Effect of Deuteration on the Infrared Characteristics of TCNQ-based Solid-Solid Charge-Transfer Systems

Ghezzal, E.; Brau, A.; Farges, J.; Dupuis, P.

doi:10.1080/10587259208025832

Cited by 11 publications

(2 citation statements)

References 6 publications

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“…The frequency values, especially the ν 50 band, are intermediate between the usual values of the neutral and mononegative TCNQ, suggesting that the acceptor has a formally nonintegral oxidation state. More noticeable is the fact that all these bands appear superimposed on a low-energy electronic absorption centered at 3180 cm -1 for compound 6 and at 3960 cm -1 for 7 and is attributed to a charge-transfer band (CT 2 ) between adjacent radical anionic and neutral TCNQ groups, a typical feature of the presence of partially reduced TCNQ stacks showing some degree of electronic delocalization . These compounds usually show a semiconducting behavior as observed by the room-temperature values of the electrical conductivity of 6 , 7.7 × 10 -4 S cm -1 , and 7 , 3.1 × 10 -4 S cm -1 .…”

Section: Resultssupporting

confidence: 86%

Hexaazamacrocyclic Nickel and Copper Complexes and their Reactivity with Tetracyanoquinodimethane

et al. 2007

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The hexaazamacrocycle 1,4,7,10,13,16-hexaazacyclooctadecane, [18]ane-N6, forms mono- and dinuclear derivatives with copper chloride depending on the reaction stoichiometries and times. The mononuclear derivative, [Cu([18]ane-N6)]Cl2.H2O, presents the macrocycle wrapped around the metal atom in a distorted octahedral coordinative environment, while the dinuclear derivative, [Cu2([18]ane-N6)Cl2]Cl2.4H2O, is formed by a central Cu2Cl2 core surrounded by an almost planar macrocycle. The crystal structure of both derivatives is stabilized by a network of hydrogen bonds involving the amine macrocyclic groups, the chloride anions, and the crystallization water molecules. The copper atoms in the dinuclear derivative show a strong antiferromagnetic coupling, as expected for the crystal structure parameters. A mononuclear nickel derivative has also been obtained from nickel nitrate by following the same synthetic procedure. These compounds react with TCNQ salts with formation of two types of derivatives, [M([18]ane-N6)](TCNQ)2 and [M([18]ane-N6)](TCNQ)4, depending on the use of radical-anionic or mixed-valence TCNQ salts in the reaction. The crystal structures of the nickel derivatives show that the former derivatives are built up by macrocyclic metal cations surrounded by dimeric dianions (TCNQ)22-, either isolated or stacked along the crystal. The derivative with four TCNQ units/formula consists of alternated chains of metallomacrocyclic cations and stacked TCNQ anions. The crystal parameters suggest that every TCNQ holds approximately 0.5 electrons and overlaps with a neighboring unit to form dimeric monoanions, (TCNQ)2-.

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Section: Resultssupporting

confidence: 86%

Hexaazamacrocyclic Nickel and Copper Complexes and their Reactivity with Tetracyanoquinodimethane

et al. 2007

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“…Optical Spectra. In consonance with the delocalization suggested by the conductivity values, the IR spectra of both compounds present a very broad electronic absorption centered around 3200 cm -1 with the TCNQ vibronic modes superimposed on it, a characteristic feature of derivatives showing electronic delocalization (Figure ) 5 IR spectrum in a KBr pellet of [Ni( cis -dieneN 4 )](TCNQ) 3 .…”

Section: Resultsmentioning

confidence: 99%

Delocalized TCNQ Stacks in Nickel and Copper Tetraazamacrocyclic Systems

Ballester¹,

Am²,

Gutiérrez³

et al. 2000

Inorg. Chem.

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New derivatives of formula [M(dieneN4)](TCNQ)3, M = Ni or Cu and dieneN4 = cis- or trans-hexamethyltetraazacyclotetradecadiene, have been obtained. The TCNQ units show electronic delocalization and formation of 1D stacks, with no direct interactions with the metal cations. The stack is not uniform and can be seen as formed by trimeric dianions (TCNQ)3(2-). The electronic delocalization favors the conductivity in these materials, which behave as good semiconductors. The crystal structures of the trans derivatives have been solved: [Ni(transdieneN4)](TCNQ)3, triclinic, P-1, a = 8.809(2) A, b = 10.896(2) A, c = 13.727(2) A, alpha = 103.04(1) degrees, beta = 101.23(2) degrees, gamma = 109.37(2) degrees, Z = 1; [Cu(trans-dieneN4)](TCNQ)3: triclinic, P-1, a = 7.872(1) A, b = 9.840(1) A, c = 14.819(1) A, alpha = 92.32(1) degrees, beta = 95.05(1) degrees, gamma = 95.66(1) degrees, Z = 1.

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Radical Ion Salts Obtained from Substituted Ferrocene Cations and the Organic Acceptor TCNQ − Synthesis, Structure and Physical Properties

et al. 2003

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The compounds [Fe(C5H5)(C5H4CH2NMe3)][TCNQ] (1), [Fe(C5H5)(C5H4CH2NMe3)][TCNQ]2.MeCN (2) and [Fe(C5H5)(C5H4CH=CH‐p‐C5H4NMe)][TCNQ] (3) have been obtained from reaction of the corresponding ferrocene iodide and TCNQ or LiTCNQ. Their crystal structures have been determined, showing that 1 and 3 have only mononegative TCNQ radicals forming one‐dimensional stacks. In compound 3 the pyridine substituent also overlaps with the stacked TCNQ. The formation reaction of 2 implies the reduction of neutral TCNQ by the iodide anion; in this reaction the reduction is partial and the formal charge of every TCNQ is approximately 0.5 e− with some degree of electron delocalization. The TCNQs also overlap to form a one‐dimensional stack in the solid. The three compounds are diamagnetic, indicating a strong antiferromagnetic coupling between the TCNQ spins. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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Effect of Deuteration on the Infrared Characteristics of TCNQ-based Solid-Solid Charge-Transfer Systems

Cited by 11 publications

References 6 publications

Hexaazamacrocyclic Nickel and Copper Complexes and their Reactivity with Tetracyanoquinodimethane

Hexaazamacrocyclic Nickel and Copper Complexes and their Reactivity with Tetracyanoquinodimethane

Delocalized TCNQ Stacks in Nickel and Copper Tetraazamacrocyclic Systems

Radical Ion Salts Obtained from Substituted Ferrocene Cations and the Organic Acceptor TCNQ − Synthesis, Structure and Physical Properties

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