NDLI: Structure, dielectric relaxation and electrical conductivity of 2,3,7,8-tetramethoxychalcogenanthrene–2,3-dichloro-5,6-dicyano-l,4-benzoquinone 1 : 1 charge-transfer complexes

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Structure, dielectric relaxation and electrical conductivity of 2,3,7,8-tetramethoxychalcogenanthrene–2,3-dichloro-5,6-dicyano-l,4-benzoquinone 1 : 1 charge-transfer complexes

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Journal of Materials Chemistry Vol - 6 Issue - 3

Journal of Materials Chemistry Vol - 6 Issue - 2

Journal of Materials Chemistry Vol -5

Journal of Materials Chemistry Vol -4

Journal of Materials Chemistry Vol -3

Structure, dielectric relaxation and electrical conductivity of 2,3,7,8-tetramethoxychalcogenanthrene–2,3-dichloro-5,6-dicyano-l,4-benzoquinone 1 : 1 charge-transfer complexes

Content Provider	Royal Society of Chemistry (RSC)
Author	Gunßer, Walter Franke, Ursula Zimmer, Bärbel Klar, Günter Kudnig, Jens Olbrich, Falk Sanchis, Maria J. Behrens, Ulrich Martínez, Enrique Sánchez Dötze, Mark Calleja, Ricardo Díaz
Copyright Year	1996
Abstract	2,3,7,8-Tetramethoxychalcogenanthrenes (5,10-chalcogena-cyclo-diveratrylenes, ‘Vn2E2’, E = S, Se) form isotypical 1 : 1 charge-transfer (CT) complexes with 2,3-dichloro-5,6-dicyano-l,4-benzoquinone (DDQ). X-ray analysis of Vn2S2·DDQ shows the compound to have a columnar structure with segregated stacks of donors and acceptors. The donors are virtually planar in accordance with a formulation of [Vn2E2]+[DDQ]–. Donor cations and acceptor anions are equidistant in their respective stacks, but in each case they inclined to the stacking axis, nevertheless guaranteeing an optimum overlap of the half-filled frontier orbitals which are of π-type character according to MNDO calculations. Dielectric ac measurements of permittivity Îµ′ and loss factor Îµ″ clearly reveal two processes, a dielectric one at low temperatures and a conductive one at high temperatures. The dielectric process can be described by the Havriliak–Negami (HN) and the Kohlrausch–Williams–Watts (KWW) model, and the conductive process by a Debye-type plot. Using these methods, the relevant parameters are evaluated. The dc conductivities of polycrystalline samples moulded at 108 Pa show a temperature dependence in the plots of ln σ vs. T–1, which is typical of semiconductors. Two slopes are found; that in the low-temperature region (< 285 K) is explained by an easy-path model (intragrain conductivity with low activation energies), whereas in the high-temperature region conduction across the grain boundaries (with higher activation energies) is becoming predominant. The activation energies for the intrinsic conductivities obtained by the ac and dc measurements are similar. Despite the columnar structure with segregated stacks, due to stoichiometric oxidation states of the components, the absolute values of conductivity are low (ca. 10 –6 S cm–1 at 293 K), though higher (by a factor of ca. 103) than those of compounds like Vn2E22·TCNQ with stacks in which donor and acceptor molecules alternate.
Starting Page	547
Ending Page	553
Page Count	7
File Format	PDF
ISSN	09599428
Volume Number	6
Issue Number	4
Journal	Journal of Materials Chemistry
DOI	10.1039/JM9960600547
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Williams Watts Benzoquinone 3-Dichloro-5 6-dicyano-1 4-benzoquinone X-ray crystallography MNDO Dielectric Crystallite Dependent and independent variables Stoichiometry
Content Type	Text
Resource Type	Article
Subject	Chemistry Materials Chemistry

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