Dr Scott Turner


Senior Lecturer in Solid State Materials
BSc(Hons) MRSC PhD
+44 (0)1483 686847
33 AZ 03

Biography

Areas of specialism

Coordination chemistry; Molecular Materials; Magnetic properties; Electrical and ionic conductivity; Metal organic frameworks

University roles and responsibilities

  • Department Exams Officer
  • University Academic Integrity Officer

My qualifications

1990
BSc (Hons) in chemistry
University of Manchester
1993
PhD in chemistry: synthesis of coordination polymers and EPR spectroscopy
University of Manchester

Affiliations and memberships

MRSC
Member of the Royal Society of Chemistry

Research

Research interests

Research collaborations

My teaching

My publications

Publications

Chmel NP, Allan LEN, Becker JM, Clarkson GJ, Turner SS, Scott P (2011) TTF salts of optically pure cobalt pyridine amidates; detection of soluble assemblies with stoichiometry corresponding to the solid state, DALTON TRANSACTIONS 40 (8) pp. 1722-1731 ROYAL SOC CHEMISTRY
Chmel NP, Clarkson GJ, Troisi A, Turner SS, Scott P (2011) Chiral Semiconductor Phases: The Optically Pure D-3(M-III(S,S-EDDS)](2) (D = TTF, TSF) Family, INORGANIC CHEMISTRY 50 (9) pp. 4039-4046 AMER CHEMICAL SOC
Le Pevelen D, Turner SS, Day P, Prout K (2001) TTF based molecular magnets : Structural and physical properties of new salts involving the [Cr(NCS)(phen)] anion, Synthetic Metals 121 (1-3) pp. 1842-1843
Our group has recently focused on obtaining new molecular magnets based on radical BEDT-TTF or TTF derivatives. In these series, the aim is to combine the magnetic and conducting properties in the same material via the radical donor. We report here the structural and the physical properties of three salts with donors TTF (ferrimagnetic insulator), TMTTF (antiferromagnetic insulator) and TMTSF (paramagnetic semiconductor), containing the Reinekes anion derivative [Cr(NCS)4(phenanthroline)]. The role of the crystal packing in determining the physical properties is discussed.
Akutsu H, Yamada J-I, Nakatsuji S, Turner SS (2013) Structures and properties of a BEDT-TTF-based organic charge transfer salt and the zwitterion of ferrocenesulfonate, DALTON TRANSACTIONS 42 (46) pp. 16351-16354 ROYAL SOC CHEMISTRY
Akutsu H, Yamashita S, Yamada J-I, Nakatsuji S, Turner SS (2008) Novel purely organic conductor with an aminoxyl radical, ±-(BEDT-TTF)(PO-CONHCHSO) ·2HO (PO = 2,2,5,5-tetramethyl-3-pyrrolin-1-oxyl free radical), Chemistry Letters 37 (8) pp. 882-883
A novel bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF)-based salt with an aminoxyl radical 2,2,5,5-tetramethyl-3-pyrrolin-1-oxyl (PO) has been prepared. The salt has ±-type 2-D conducting sheets and is a semiconductor with Á = 26 ©·cm and E = 0.31 eV. The temperature dependence of the magnetic susceptibility suggests that both the aminoxyl radical and the BEDT-TTF layer have local spin moments at room temperature. Copyright © 2008 The Chemical Society of Japan.
Akutsu H, Yamada J-I, Nakatsuji S, Turner SS (2009) A new anionic acceptor, 2-sulfo-3,5,6-trichloro-1,4-benzoquinone and its charge-transfer salts, CRYSTENGCOMM 11 (12) pp. 2588-2592 ROYAL SOC CHEMISTRY
Akutsu H, Sasai T, Yamada J, Nakatsuji S, Turner SS (2010) New anionic acceptors Br(2)XQNHCH(2)SO(3)(-) [X=Br, BryCl1-y (y approximate to 0.5), and Cl; Q=1,4-benzoquinone) and their charge-transfer salts, PHYSICA B-CONDENSED MATTER 405 (11) pp. S2-S5 ELSEVIER SCIENCE BV
We have prepared new organic anionic acceptors Br(2)XQNHCH(2)SO(3)(-) (2 X=Br 3 X=BryCl1-y (y approximate to 0 5) 4 X=Cl Q=1 4-benzoquinone) that possess both an electron acceptor part (1 4-benzoquinone) and an anionic part (sulfonate) The reduction potentials of the PPh4 salts of 2 3 and 4 are -0 45 -0 45 and 0 46 V (vs SCE in CH3CN) respectively The results indicate that they are weaker acceptors than chloranil (-0 13 V) and bromanil (-0 12 V) Each anionic acceptor (AA) provided two BEDT-TTF salts beta-(ET)(5)(AA)(2) DCE zH(2)O and -(ET)(2)(AA) CH3OH (AA=2 3 or 4 z=2 0 97 3 0 83 and 4 0 40) The structures and transport properties of the salts are reported (C) 2009 Elsevier B V All rights reserved
Akutsu H, Maruyama Y, Yamada J-I, Nakatsuji S, Turner SS (2011) A new BEDT-TTF-based organic metal with an anionic weak acceptor 2-sulfo-1,4-benzoquinone, Synthetic Metals 161 (21-22) pp. 2339-2343
