BEDT-TTF salts with square platinates(II) as counterions: [BEDT-TTF]4[Pt(C2O4)2], A new organic metal

Gärtner, S.; Heinen, I.; Schweitzer, Dieter; Nuber, Bernhard; Keller, Heimo J.

doi:10.1016/0379-6779(89)90815-1

Cited by 19 publications

(9 citation statements)

References 15 publications

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“…For instance, there are three salts in which the anion part exhibits monomeric units: (BEDT-TTF) 4 -[Pt(C 2 O 4 ) 2 ] [24] and (BEDT-TTF) 4 [Cu(C 2 O 4 ) 2 ], [25] which show a metal±insulator transition at about 60±65 K, and the semiconducting (BEDT-TTF) 2 [Ge IV (C 2 O 4 ) 3 ]´BN. [26] Metal oxalate dimer anions have been found in the radical cation salts (BEDT-TTF) 4 [27] and (BEDT-TTF) 5 [Cr 2 (C 2 O 4 )(NCS) 8 ].…”

Section: (H 3 O)[cr(c 2 O 4 ) 3 ] 2 [(H 3 O)mentioning

confidence: 99%

Molecular Metals Based on BEDT‐TTF Radical Cation Salts with Magnetic Metal Oxalates as Counterions: β″‐(BEDT‐TTF)₄A[M(C₂O₄)₃]·DMF (A = NH₄⁺, K⁺; M = Cr^III, Fe^III)

Prokhorova

Khasanov

Zorina

et al. 2003

Adv Funct Materials

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Four (BEDT‐TTF)4A[M(C2O4)3]·DMF (DMF = dimethylformamide) salts of the organic donor molecule bis(ethylenedithio)tetrathiafulvalene (BEDT‐TTF) with metal oxalate anions, where A = (NH4, K), M = Cr (1); A = NH4, M = Fe (2); A = K, M = Cr (3); and A = NH4, M = Cr (3′) were prepared by electrocrystallization. These salts were characterized by single‐crystal X‐ray diffraction, electron spin resonance (ESR) spectroscopy, electrical resistance measurements, and electronic band structure calculations. The structures (with space group C2/c) consist of alternating β″‐type layers of BEDT‐TTF and an approximately hexagonal network formed by the A+ cation and the metal, with the solvent molecule, DMF, occupying hexagonal cavities in the anion layer. All of the salts are two‐dimensional organic metals down to 4.2 K and do not exhibit superconductivity. Their electronic band structure is similar to that of the known organic superconductor β″‐(BEDT‐TTF)4H3O[Fe(C2O4)3]·BN. The ESR spectra of salts 1 and 3′ are characterized by two resonances, one of Gaussian shape arising from the 3d localized electrons of Cr3+ and the other of Lorentzian (and Dysonian) shape due to the conduction electrons in the organic layers. On the basis of the calculated Fermi surfaces it is suggested that these salts could exhibit an interesting magnetoresistance behavior if disorder does not prevent the observation of the Shubnikov‐de Haas oscillations.

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Section: (H 3 O)[cr(c 2 O 4 ) 3 ] 2 [(H 3 O)mentioning

confidence: 99%

Molecular Metals Based on BEDT‐TTF Radical Cation Salts with Magnetic Metal Oxalates as Counterions: β″‐(BEDT‐TTF)₄A[M(C₂O₄)₃]·DMF (A = NH₄⁺, K⁺; M = Cr^III, Fe^III)

Prokhorova

Khasanov

Zorina

et al. 2003

Adv Funct Materials

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“…On the other hand, the 4 : 1 complex is metallic and the crystal structure of it resembles those of the 4 : 1 complexes of M(ox) 2 (M~Pt or Cu). 11,15 Table 6 compares the bond distances of an ET molecule of different charge and those in the M(dto) 2 complexes. The bond lengths a and b are more sensitive to the charge than those of c and d and they show an approximately linear relation to the charge.…”

