Molecular conductors from bis(ethylenedithio)tetrathiafulvalene with tris(oxalato)rhodate (original) (raw)
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Russian Journal of General Chemistry, 2019
The radical-cationic salts based on tetrathiafulvalene derivatives and bis(dicarbollide) transition metal complexes [3,3'-M(1,2-C 2 B 9 H 11) 2 ]-(M = Co, Ni, Fe, Cr) are promising for the creation of new molecular conductive materials due to the almost unlimited possibilities of their modification. The relationships between the properties of both components of the cation-radical salts, their crystal structure, and electrical and magnetic properties have been analyzed on the basis of the literature and our own data. The effect of various substituents in metallacarborane anions on the structure and physical properties of their radical cation salts based on tetrathiafulvalene and its derivatives has been revealed. Data on the structure and properties of the radical cation salts with other borate anions are presented for comparison.
Novel Bis(ethylenedithio)tetrathiafulvalene-Based Organic Conductor with 1,1‘-Ferrocenedisulfonate
Inorganic Chemistry, 2007
A new bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF)-based salt with a ferrocenyl moiety, R′′′-(BEDT-TTF) 4 (Fe(C 5 H 4 SO 3) 2)‚6H 2 O, has been prepared. The ferrocenyl part of this salt is neutral and diamagnetic, but the magnetic susceptibility is well modeled by a Curie−Weiss law with C) 0.142 emu‚K‚mol-1 (≈ 1 / 3 of s) 1 / 2 spin). The spin is likely to be localized on the donor layer because of its unique charge disproportionation. Charge-transfer salts of the electron donor molecule bis-(ethylenedithio)tetrathiafulvalene (BEDT-TTF) exhibit a wide range of ground states, including metallic, superconducting, semiconducting, or insulating. 1a Typically, their structures consist of stacks of positively charged BEDT-TTF molecules that form layers that are interleaved by layers of counterions. The donor molecules pack in a variety of ways, leading to phases that are designated by the letters R, , γ, κ, λ, etc. 1,2 Evidently, the packing motifs play a crucial role in determining the electronic ground states. However, salts that have the same packing motif but different counteranions often have different ground states. In other words, additional structural subtlety can modify the ground states. 1a,d Recently, insulating states have been of interest to many researchers and various types of insulating states have been established, 1 such as charge-density wave, spin-density wave, Mott
Chemistry of Materials, 1995
The electrochemical synthesis and physical characterization of a series of new bis-(ethy1enethio)tetrathiafulvalene (BET-TTF) based salts, (BET-TTFIPFs, and (BET-TTF)z X (X = PF6, AsF6, and SbFe), are reported. In all X-ray crystal structures, only the E isomer of BET-TTF is present. The (BET-TTF)PFe (2) salt crystallizes in the centrosymmetric group P21/a, in which donors stack uniformly along the b crystallographic axis in a herringbone pattern with a crystal packing similar to a-phases of BEDT-TTF. The three 2:l salts crystallize in the triclinic P-1 space group and are isostructural, being the crystal packing motif very similar to the ,&phases of BEDT-TTF. In salts (BET-TTF)~AsF~ (4) and (BET-TTFhSbF6 (5) a structural disorder due to the external sulfur positions of BET-TTF is observed. Band electronic calculations on these structures indicate a quasi-2D electronic character for salts 4 and 5. All 2:l salts show metallic character down to -100 K, where a very broad transition toward an activated conductivity is observed. The relationships between the crystal structures, physical properties, and electronic structures are discussed.