Mas-Torrent M, Vidal-Gancedo J, Ribas X, Veciana J, Rovira C, Turner SS, Day P, Wurst K (2003) Bulk Spontaneous Magnetization in the New Radical Cation Salt TM-TTF[Cr(NCS)(isoquinoline)] (TM-TTF = Tetramethyltetrathiafulvalene), Inorganic Chemistry 42 (23) pp. 7544-7549
A new organic-inorganic hybrid salt [TM-TTF][Cr(NCS) (isoquinoline)] (1) (TM-TTF = Tetramethyltetrathiafulvalene) has been synthesized. Compound 1 crystallizes in the triclinic P1 space group with a = 8.269(1), b = 10.211(2), and c = 11.176(2) Å, ± = 89.244(9), ² = 88.114(6), and ³ = 74.277(7)°, V = 907.6(3) Å, and Z = 1. The crystal structure was resolved in the temperature range between 223 and 123 K, showing that changes in the crystal structure at low temperature result in stronger interactions between anions and cations. The packing of 1 consists of mixed anion-cation layers in the bc plane containing S···S and À-À anion-cation interactions, the layers being connected by very short S···S contacts between anions and cations. Magnetic measurements in a small external field show bulk spontaneous magnetization with a T of 6.6 K consistent with the presence of weakly coupled ferrimagnetic order in compound 1. The EPR measurements also demonstrate the interaction between the d and À electrons and the presence of an internal magnetic field brought about by the magnetic ordering.
Saygili N, Brown RJ, Hoelzl R, Mageean ER, Ozturk T, Pilkington M, Vorwerg L, Wallis JD, Day P, Turner SS, Kathirgamanathan P, Qayyum MMB (2001) Functionalised organosulfur donor molecules: Synthesis of racemic hydroxymethyl-, alkoxymethyl- and dialkoxymethyl-bis(ethylenedithio)tetrathiafulvalenes, Tetrahedron 57 (23) pp. 5015-5026 Elevier
Short synthetic routes to racemic derivatives of bis(ethylenedithio)tetrathiafulvalene carrying one hydroxymethyl (HMET), alkoxymethyl or dialkoxymethyl side chain are reported along with cyclic voltammetry measurements and conversion of HMET to (2:1) radical cation salts. © 2001 Elsevier Science Ltd.
Coldea AI, Bangura AF, Ardavan A, Singleton J, Akutsu-Sato A, Akutsu H, Turner SS, Day P (2004) Fermiology of new charge-transfer salts, ²3-(BEDT-TTF) 4[(H3O)M(C2O4)3]-solvent where M = Ga, Cr and Fe, Journal De Physique. IV : JP 114 pp. 205-209
We report high-field magnetotransport measurements on ²3-(BEDT- TTF)4[(H3O)M(C2O4) 3]· solvent, where M=Ga3+, Cr3+ and Fe3+ and solvent=C5H5N. In spite of their differing transition metal-ions, M, the three compounds exhibit similar magnetic quantum oscillation spectra superimposed on a positive magnetoresistance. At least four independent quantum oscillation frequencies have been identified, corresponding to two different hole and electron pockets of the Fermi surface which follow the rules of a compensated metal. Observation of the small pockets could be the result of the Fermi surface reconstruction induced by a possible density wave. The effective masses are very similar for different samples and for different pockets range between meff H 0.5-1.1 me whereas the Dingle temperatures varies between TD H 1.4-4 K. At low temperature, the longitudinal magnetoresistance violates Kohler's rule, suggesting that the interlayer transport in these quasi-2D systems cannot be related to a single scattering time and that the disorder plays an important role. © EDP Sciences.
Akutsu-Sato A, Akutsu H, Turner SS, Day P, Probert MR, Howard JA, Akutagawa T, Takeda S, Nakamura T, Mori T (2004) The first proton-conducting metallic ion-radical salts., Angew Chem Int Ed Engl 44 (2) pp. 292-295 Wiley-VCH Verlag
Furuta K, Akutsu H, Yamada J, Nakatsuji S, Turner SS (2006) The first organic molecule-based metal containing ferrocene, JOURNAL OF MATERIALS CHEMISTRY 16 (16) pp. 1504-1506 ROYAL SOC CHEMISTRY
Akutsu H, Yamada J-I, Nakatsuji S, Akutsu-Sato A, Turner SS, Day P, Firth S, Canadell E, Clark RJH (2004) Superstructures of donor packing arrangements in a series of molecular charge transfer salts, Chemical Communications 10 (1) pp. 18-19
Three conducting BEDT-TTF charge-transfer salts with tri-s(oxalato) metallate anions have unit cells containing both ± and ²3 donor packing motifs.
Mas-Torrent M, Vidal-Gancedo J, Veciana J, Rovira C, Turner SS, Day P, Wurst K (2003) New molecular charge-transfer salts of TM-TTF and BMDT-TTF with thiocyanate and selenocyanate complex anions [TMTTF = tetramethyltetrathiafulvalene; BMDT-TTF = bis(methylenedithio)tetrathiafulvalene], European Journal of Inorganic Chemistry (4) pp. 720-725