Section: Complex Formation Using (Tpp) 2 Cu(dto) 2 and Ttfsmentioning

confidence: 99%

“…As a comparison, the band dispersions, Fermi surfaces and DOSs of (ET) 4 [M(ox) 2 ] (M~Pt or Cu) using our parameters and reported crystal structures 11,15 are depicted in Fig. 10(b) and 10(c), respectively.…”

Section: (Bedt-ttf) 2 [Ni(dto) 2 ] the Estimated Charge Of Anmentioning

confidence: 99%

“…24 This kind of bond has well been recognized in the Pt(ox) 2 and Cu(ox) 2 salts of ET, between the CH groups of an ET molecule and oxygen atoms of CLO groups of oxalate. 11,15 Therefore, by replacement of ox by dto, the interaction between a donor especially an ET molecule and an anion will considerably be modi®ed from the viewpoints of atomic contacts.…”

Section: Introductionmentioning

confidence: 99%

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Formation of 2∶1 insulating complexes of D+·D+·A2− alternating stack and a 4∶1 semimetallic complex using M(dto)2 dianions (M = Ni, Pd or Pt and dto = dithiooxalate)

et al. 2000

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The preparation of charge transfer (CT) complexes of dithiooxalate (dto) transition metal salts M(dto) 2 (M~Ni, Pd, Pt or Cu) with a variety of electron donor molecules was examined based on the redox properties of constituent molecules. Conventional electron donors of TTF type, such as bis(ethylenedithio)-(BEDT-TTF (ET)) and bis(ethylenedioxy)-tetrathiafulvalene (BEDO-TTF (BO)), mainly afford 2 : 1 solid CT complexes composed of a donor cation dimer D z? D z? and dianion of M(dto) 2 (A 22 ) when M~Ni, Pd or Pt. The constituent molecules stack alternately to construct a D z? D z? A 22 column. Their crystal structures are unique among the ET and BO complexes so far known, namely the M(dto) 2 22 ions are isolated from each other being surrounded by six dimers of D z? in the crystals. Three kinds of 2 : 1 complex were obtained between ET and Pd(dto) 2 . The electronic spectra of the solids are characterized by the particular intradimer transition of the donor cation dimer. The infrared vibrational spectra strongly exhibit the a g modes of the donor cation due to its dimerization. All of the complexes are electrical insulators. A singlet±triplet magnetic excitation is clearly observed for some of them. A highly conductive 4 : 1 complex was obtained between ET and Pd(dto) 2 , (ET) 4 [Pd(dto) 2 ], which exhibited electronic absorption extending below 5610 3 cm 21 . The complex shows a semimetallic nature.{Bond lengths, bond angles and atomic parameters available as supplementary data (ESI). For direct electronic access see

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“…The latter are found by combining the individual 2D Fermi surface together and neglecting the surface noucrossings. In understanding the CDW instabilities of the organic conducting salts (BEDT-TTF)2ReO4 [16] and (BEDT-TTF),Pt(C204) [17], the hidden nesting concept has also been found essential [18]. Thus, it is important to probe whether or not the hidden nesting concept is also responsible for the increase of the resistivity below 35 K of the 2D metal (BEDO-TTF)zReO4.…”

Section: Introductionmentioning

confidence: 99%

Characterisation of the Fermi surface and phase transitions of (BEDO-TTF)2 ReO4�(H2O) by physical property measurements and electronic band structure calculations

