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Organic Superconductivity pp 51–66Cite as

New Ambient Pressure Organic Superconductors: α-(BEDT-TTF)2(NH4)Hg(SCN)4, βm-(BEDO-TTF)3Cu2(NCS)3, and κ-(BEDT-TTF)2Cu[N(CN)2]Br

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Abstract

More than one hundred and twenty conducting salts based on the organic donor-molecule BEDT-TTF are known, where BEDT-TTF is bis(ethylenedithio)tetrathiafulvalene (abbreviated herein as ET). Several of the early salts possessed tetrahedral and octahedral anions, such as (ET)2ClO4(TCE),1 (ET)2PF6,2 (ET)2ReO4,3 and (ET)2BrO4 4 The Perchlorate salt is metallic to 1.4 K,1 and the perrenate derivative was the first ET based organic superconductor (Tc 2 K, 4.5 kbar).3 Since the discovery of ambient pressure superconductivity in β-(ET)2I3 (Tc 1.4 K),5 other isostructural β-(ET)2X salts have been prepared with higher Tc’s. These salts are β-(ET)2IBr2 (Tc 2.8 K),6 β-(ET)2AuI2 (Tc 4.98 K),7 and β*-(ET)2l3 (Tc 8 K).8 A structure-property correlation for the β-type salts has been reviewed in this volume;9 it predicts that Tc’s higher than 8 K are possible if β-salts with linear anions longer than I3− can be synthesized. During the search for new linear anions, a variety of compounds was discovered with polymeric anions. For example, with the Ag(CN)2− anion, in addition to the expected (ET)2Ag(CN)2 salt,10 afforded the first ET salt with a polymeric anion, (ET)Ag4(CN)5.11 The linear AgI2 −12 or cubic Ag4I6 2–13 anions, yielded (ET)3Ag6.4I8 13 In a similar fashion the Cul2− anion leads to (ET)2Cu5I6.14, 15 The latter two compounds are good metals to low temperatures and consist of layers of donor molecules and polymeric anions. The report of superconductivity in κ-(ET)4Hg3X8 (X = Cl, Tc 5.3 K 29 kbar16 and X= Br, Tc 4.3 K ambient pressure17 and 6.7 K 3.5 kbar18) and κ-(ET)2Cu(NCS)2 (Tc 10.4 K)19 further stimulated the search for novel polymeric anions. A general synthetic strategy for preparing new salts containing polymeric anions is to couple a coordinatively unsaturated neutral transition metal halide/pseudohalide with a simple halide or pseudohalide during an electrocrystallization synthesis. A number of new compounds have been made in this way, for example, (ET)BiI4,20 (ET)Ag1.6(SCN)2,21 and (ET)Ag2.4Br3.22 In an attempt to replace the halide in κ-(ET)4Hg3X8 with a pseudo halide, a β-like (ET)4Hg3(SCN)8 23, 24 compound was obtained. Using slightly different experimental conditions during electrocrystallization, two entirely different salts, α-(ET)2(M)Hg(SCN)4 (M+ = K+ and NH4 +), have been reported by Oshima et al. 25, 26 In this article, we discuss three new ambient pressure organic superconductors with novel polymeric anions, α-(ET)2(NH4)Hg(SCN)4,27 βm-(BO)3Cu2(NCS)3,28 and κ-(ET)2Cu[N(CN)2]Br.29

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Authors and Affiliations

  1. Chemistry and Materials Science Divisions, Argonne National Laboratory, Argonne, Illinois, 60439, USA

    Hau H. Wang, Mark A. Beno, K. Douglas Carlson, Urs Geiser, Aravinda M. Kini, Lawrence K. Montgomery, James E. Thompson & Jack M. Williams

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Editors and Affiliations

  1. Lawrence Berkeley Laboratory, University of California, Berkeley, Berkeley, California, USA

    Vladimir Z. Kresin

  2. Stanford University, Stanford, California, USA

    William A. Little

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Wang, H.H. et al. (1990). New Ambient Pressure Organic Superconductors: α-(BEDT-TTF)2(NH4)Hg(SCN)4, βm-(BEDO-TTF)3Cu2(NCS)3, and κ-(BEDT-TTF)2Cu[N(CN)2]Br. In: Kresin, V.Z., Little, W.A. (eds) Organic Superconductivity. Springer, Boston, MA. https://doi.org/10.1007/978-1-4899-2605-0_7

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  • DOI: https://doi.org/10.1007/978-1-4899-2605-0_7

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