Three new charge-transfer salts of tetrathiafulvalene (TTF)-based donors with thiocyanato- or selenocyanato-metal complex anions have been synthesised. The salts isolated were [BMDT-TTF][Cr(NCS)] (1), [TM-TTF][Cr(NCS)]·2CHCN (2) and [TM-TTF][Cr(NCSe)]·2CHCN (3) [BMDT-TTF = bis-(methylenedithio)tetrathiafulvalene and TM-TTF = tetramethyltetrathiafulvalene]. Single crystals of compound 1 crystallise in the monoclinic C2/c space group with a = 37.286(3), b= 10.0539(6), c= 21.069(2) Å, ² = 124.348(4)°, V = 6520.9(9) Å and Z = 4. Compound 3 was also suitable for an X-ray diffraction study, however the anionic part, [Cr(NCSe)] was highly disordered and the best solution gave a final R factor of 16.4%. A solution was found for the monoclinic space groupo C2/m with a = 113.787(3), b= 19.507(3), c = 14.735(5) Å, ² = 102.90(3)°, V = 3862.9(17) Å and Z = 2. For compound 1 there are several S ï S close atomic contacts between the donors and acceptors, but there is no discernible magnetic exchange between ions. Such an interaction was previously observed in related salts such as [TTF][Cr(NCS)(phenanthroline)] and [donor] [M(NCS)(isoquinoline)] [M = Cr, Fe and donor = TTF, BEDT-TTF or TM-TTF (tetramethyltetrathiafulvalene)]. Compounds 1 to 3 are all paramagnetic semiconductors in which the magnetic susceptibility is dominated by the Cr-containing anions. The structure-function relationship, along with a comparison with related compounds, indicates that there is no long-range magnetic order because there are no À-stacking interactions between donor and acceptor; these types of interactions are seen in all of the bulk magnets of this type in which the donor spin is magnetically coupled to the anion. © Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
Akutsu H, Yamashita S, Yamada J-I, Nakatsuji S, Hosokoshi Y, Turner SS (2011) A Purely Organic Paramagnetic Metal, kappa-beta ''-(BEDT-TTF)(2)(PO-CONHC2H4SO3), Where PO=2,2,5,5-Tetramethyl-3-pyrrolin-1-oxyl Free Radical, CHEMISTRY OF MATERIALS 23 (3) pp. 762-764 AMER CHEMICAL SOC
Li L, Clarkson GJ, Evans DJ, Lees MR, Turner SS, Scott P (2011) Isomeric Fe(ii) MOFs: from a diamond-framework spin-crossover material to a 2D hard magnet., Chem Commun (Camb) 47 (47) pp. 12646-12648
Two Fe(ii) coordination polymers formed from isomeric ligands give a diamond-like 3D network exhibiting a gradual SCO and a 2D hard magnet with a large coercive field.
Kurmaev EZ, Galakhov VR, Moewes A, Shimada S, Endo K, Turner SS, Day P, Lyubovskaya RN, Ederer DL, Iwami M (2000) Electronic structure of molecular superconductors containing paramagnetic 3d ions, Physical Review B - Condensed Matter and Materials Physics 62 (17) pp. 11380-11383
The results of x-ray fluorescence measurements of the molecular superconductors (ET)4[(H3O)Fe(C2O4) 3]·C6H5CN (Tc = 8.5 K) and (ET)4[(H3O)Cr(C2O4) 3]·C6H5CN (Tc
Li L, Becker JM, Allan LE, Clarkson GJ, Turner SS, Scott P (2011) Structural and electronic modulation of magnetic properties in a family of chiral iron coordination polymers., Inorg Chem 50 (13) pp. 5925-5935
The complexes FeL(2) [L = bidentate Schiff base ligands obtained from (R)-(+)-±-phenylethanamine and 4-substituted salicylaldehydes, substituent R = H, (t)Bu, NO(2), OMe, CN, OH] react with ditopic proligands 1,4-pyrazine (pz) or 4,4'-bipyridine (bpy), to give a family of optically pure Fe(II) polymeric chain complexes of formula {FeL(2)(¼-pz)}(?) and {FeL(2)(¼-bpy)}(?). Crystallographic studies show that a range of structures are formed including unidirectional and bidirectional linear polymers and canted zigzag chains. Interchain interactions via À-contacts and hydrogen bonding are also observed. SQuID magnetometry studies on all of the complexes reveal antiferromagnetic interactions, the magnitudes of which are rationalized on the basis of substituent electronic properties and bridging ligand identity. For complexes with bridging pz, the antiferromangnetic interaction is enhanced by electron-releasing substituents on the Fe units, and this is accompanied by a contraction in the intrachain distance. For complexes bridged with the longer bpy the intrachain antiferromagnetic couplings are much weaker as a result of the longer intrachain distance. The magnetic data for this series of chain complexes follow a Bonner-Fisher 1D chain model, alongside a zero field splitting (ZFS) model for Fe(II) (S = 2) as appropriate. The intrachain antiferromagnetic coupling J values, g-factors, and the axial ZFS parameter D were obtained.
