Section: The Tcnq Units and The Tcnq Stackmentioning

confidence: 99%

The crystal structure of the 2:3 complex of rubidium and 7,7,8,8-tetracyanoquinodimethane, Rb₂TCNQ₃, at 113 K

Wal¹,

Bodegom²

1979

Acta Crystallogr Sect B

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RbETCNQ3 [Rb2(Ct2H4N4) 3, C36H12N12Rb2] is isostructural with Cs2TCNQ3. The space group is P2~/c with a = 7.269 (2), b = 10.264 (3), c = 21.328 (6)/~, fl = 97.11 (2) ° , U = 1579.2 /~a and Z = 2. The intensities were collected at 113 K with Mo radiation on an automatic Nonius CAD-3 diffractometer. Anisotropic least-squares refinement decreased the weighted residual R e to 0.038 for 3631 observed reflexions. The TCNQ groups are stacked in columns along the b axis and lie either at inversion centers (groups c) or at general positions (groups nc) in the arrangement nc... c...nc...nc...c...nc.., etc. Comparison with the room-temperature structure shows that decreasing the temperature from 300 to 110 K gives the same percentage reduction in the nc...c and nc...nc distances. Rb ions also lie in linear arrays along b and are surrounded by edge-sharing cubes of eight N atoms. The cubes show an elongation in the stacking direction which is much more pronounced for the Rb than for the Cs salt. Within the TCNQ stack the shifts 'parallel' to the TCNQ planes do not depend on the temperature but quite strongly on the atomic radii, whereas the reverse is the case for the distances between the planes.

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The UV spectra and their calculation of TCNQ and its mono- and di-valent anion

Cited by 145 publications

References 12 publications

Ab initio SCF MO calculation of ionisation energies and charge distributions of TCNQ and its mono- and divalent anions

Ab initio SCF MO calculation of ionisation energies and charge distributions of TCNQ and its mono- and divalent anions

Quantitative Dedoping of Conductive Polymers

The crystal structure of the 2:3 complex of rubidium and 7,7,8,8-tetracyanoquinodimethane, Rb₂TCNQ₃, at 113 K

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The UV spectra and their calculation of TCNQ and its mono- and di-valent anion

Cited by 145 publications

References 12 publications

Ab initio SCF MO calculation of ionisation energies and charge distributions of TCNQ and its mono- and divalent anions

Ab initio SCF MO calculation of ionisation energies and charge distributions of TCNQ and its mono- and divalent anions

Quantitative Dedoping of Conductive Polymers

The crystal structure of the 2:3 complex of rubidium and 7,7,8,8-tetracyanoquinodimethane, Rb2TCNQ3, at 113 K

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About

The crystal structure of the 2:3 complex of rubidium and 7,7,8,8-tetracyanoquinodimethane, Rb₂TCNQ₃, at 113 K