Molecular conductors with the common and robust building block (BEDT-TTF)2NP (NP = [FeNO(CN)5]2−) but different band filling

Two new organic conductors based on BEDT-TTF radical cation salts with the [FeNO(CN)5]2− anion have been synthesized. β″-(BEDT-TTF)2[FeNO(CN)5] (1) and β″-(BEDT-TTF)3[FeNO(CN)5]·EG (2) have been characterized by single-crystal X-ray diffraction, electrical resistance measurements, and electronic band-structure calculations. A detailed comparison of 1 and 2 with β″-(BEDT-TTF)4A[FeNO(CN)5]2 (3) is reported. 2 and 3 are organic metals stable down to low temperatures while 1 is a semiconductor. Analysis of the correlation between the crystal and electronic structures as well as the transport properties of these molecular conductors suggests the possibility of changing their physical properties through chemical control of the composition of the anionic layers.

[1]  R. Shibaeva,et al.  Variety of molecular conducting layers in the family of radical cation salts based on BEDT-TTF with the metal mononitrosyl complex [OsNOCl5]2- , 2005 .

[2]  R. Shibaeva,et al.  New Organic Metals Based on BDH‐TTP Radical Cation Salts with the Photochromic Nitroprusside Anion [FeNO(CN)5]2– , 2004 .

[3]  R. Shibaeva,et al.  Exploitation of the photochromic nitroprusside anion [FeNO(CN)5]2- as counterion for constructing molecular conductors: The first radical cation salts based on BDH-TTP and the amide functionalized derivatives of EDT-TTF , 2004 .

[4]  R. Rousseau,et al.  Step‐by‐Step Construction of the Electronic Structure of Molecular Conductors: Conceptual Aspects and Applications , 2004 .

[5]  R. Shibaeva,et al.  Structure-properties relationships in organic molecular conductors based on radical cation salts with octahedral metal complexes as counterions , 2003 .

[6]  R. Shibaeva,et al.  The First Mixed Valence Radical Cation Salts of BEDT-TTF with the Photochromic Metal Mononitrosyl Complexes [RuNOX5]2− (X=Br, Cl) as Counterions , 2002 .

[7]  R. Rousseau,et al.  An In‐Depth Correlation of the Perturbation of the Organic–Inorganic Interface Topology, Electronic Structure, and Transport Properties within an Extended Series of 21 Metallic Pseudopolymorphs, β″‐(BEDT‐TTF)4⋅(guest)n⋅[Re6Q6Cl8], (Q=S, Se) , 2002 .

[8]  E. Yagubskii,et al.  Photoinduced transition of [Fe(CN)5NO] nitroprusside anions to metastable states and electron localization in the (BEDT-TTF)4K[Fe(CN)5NO]2 molecular metal , 2002 .

[9]  R. Shibaeva,et al.  Radical Cation Salts of Tetrathiotetracene and Tetraselenotetracene with Photochromic Anion [Fe(NO)(CN)5]2– , 2002 .

[10]  R. Shibaeva,et al.  Crystal and electronic structures of the radical cation salt based on EDT-TTF and the photochromic nitroprusside anion, (EDT-TTF)3[Fe(CN)5NO] , 2002 .

[11]  E. Yagubskii,et al.  Anion Conformation and Physical Properties in BETS Salts with the Nitroprusside Anion and its Related Ruthenium Halide (X = Cl, Br) Mononitrosyl Complexes: θ‐(BETS)4[Fe(CN)5NO], (BETS)2[RuBr5NO], and (BETS)2[RuCl5NO] , 2001 .

[12]  C. Rovira,et al.  Hybrid molecular materials based upon organic pi-electron donors and metal complexes. Radical salts of bis(ethylenethia)tetrathiafulvalene (BET-TTF) with the octahedral anions hexacyanoferrate(III) and nitroprusside. The first kappa phase in the BET-TTF family. , 2001, Inorganic chemistry.

[13]  R. Shibaeva,et al.  Structure of (BEDT-TTF)-Based Organic Metals with Photochromic Nitroprusside Anion (BEDT-TTF)4M[FeNO(CN)5]2, where M = Na+, K+, NH+4, Tl+, Rb+, and Cs+ , 2001 .

[14]  R. Shibaeva,et al.  A new stable organic metal based on the BEDO-TTF donor and the doubly charged nitroprusside anion, (BEDO-TTF)4[Fe(CN)5NO] , 2000 .

[15]  Louis J. Farrugia,et al.  WinGX suite for small-molecule single-crystal crystallography , 1999 .

[16]  R. Shibaeva,et al.  Band structure and Fermi surface of the (BEDT-TTF)4M[Fe(CN)5NO]2 (M=Na, K, Rb,…) molecular metals containing the photochromic nitroprusside anion , 1999 .

[17]  C. Kepert,et al.  Structural Properties of the Superconducting Salt (BEDT-TTF)3Cl2·(H2O)2 at Low Temperatures , 1999 .

[18]  J. Fabre,et al.  Molecular conductors based upon TTF-type donors and octahedral magnetic complexes , 1999 .

[19]  R. Shibaeva,et al.  Molecular metals based on radical cation salts of ET and some its analogues with the photochromic nitroprusside anion, [Fe(CN)5NO]2− , 1999 .

[20]  Takehiko Mori.  Structural Genealogy of BEDT-TTF-Based Organic Conductors I. Parallel Molecules: .BETA. and .BETA." Phases. , 1998 .

[21]  M. Carducci,et al.  Diffraction Studies of Photoexcited Crystals: Metastable Nitrosyl-Linkage Isomers of Sodium Nitroprusside , 1997 .

[22]  A. Pénicaud,et al.  Hydrogen-bond tuning of macroscopic transport properties from the neutral molecular component site along the sries of metallic organic-inorganic solvates (BEDT-TTF)4Re6Se5Cl9.[guest], [guest = DMF, THF, dioxane] , 1993 .

[23]  M. C. Etter.  Encoding and decoding hydrogen-bond patterns of organic compounds , 1990 .

[24]  R. M. Lobkovskaya,et al.  Crystal structures and electrical properties of ET3Cl2.2H2O and ET4Cl2.4H2O organic metals , 1988 .

[25]  M. Rosseinsky,et al.  A novel conducting charge-transfer salt: (BEDT-TTF)3Cl2·2H2O , 1988 .

[26]  Takehiko Mori,et al.  Superconductivity in (BEDT-TTF)3Cl22H2O , 1987 .

[27]  MoriTakehiko,et al.  Structural and Electrical Properties of (BEDT-TTF)3CI2(H2O)2 , 1987 .

[28]  Takehiko Mori,et al.  Structural and electrical properties of (BEDT-TTF)3Cl2(H2O)2. , 1987 .

[29]  R. Hoffmann,et al.  The band structure of the tetracyanoplatinate chain , 1978 .

[30]  R. Hoffmann,et al.  Counterintuitive Orbital Mixing in Semiempirical and ab Initio Molecular Orbital Calculations , 1978 .