Akutsu H, Yamada JI, Nakatsuji S, Turner SS (2006) A novel BEDT-TTF-based purely organic magnetic conductor, ± - (BEDT - TTF)2(TEMPO - N(CH3)COCH2SO3) {dot operator} 3H2O, Solid State Communications 140 (5) pp. 256-260
A new BEDT-TTF-based salt with an organic free radical TEMPO has been prepared. The salt consists of alternate layers of conducting and magnetic sheets, between which are short S(BEDT-TTF) ...O(TEMPO) contacts. The magnetic susceptibility is well modelled by the combination of a 2D Heisenberg and a Curie-Weiss model with J = - 89 K and ¸ = + 0.05 K. © 2006 Elsevier Ltd. All rights reserved.
Kurmaev EZ, Shamin SN, Moewes A, Winarski RP, Ederer DL, Feng JY, Turner SS (2002) Characterization of CN films by X-ray emission measurements, Thin Solid Films 402 (1-2) pp. 60-64
The local atomic bonding structure of carbon nitride films synthesized by the reactive ionized cluster beam method using X-ray emission spectra (XES) was examined. An ionized cluster beam system was used to prepare the carbon nitride films. The composition of carbon nitride films was measured with Rutherford backscattering spectroscopy techniques and the N/C ratio was found to be approximately 0.25. The XES measurements of the carbon nitride films showed a predominant proportion of sp bonded carbon and nitrogen atoms.
Bangura AF, Coldea AI, Singleton J, Ardavan A, Akutsu-Sato A, Akutsu H, Turner SS, Day P, Yamamoto T, Yakushi K (2005) Robust superconducting state in the low-quasiparticle-density organic metals ²3-(BEDT-TTF)4[(H3O)M(C2O4)3]Y: Superconductivity due to proximity to a charge-ordered state, Physical Review B - Condensed Matter and Materials Physics 72 (1)
We report magnetotransport measurements on the quasi-two-dimensional charge-transfer salts ²3-(BEDT-TTF)4[(H3O)M(C2O4)3]Y, with Y=C6H5NO2 and C6H5CN using magnetic fields of up to 45 T and temperatures down to 0.5 K. A surprisingly robust superconducting state with an in-plane upper critical field Bc2 33T, comparable to the highest critical field of any BEDT-TTF superconductor, and critical temperature Tcâ 7K is observed when M=Ga and Y=C6H5NO2. The presence of magnetic M ions reduces the in-plane upper critical field to 18T for M=Cr and Y=C6H5NO2 and M=Fe and Y=C6H5CN. Prominent Shubnikov-de Haas oscillations are observed at low temperatures and high magnetic fields, showing that the superconducting salts possess Fermi surfaces with one or two small quasi-two-dimensional pockets, their total area comprising 6% of the room-temperature Brillouin zone; the quasiparticle effective masses were found to be enhanced when the ion M was magnetic (Fe or Cr). The low effective masses and quasiparticle densities, and the systematic variation of the properties of the ²3-(BEDT-TTF)4[(H3O)M(C2O4)3]Y salts with unit-cell volume points to the possibility of a superconducting groundstate with a charge-fluctuation-mediated superconductivity mechanism such as that proposed by Merino and McKenzie [Phys. Rev. Lett. 87, 237002 (2001)], rather than the spin-fluctuation mechanism appropriate for the º-(BEDT-TTF)2X salts. © 2005 The American Physical Society.
Yamamoto T, Yamamoto HM, Kato R, Uruichi M, Yakushi K, Akutsu H, Sato-Akutsu A, Kawamoto A, Turner SS, Day P (2008) Inhomogeneous site charges at the boundary between the insulating, superconducting, and metallic phases of beta '-type bis-ethylenedithio-tetrathiafulvalene molecular charge-transfer salts, PHYSICAL REVIEW B 77 (20) ARTN 205120 AMER PHYSICAL SOC
Rashid S, Turner SS, Le Pevelen D, Day P, Light ME, Hursthouse MB, Firth S, Clark RJH (2001) ²3-(BEDT-TTF)[(HO)Cr(CO )]CHCl: Effect of included solvent on the structure and properties of a conducting molecular charge-transfer salt, Inorganic Chemistry 40 (20) pp. 5304-5306 American Chemical Society
The new charge-transfer salt ²3-(BEDT-TTF)[(HO)Cr(CO )]S, where BEDT-TTF = bis-(ethylenedithio)tetrathiafulvalene and S = CHCl has a broad metal-insulator transition at approximately 150 K. This differs from similar salts in the BEDT-TTF tris(oxalato) metalate series, notably the superconducting materials with S = PhCN and the salt with S = CHN, which has a sharp metal-insulator transition.
