New multicomponent organic semiconductors based on ET with polymeric Anions: α″-(ET)2N(CN)2·2H2O and α‴-(ET)6(NO3)3·2C2H5O2N3

Kazakova, A. V.; Kushch, N. D.; Chekhlov, A. N.; Dubrovskiĭ, A. D.; Yagubskiǐ, É. B.; Ван, К. В.

doi:10.1134/s1070363208010027

Cited by 6 publications

(2 citation statements)

References 25 publications

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“…The shift along the molecular long axis (∥ a ) to an adjacent ET molecule, so as to engage with the anionic layers, was estimated to be 1.72 Å. Similar wavy arrangements have been found for some α″-(ET) 2 X salts with X = Ag(CN) 2 – and Au(CN) 2 – , , whereas the salts with X = Cu 5 I 6 – , , CsHg(SCN) 4 – , KCu(SCN) 4 – , and N(CN) 2 – ·2H 2 O involve flat ET layers.…”

Section: Resultssupporting

confidence: 58%

Bis(ethylenedithio)tetrathiafulvalene Cation Radical Salts Composed of Nonuniform Silver(I) Complex Polyanions

et al. 2019

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Rational control of the molecular arrangement in solids has been the subject of intense research for many years. In particular, the structural control of bis(ethylenedithio)tetrathiafulvalene (ET) radical cations has attracted special interest because of the primary effect on the electronic properties of the salts. In this study, we obtained the first ET cation radical salts formed with nonuniform silver(I) complex polyanions, which involve multiple kinds of openings in the anionic layer, by an electrocrystallization method. θ-(ET)2Ag2(CN)[N(CN)2]2 (1) with a θ-type ET packing motif contains double helical chains composed of AgN(CN)2, whereas α″-(ET)2Ag2(CN)(SCN)2 (2) with an α″-type ET packing motif contains zigzag ladders composed of AgSCN. Both silver(I)-based tube-like assemblies are connected to each other by a cyano group, affording nonuniform polyanionic structures. Although both salts show semiconducting behavior, there is a distinct difference in their spin geometry, with an S = 1/2 Heisenberg antiferromagnetic square lattice in 1, which is associated with charge disproportionation or dynamical charge fluctuation in the ET layers, and an S = 1/2 Heisenberg anisotropic triangular lattice in 2, which results in spin frustration in the ET layers. The ability of the nonuniform polymeric structures in the anionic layers to act as templates for various arrangements of ET radical cations is demonstrated.

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Section: Resultssupporting

confidence: 58%

Bis(ethylenedithio)tetrathiafulvalene Cation Radical Salts Composed of Nonuniform Silver(I) Complex Polyanions

et al. 2019

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“…If we limit the search to ET, there are only five salts prepared with TCNQ and its derivatives (Table 1): (ET)(Me 2 TCNQ), (ET)(ClMeTCNQ) [25], (ET)(F-TCNQ), (ET)(F 2 TCNQ) 0.5 (TCNQ) 0.5 [26], and (ET)(TCNQ) [27], seven salts with polycyano anions (Table 2) [34], three phases with dca − (Table 3) [24,35,36] and five other compounds involving the dca − anion and transition metal ions: [37] and (ET) 2 [CuMn(dca) 4 ] [21,38]. A possible reason explaining this lack of radical salts with this kind of anions may be the difficulty of obtaining single crystals of these compounds given the rigidity of the cyano groups and the lack of planarity of the -X(CN) 2 groups in the corresponding anions (except in the dca − anion, which, accordingly, is the most successful one).…”

Section: Formula Ccdc Code Anionmentioning

confidence: 99%

Polymorphism and Metallic Behavior in BEDT-TTF Radical Salts with Polycyano Anions

et al. 2012

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Up to five different crystalline radical salts have been prepared with the organic donor BEDT-TTF and three different polynitrile anions. With the polynitrile dianion tcpd 2− (=C[C(CN) 2 ] 3 2−), two closely related radical salts: α'-(ET) 4 tcpd· THF (1) (THF = tetrahydrofurane) and α'-(ET) 4 tcpd· H 2 O (2) have been prepared, depending on the solvent used in the synthesis. With the mono-anion tcnoetOH − (=[(NC) 2 CC(OCH 2 CH 2 OH)C(CN) 2 ] −) two polymorphs with similar physical properties but different crystal packings have been synthesized: θ-(ET) 2 (tcnoetOH) (3) and β''-(ET) 2 (tcnoetOH) (4). Finally, with the mono-anion tcnoprOH − (=[(NC) 2 CC(OCH 2 CH 2 CH 2 OH)C(CN) 2 ] −) we have prepared a metallic radical salt: β''-(ET) 2 (tcnoprOH)(CH 2 Cl 2 CH 3 Cl) 0.5 (5). Salts 1-4 are semiconductors with high room temperature conductivities and activation energies in the range 0.1-0.5 eV, whereas salt 5 is metallic down to 0.4 K although it does not show any superconducting transition above this temperature.

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First radical cаtion salt of bis(ethylenedithio)tetrathiafulvalene with organic anion [С(NCN)2NH2]–: synthesis, structure, and conducting properties

et al. 2016

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New multicomponent organic semiconductors based on ET with polymeric Anions: α″-(ET)2N(CN)2·2H2O and α‴-(ET)6(NO3)3·2C2H5O2N3

Cited by 6 publications

References 25 publications

Bis(ethylenedithio)tetrathiafulvalene Cation Radical Salts Composed of Nonuniform Silver(I) Complex Polyanions

Bis(ethylenedithio)tetrathiafulvalene Cation Radical Salts Composed of Nonuniform Silver(I) Complex Polyanions

Polymorphism and Metallic Behavior in BEDT-TTF Radical Salts with Polycyano Anions

First radical cаtion salt of bis(ethylenedithio)tetrathiafulvalene with organic anion [С(NCN)2NH2]–: synthesis, structure, and conducting properties

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