Kahlich

Schweitzer

Rovira

et al. 1994

Z. Physik B - Condensed Matter

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Abstract. The electronic properties of the organic superconductor (BEDO-TTF)2 ReO4.(H20 ) were investigated by temperature dependent resistivity, ESR, Hall effect and magnetoresistance measurements. Shubnikov-de Haas (SdH) oscillations were observed in magnetic fields up to 24 T in the temperature range 0.5 K to 4.2 K. The electronic band structure of (BEDO-TTF)2 ReO 4. (H20) was calculated by employing the extended Hiickel tight binding method on the basis of its room temperature crystal structure. The two observed SdH frequencies of 75 T and 37 T correspond very well with two cross-sectional areas of the hole and electron Fermi surface pockets obtained from the tight binding calculation. From the temperature dependence of the SdH oscillation amplitudes, the cyclotron effective mass (me) belonging to the larger and smaller pockets were found to be 0.9 m o and mc = 1.15 m 0 respectively. Measurements of the angular dependence of the SdH frequencies show no deviation from that expected for a cylindrical Fermi surface. In terms of our tight binding calculations and experimental measurements, probable causes for the 213K and 35 K phase transitions are discussed. The calculations show that (BEDO-TTF)2 ReO 4.(H20 ) is a two dimensional semimetal but possesses a hidden nesting. The latter is likely to cause an SDW instability leading to the 35 K transition. The resistivity drop associated with the 213 K transition is likely to be induced by an abrupt increase in the relaxation time. The excellent agreement between the calculated and experimentally observed Fermi surface implies that, with decreasing temperature be-

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BEDT-TTF salts with square platinates(II) as counterions: [BEDT-TTF]4[Pt(C2O4)2], A new organic metal

Abstract: The title compound, [BEDT-TTF]

Cited by 19 publications

References 15 publications

Molecular Metals Based on BEDT‐TTF Radical Cation Salts with Magnetic Metal Oxalates as Counterions: β″‐(BEDT‐TTF)₄A[M(C₂O₄)₃]·DMF (A = NH₄⁺, K⁺; M = Cr^III, Fe^III)

Molecular Metals Based on BEDT‐TTF Radical Cation Salts with Magnetic Metal Oxalates as Counterions: β″‐(BEDT‐TTF)₄A[M(C₂O₄)₃]·DMF (A = NH₄⁺, K⁺; M = Cr^III, Fe^III)

Formation of 2∶1 insulating complexes of D+·D+·A2− alternating stack and a 4∶1 semimetallic complex using M(dto)2 dianions (M = Ni, Pd or Pt and dto = dithiooxalate)

Characterisation of the Fermi surface and phase transitions of (BEDO-TTF)2 ReO4�(H2O) by physical property measurements and electronic band structure calculations

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BEDT-TTF salts with square platinates(II) as counterions: [BEDT-TTF]4[Pt(C2O4)2], A new organic metal

Abstract: The title compound, [BEDT-TTF]

Cited by 19 publications

References 15 publications

Molecular Metals Based on BEDT‐TTF Radical Cation Salts with Magnetic Metal Oxalates as Counterions: β″‐(BEDT‐TTF)4A[M(C2O4)3]·DMF (A = NH4+, K+; M = CrIII, FeIII)

Molecular Metals Based on BEDT‐TTF Radical Cation Salts with Magnetic Metal Oxalates as Counterions: β″‐(BEDT‐TTF)4A[M(C2O4)3]·DMF (A = NH4+, K+; M = CrIII, FeIII)

Formation of 2∶1 insulating complexes of D+·D+·A2− alternating stack and a 4∶1 semimetallic complex using M(dto)2 dianions (M = Ni, Pd or Pt and dto = dithiooxalate)

Characterisation of the Fermi surface and phase transitions of (BEDO-TTF)2 ReO4�(H2O) by physical property measurements and electronic band structure calculations

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Molecular Metals Based on BEDT‐TTF Radical Cation Salts with Magnetic Metal Oxalates as Counterions: β″‐(BEDT‐TTF)₄A[M(C₂O₄)₃]·DMF (A = NH₄⁺, K⁺; M = Cr^III, Fe^III)

Molecular Metals Based on BEDT‐TTF Radical Cation Salts with Magnetic Metal Oxalates as Counterions: β″‐(BEDT‐TTF)₄A[M(C₂O₄)₃]·DMF (A = NH₄⁺, K⁺; M = Cr^III, Fe^III)