Akutsu H, Akutsu-Sato A, Turner SS, Day P, Tocher DA, Probert MR, Howard JAK, Le Pevelen D, Klehe A-K, Singleton J, Laukhin VN (2003) Structures and properties of new superconductors, ²3-(ET)[(HO)Ga(CO) ]Sol [Sol = nitrobenzene and pyridine], Synthetic Metals 137 (1-3) pp. 1239-1240
The title compounds containing diamagnetic Ga are superconductors. The nitrobenzene salt shows a broad metal-semiconductor transition at 160 K but becomes superconductor below 7.5 K. The Meissner volume of a powder sample at 1.8 K is estimated at 31%. The pyridine salt also has a broad upturn in resistance at 130 K, a re-entrant metallic phase below 60 K, and a resistance loss below 1.5 K. The loss vanishes with applying magnetic field, suggesting that it is also superconductor.
Turner SS, Day P (2005) Ion-radical salts: A new type of molecular ferrimagnet, Journal of Materials Chemistry 15 (1) pp. 23-25
Long-range ferrimagnetic order in which one magnetic sub-lattice is formed from partly-occupied p-orbitals and the other from d-orbitals can be achieved in molecular ion-radical salts where the cations are oxidised organo-chalcogen donors and the anions are 3d-metal complexes containing both N-bonded NCS and planar N-heterocyclic ligands. Overlaps between p-orbitals of the radical cations and those of the heterocycle are implicated in the cation-anion exchange pathway.
Narduzzo A, Ardavan A, Coldea AI, Singleton J, Akutsu-Sato A, Akutsu H, Turner SS, Day P (2003) Millimetre-wave response of the novel organic superconductors ²3-ET[(HO)M(CO)].S (M=Fe, S= CHCN and CHNO), Synthetic Metals 137 (1-3) pp. 1225-1226
The millimeter-wave response of the novel organic superconductors was studied. The magneto-optical response of the two samples containing Fe ions and the host solvents benzonitrile and nitrobenzene. The angle dependence of the electron paramagnetic resonance (EPR) spectra and the anisotropy of the g-factors for the two materials were presented. The angle of dependence of the absorption spectra at 1.4 K for the two samples were compared.
Setifi F, Golhen S, Ouahab L, Turner SS, Day P (2002) Preparation, X-ray crystal structures and properties of ±-(BEDT-TTF)[Fe(phen)(NCS)[· 2CHCl and (BEDT-TTF)]Cr(isoq) (NCS)[ (phen = 1,10-phenanthroline; Isoq = isoquinoline), CrystEngComm 4 (1) pp. 1-6
This paper reports the preparation, X-ray crystal structure, conducting and magnetic properties of ±-(BEDT-TTF)]Fe(phen) (NCS)[ (1) [BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene, phen = 1,10-phenanthroline] together with the crystal structure of (BEDT-TTF)]Cr (isoq)(NCS)[ (2) (isoq = isoquinoline) for which the physical properties have been reported previously. Compound 1 crystallizes in the triclinic space group P1 (no. 2), a = 12.1528(1), b = 16.8269(3), c = 27.0703(4) Å, ± = 95.726(1), ² = 95.834(1), ³ = 108.080(1)°, Z = 4, R = 0.0610 for 9764 reflections with I > 2Ã(I); 2 crystallizes in the monoclinic space group P2/c (no. 14), a =10.623(5), b = 14.656(8), c = 12.701(7) Å, ² = 100.19(2)°, Z = 2, R = 0.0737 for 2747 reflections with I > 2Ã(I). The magnetic and transport properties have shown that compound 1 is a paramagnetic semiconductor with à = 2.2 × 10 © cm. © 2002 The Royal Society of Chemistry.
Yamamoto T, Nakazawa Y, Kato R, Yakushi K, Akutsu H, Akustu AS, Yamamoto H, Kawamoto A, Turner SS, Day P (2009) Charge fluctuation of the superconducting molecular crystals, PHYSICA B-CONDENSED MATTER 405 (11) pp. S237-S239 ELSEVIER SCIENCE BV
Kanbayashi N, Akutsu H, Yamada JI, Nakatsuji S, Turner SS (2012) A new ferrocene-containing charge-transfer salt, (TTF) 2[Fe(C 5H 4-CH(CH 3)NHCOCH 2SO 3) 2], Inorganic Chemistry Communications 21 pp. 122-124
A novel ferrocene-containing dianion, Fe(C 5H 4- CH(CH 3)NHCOCH 2SO 3-) 2 (1), has been prepared. The oxidation potential of the PPh 4 salt is + 0.35 V (vs. SCE in PhCN), indicating that it is a stronger donor than TTF (tetrathiafulvalene) by + 0.03 V. The dianion provided a TTF salt, the structure and physical properties of which are reported. © 2012 Elsevier B.V. All rights reserved.
Bangura AF, Coldea AI, Singleton J, Ardavan A, Klehe AK, Akutsu-Sato A, Akutsu H, Turner SS, Day P (2003) Magnetotransport measurements on ²"-(BEDT-TTF)[(HO)Ga(CO)]. CHNO, Synthetic Metals 137 (1-3) pp. 1313-1314