Synthesis and Electroconductive Properties of Radical Salts Derived from Tetrathiafulvalene Dimers
Journal of Solid State Chemistry, 2002
Palladium(II)-or copper(II)-catalyzed homo-coupling reaction of either trimethylstannyltetrathiafulvalene or tetrathiafulvalenylzinc chloride produces symmetrical bitetrathiafulvalenes (bi-TTFs) in good yields, whereas palladium(0)catalyzed cross-coupling reaction of tetrathiafulvalenylzinc chloride with 4-iodotetrathiafulvalenes leads to the corresponding unsymmetrically substituted bi-TTFs in moderate-to-high yields. The X-ray analysis of bi-TTF derivatives showed planar structures, and the cyclic voltammetry suggested that bi-TTFs have good donor ability comparable to that of BEDT-TTF. The symmetrical bi-TTFs formed the corresponding CT-complexes and cation radical salts. These CT-complexes and radical salts were found to be metallic or semiconducting, reflecting the effect of stoichiometry control in the dimeric TTF system. The X-ray structures of two cation radical salts revealed a unique stacking, and the precise conducting path in BEDO-bi-TTF . ClO 4 was discussed on the basis of MO calculations. # 2002 Elsevier Science (USA)
Crystal Growth & Design, 2019
Two salts of the dissymmetric TTF-derivative 4-cyanobenzene-ethylenedithiotetrathiafulvalene (4-CNB-EDT-TTF) with bromide and tribromide anions and with different stoichiometries, namely (1:1) (4-CNB-EDT-TTF)Br 3 (1) and (4:1) (4-CNB-EDT-TTF) 4 Br (2) were obtained by electrocrystallisation and diffusion methods, respectively. The crystal structures of these compounds, as determined by single crystal X-ray diffraction, are based on head-to-tail donor dimers with ring over ring overlap and donor stack arrangement, interleaved by anions depending on (1:1) or (4:1) salt, respectively. The 4:1 salt behaves as a Mott insulator. In both salts the donors are connected to adjacent donors through C-N … H-C interactions which can be described as an modified R 2 4 (10)* synthon for 1 and a combination of R 2 2 (10) and R 2 4 (10) synthons for 2. 1. INTRODUCTION
Molecular conductors with anti-7,7′:8,8′-bis(dithio)bis(7,8-dicarbaundecaborate) anion
Inorganic Chemistry Communications, 2013
New radical cation salts (BEDT-TTF) 2 [anti-7,7′:8,8′-bis(dithio)bis(7,8-dicarba-undecaborate)] and (TMTTF) 2 [anti-7,7′:8,8′-bis(dithio)bis(7,8-dicarbaundecaborate)] were obtained by electrocrystallization from solution of bis(ortho-carboranyl-1,2-dithiolate)cobalt(II) complex (Me 4 N) 2 [Co(1,2-S 2 C 2 B 10 H 10) 2 ] and BEDT-TTF or TMTTF, respectively, in acetonitrile-1,1,2-thrichloroethane. The process is accompanied with the complex demetallation, partial deboronation of the carborane cage and oxidation of dithiolate to cyclic bis(disulfide). X-ray crystal structures and electrical conductivities of the compounds synthesized were determined.
International Journal of Molecular Sciences, 2014
The synthesis of new unsymmetrically benzene-fused bis (tetrathiafulvalene) has been carried out by a cross-coupling reaction of the respective 4,5-dialkyl-1,3-dithiole-2-selenone 6-9 with 2-(4-(p-nitrophenyl)-1,3-dithiole-2-ylidene)-1,3,5,7-tetrathia-sindacene-6-one 5 prepared by olefination of 4-(p-nitrophenyl)-1,3-dithiole-2-selenone 3 and 1,3,5,7-tetrathia-s-indacene-2,6-dione 4. The conversion of the nitro moiety 10a-d to amino 11a-d then dibenzylamine 12a-d groups respectively used reduction and alkylation methods. The electron donor ability of these new compounds has been measured by cyclic voltammetry (CV) technique. Charge transfer complexes with tetracyanoquino-dimethane (TCNQ) were prepared by chemical redox reactions. The complexes have been proven to give conducting materials.
2014
Abstract: The synthesis of new unsymmetrically benzene-fused bis (tetrathiafulvalene) has been carried out by a cross-coupling reaction of the respective 4,5-dialkyl-1,3-dithiole-2-selenone 6–9 with 2-(4-(p-nitrophenyl)-1,3-dithiole-2-ylidene)-1,3,5,7-tetrathia-s-indacene-6-one 5 prepared by olefination of 4-(p-nitrophenyl)-1,3-dithiole-2-selenone 3 and 1,3,5,7-tetrathia-s-indacene-2,6-dione 4. The conversion of the nitro moiety 10a–d to amino 11a–d then dibenzylamine 12a–d groups respectively used reduction and alkylation methods. The electron donor ability of these new compounds has been measured by cyclic voltammetry (CV) technique. Charge transfer complexes with tetracyanoquino-dimethane (TCNQ) were prepared by chemical redox reactions. The complexes have been proven to give conducting materials.