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Crystals 2018, 8(4), 142; https://doi.org/10.3390/cryst8040142

β”-(CNB-EDT-TTF)4BF4; Anion Disorder Effects in Bilayer Molecular Metals

1
C2TN, Centro de Ciências e Tecnologias Nucleares, Instituto Superior Técnico, Universidade de Lisboa, E.N. 10, P-2695-066 Bobadela LRS, Portugal
2
Institut de Ciencia de Materials de Barcelona (ICMAB-CSIC), Campus UAB, E-08193 Bellaterra, Spain
*
Author to whom correspondence should be addressed.
Received: 3 March 2018 / Revised: 17 March 2018 / Accepted: 18 March 2018 / Published: 21 March 2018
(This article belongs to the Special Issue Advances in Organic Conductors and Superconductors)
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Abstract

The preparation and characterization of new salts based on the dissymmetrical TTF derivative CNB-EDT-TTF (cyanobenzene-ethylenedithio-tetrathiafulvalene) and BF4 anions, are reported. Depending on the electrocrystallization conditions salts with different stoichiometries, (CNB-EDT-TTF)BF4 and β”-(CNB-EDT-TTF)4BF4, can be obtained. The 1:1 salt is an electrical insulator isostructural to the ClO4 analogue previously described. The 4:1 salt is a new member of the family of 2D metals of this donor with different small anions X, (CNB-EDT-TTF)4X, characterized by a bilayer arrangement of the donors and it was obtained in a monoclinic polymorph with a β”-type donor packing pattern. The small anions in this compound are severely disordered between the donor bilayers, which present slightly larger lattice parameters than the isostructural ClO4 analogue. Both electrical conductivity and thermoelectric power measurements in single crystals denote metallic properties as predicted by electronic band structure calculations. As a consequence of the anion disorder the metallic regime of the electrical conductivity denotes electronic localization effects with a progressive increase of resistivity below ~25 K. Because of the larger lattice parameters the intermolecular interactions and electronic bandwidth are decreased compared to other (CNB-EDT-TTF)4X salts. The large and positive thermoelectric power S of this compound (~110 μV/K in the range 100–330 K) and its electrical conductivity σ = 20 S/cm at room temperature lead to a power factor S2σ = 24 μW/K2m, quite large among molecular conductors, placing these compounds as potential candidates for thermoelectric materials. View Full-Text
Keywords: molecular conductors; bilayer metals; radical cation salts; CNB-EDT-TTF; thermoelectrics molecular conductors; bilayer metals; radical cation salts; CNB-EDT-TTF; thermoelectrics
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Rabaça, S.; Oliveira, S.; Gama, V.; Santos, I.C.; Oliveira, G.; Lopes, E.B.; Canadell, E.; Almeida, M. β”-(CNB-EDT-TTF)4BF4; Anion Disorder Effects in Bilayer Molecular Metals. Crystals 2018, 8, 142.

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