Transport measurements have been carried out on single crystals of the charge transfer salt ²3-(BEDT-TTF)[(HO)Ga(CO)]. CHNO, using magnetic fields of up to 33 T and temperatures down to 0.55 K. The material is found to be superconducting with T H 7.5 K and an in-plane critical field B e 33 T, and to exhibit Shubnikov-de Haas (SdH) oscillations. The temperature and angle dependence of the Shubnikov-de Haas oscillations and the upper critical field are reported, allowing information about the anisotropy of the upper critical field, effective mass m*, and the Fermi-surface (FS) of the material to be deduced.
Akutsu-Sato A, Kobayashi A, Mori T, Akutsu H, Yamada J, Nakatsuji S, Turner SS, Day P, Tocher DA, Light ME, Hurstho MB (2005) Structures and physical properties of new ²2-BEDT-TTF tris-oxalatometallate (III) salts containing chlorobenzene and halomethane guest molecules, Synthetic Metals 152 (1-3) pp. 373-376
We report the structures and physical properties of new ²2-(BEDT-TTF)[Fe(oxalate)]·G salts where A = HO, G = PhCl; A = Rb G = Pyridine. The structure of the PhCl salt is isomorphous with ²2-(BEDT-TTF)[(HO)M(oxalate)] with other guest molecules. PhCl is ordered in die hexagonal pockets formed by the [(HO)Fe(oxalate)] layer. The electrical conductivity is metallic down to 100 K, below which the resistivity increases with decreasing temperature. The specific conductivity at room temperature is about 10 S/cm. We also report the salt ²2-(BEDT-TTF) [RbFe(oxalate)]·Pyridine where Rb replaces HO. The electrical resistivity shows metallic behavior down to 100 K. and turns up gradually to a maximum at 65 K below which the system re-enters the metallic state down to liquid helium temperature. Neither salt shows superconductivity down to 2 K. In addition, other new ²2-(BEDT-TTF)[(HO)M(oxalate) ]·salts with M = Cr, Ga, Fe; G = CHCl , CHClBr, CHBr are also reported. © 2005 Elsevier B.V. All rights reserved.
Lethbridge ZAD, Clarkson GJ, Turner SS, Walton RI (2009) Polymorphism and variable structural dimensionality in the iron(III) phosphate oxalate system: a new polymorph of 3D [Fe-2(HPO4)(2)(C2O4)(H2O)(2)]center dot 2H(2)O and the layered material [Fe-2(HPO4)(2)(C2O4)(H2O)(2)], DALTON TRANSACTIONS (42) pp. 9176-9182 ROYAL SOC CHEMISTRY
Rashid S, Turner SS, Day P, Howard JAK, Guionneau P, McInnes EJL, Mabbs FE, Clark RJH, Firth S, Biggs T (2001) New superconducting charge-transfer salts (BEDT-TTF)(4)[A center dot M(C2O4)(3)]center dot C6H5NO2 (A = H3O or NH4, M = Cr or Fe, BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene), JOURNAL OF MATERIALS CHEMISTRY 11 (9) pp. 2095-2101 ROYAL SOC CHEMISTRY
Rashid S, Turner SS, Day P, Light ME, Hursthouse MB, Guionneau P (2001) Novel charge transfer salts of BEDT-TTF with metal oxalate counterions, Synthetic Metals 120 (1-3) pp. 985-986 Elsevier
The preparation, crystal structures and properties of three new BEDT-TTF, bis(ethylenedithio)tetrathiafulvalene, (ET for short), charge transfer salts ²3(ET).[(HO)Cr(C O)].CHNOI, ²3(ET).[(HO)Fe(C O)].CHNO II and (ET).[Fe(CO)] III are reported. The structures of I and II consist of alternating layers of ET and an approximately hexagonal network formed by HO and the metal with the solvent molecule, CHNO, occupying hexagonal cavities in the anion layer. Both CHNO salts are superconducting, the iron salt having a T of 6.2 K and the chromium salt having a T of 5.8 K. The structure of (ET)[Fe(CO)] consists of an iron oxalate bridged dimer, (Fe-Fe distance 5.472 Å), interspersed with ET in a "checker board" arrangement. It is monoclinic and crystallises in the P2/n space group. At 150 K a = 16.8068 (3) Å, b = 10.9556 (2) Å, c = 19.4109 (3) Å, ² = 102.1593 (9)° and V = 3493.92 (10) Å. Squid measurements show short range antiferromagnetic ordering.
Akutsu H, Hashimoto R, Yamada J-I, Nakatsuji S, Nakazawa Y, Turner SS (2015) Structures and properties of new ferrocene-based paramagnetic anion octamethylferrocenedisulfonate and its ITF salt, INORGANIC CHEMISTRY COMMUNICATIONS 61 pp. 41-47 ELSEVIER SCIENCE BV
Akutsu H, Ohnishi R, Yamada J-I, Nakatsuji S, Turner SS (2007) Novel bis(ethylenedithio)tetrathiafulvalene-based organic conductor with 1,1 '-ferrocenedisulfonate, INORGANIC CHEMISTRY 46 (21) pp. 8472-8474 AMER CHEMICAL SOC
Turner SS, Michaut C, Durot S, Day P, Elbrich T, Hursthouse MB (2000) TTF based charge transfer salts of [M(NCS)(CHN)] where M = Cr, Fe and CHN = isoquinoline; observation of bulk ferrimagnetic order, Journal of the Chemical Society, Dalton Transactions (6) pp. 905-909
Three new charge transfer salts of BEDT-TTF and TTF with the counter ions [M(NCS)4(C9H7N)J~ (M = Cr, Fe; C9H7N = isoquinoline) are described. The materials are prepared by standard electrocrystallisation techniques. The nature of the anion is verified in the crystal structure of the salt [C9H8N][Cr(NCS)4(C9H7N)]-C,2H24O6-H2O which is used as the electrolyte when M = Cr. All of the charge transfer salts display long range ferrimagnetic order originating from the interaction between M (5=3/2 or 5= 5/2) and the donor (5= 1/2). The measured critical temperatures are 4.2 K (BEDT-TTF, M = Cr), 4.5 K (BEDT-TTF, M = Fe) and 8.9 K (TTF, M = Cr). Each of the compounds also shows a modest magnetic hysteresis of 338, 18 and 75 Oe for BEDT-TTF salts of M = Cr, Fe and the TTF salt of Cr, respectively. © The Royal Society of Chemistry 2000.
Li L, Liu Z, Liao D, Jiang Z, Yan S, Turner SS (2003) The first one-dimensional copper(II)-radical system with alternating double end-on and end-to-end azido bridges, New Journal of Chemistry 27 (4) pp. 752-755
A novel one-dimensional copper(II)-radical complex [Cu(NITmPy)(N)(CHOH)] [NITmPy = 2-(32-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide] has been synthesized and structurally characterized. The structure consists of neutral chains of copper(II) ions alternatively bridged by double symmetric end-on and asymmetric end-to-end azide groups. The NITmPy radical ligand coordinates to the copper(II) ions through the nitrogen atom of the pyridyl ring. The magnetic properties were investigated in the temperature range 5-300 K. The complex exhibits ferromagnetic interactions between the copper(II) ions through the end-on and end-to-end azido bridging ligands, and between the copper(II) ion and NITmPy radical. The magnetic behavior is discussed with reference to the crystal structure.
Narduzzo A, Coldea AI, Ardavan A, Singleton J, Pardi L, Bercu V, Akutsu-Sato A, Akutsu H, Turner SS, Day P (2006) A spin resonance investigation of magnetism and dynamics in the charge transfer salts ß??-(BEDT-TTF)4[(H3O)M(C2O4)3S], J. Low Temp. Phys 142 pp. 585-588
Rashid S, Turner SS, Le Pevelen D, Day P, Light ME, Hursthouse MB, Firth S, Clark RJ (2001) beta' '-(BEDT-TTF)4[(H3O)Cr(C2O4)3]CH2Cl2: effect of included solvent on the structure and properties of a conducting molecular charge-transfer salt., Inorg Chem 40 (20) pp. 5304-5306
Akutsu H, Yamada JI, Nakatsuji S, Turner SS (2012) A New BEDT-TTF-based organic charge transfer salt with a new anionic strong acceptor, N,N'-disulfo-1,4-benzoquinonediimine, Crystals 2 (2) pp. 182-192
A novel organic dianion, N,N'-Disulfo-1,4-benzoquinonediimine (1) has been prepared, which is a strong electron acceptor. The reduction potential of the PPh4 salt indicates that 1 is a stronger acceptor than DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone). The dianionic acceptor provided a BEDT-TTF salt, (BEDT-TTF)41·3H2O, the structures and physical properties of which are reported. © 2011 by the authors; licensee MDPI, Basel, Switzerland.
Turner SS, Le Pévelen D, Day P, Prout K (2002) Synthesis, crystal structures and physical properties of TTF-based conducting charge transfer salts with anions containing selenocyanate ligands, Journal of Solid State Chemistry 168 (2) pp. 573-581
Three new charge transfer salts of tetrathiafulvalene (TTF)-based donors with selenocyanate-metal complex anions have been synthesized. The salts have been characterized as BEDT-TTF[Cr(NCSe)]·CHCl , II, TTF[Cr(NCSe)phen], III and BEDT-TTF[Cr(NCSe)phen]·CHCl , IV, where phen = 1,102-phenanthroline and BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene. At 120 K, II crystallizes in the P2/m space group with a = 10.454(1), b = 31.990(1), c = 12.339(1) Å, ² = 113.163(2)°, V = 3793.8 Å, Z = 4 and at 240 K in the same space group with a = 10.530(1), b = 32.122(1), c = 12.396(1) Å, ² = 113.186(3)°, V = 3854.2 Å, Z = 4. At 240 K III crystallizes in the C2/c space group, a = 38.9272(5), b = 11.2992(1), c = 15.2540(3) Å, ² = 106.8877(6)°, V = 6420.1 Å, Z = 8. The structure of IV has been solved in the P1? space group with a = 8.7629(3), b = 11.7977(4), c = 26.6031(9), ± = 81.697(2), ² = 87.858(3), ³ = 74.8471(14), V = 2626.8 Å, Z = 2. All of the salts have numerous SïSe close atomic contacts between donors and acceptors but there is no magnetic exchange between ions, as previously seen in closely related salts such as TTF[Cr(NCS)phen] and (donor)[M(NCS)(isoquinoline)], where M = Cr, Fe and donor = TTF, BEDT-TTF or TMTTF (tetramethyltetrathiafulvalene). Indeed, II and IV are paramagnetic semiconductors whereas IlI is a paramagnetic insulator. The absence of long-range magnetic order is discussed in terms of structure-function relations since there are no À-stacking interactions between donor and acceptor, which are seen in all of the bulk magnets of this type where the donor spin is magnetically coupled to the anion. The synthesis and crystal structure of the starting material, [(CH)N][Cr(NCSe) ], I, is also reported; it crystallizes in the P1? space group with a = 12.220(1), b = 12.814(1), c = 13.008(1) Å, ± = 99.608(6), ² = 114.028(5), ³ = 92.637(6)°, V = 1819.5 Å, Z = 2. © 2002 Elsevier Science (USA).
Akutsu H, Akutsu-Sato A, Turner SS, Le Pevelen D, Day P, Laukhin V, Klehe AK, Singleton J, Tocher DA, Probert MR, Howard JAK (2002) Effect of included guest molecules on the normal state conductivity and superconductivity of ²2-(ET)4 [(H3O)Ga(C2O4)3]·G (G = pyridine, nitrobenzene), Journal of the American Chemical Society 124 (42) pp. 12430-12431
Normal state conductivity and superconductivity together with bulk magnetic susceptibility and magnetization measurements have been measured for two molecular charge-transfer salts: ²-(ET)4[(H3O)Ga(C2O4)3]G (ET = bis(ethylenedithio)tetrathiafulvalene, G = pyridine for compound I and nitrobenzene for compound II). With the exception of the included guest molecules (G) the crystal structures are almost identical. Both show minima in their electrical transport at 130 K for I and at 160 K for II, but at lower temperatures their behaviors differ markedly. The resistance of I reaches a maximum at 50 K with a further small peak at 2 K and possible superconductivity only below 2 K, whereas that of II increases continuously down to 7.5 K, where an abrupt transition to a superconducting state occurs. Copyright © 2002 American Chemical Society.
Li L, Liu S, Liao D, Jiang Z, Yan S, Turner SS (2003) Crystal structure and magnetic properties of a one-dimensional polymer [Mn(im2-py)(tp)(HO)]·1.25HO, Journal of Coordination Chemistry 56 (5) pp. 383-388
A new manganese(II) complex [Mn(im2-py)(tp)(HO)]·1.25HO (im2-py = 2-(22-pyridyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl and tp = terephthalato dianion) has been synthesized and characterized structurally and magnetically. The crystal structure consists of neutral chains of manganese(II) ions linked by the terephthalate ligand. Variable temperature magnetic susceptibility data exhibit a weak antiferromagnetic coupling between the manganese(II) ion and the imino nitroxide radical.
Li L, Clarkson GJ, Lees MR, Howson SE, Tan SY, Turner SS, Scott P (2015) Iron and Manganese Complexes of 2-Carbonyl Pyrrolyls: Scorpionate Sandwich Anions and Extended Structures, Organometallics 34 (11) pp. 2543-2549
© 2015 American Chemical Society. Attempts to synthesize complexes of Fe and Mn(II) with 2-amidopyrrolyl ligands (N-O) were unsuccessful, and only small amounts of the trivalent tris complexes M(N-O)3 were detected, although unusually in the case of Fe(III) a fac structure is observed. In contrast the 2-benzoylpyrrolyl systems give M(II) complexes, and in all instances thus far where Na+ is present, a scorpionate fac-[MII(N-O)3]- unit self-assembles into sandwich anions [MII(N-O)3Na(O-N)3MII]- in which the central metal is efficiently encapsulated by interdigitation of the aryl units. Extended structures are readily made through the use of a 2-(4-pyridinoyl)pyrrolylamide ligand. When Li+ is used, the scorpionate ligand is not assembled, and instead [M(N-O)2] units give rhombic 2D grids. The Fe system displays spin-crossover at 120 K. (Figure Presented).
Darton RJ, Turner SS, Sloan J, Lees MR, Walton RI (2010) Hydrothermal Synthesis of a B-Site Magnetic Ruthenate Pyrochlore, CRYSTAL GROWTH & DESIGN 10 (8) pp. 3819-3823 AMER CHEMICAL SOC
Akutsu-Sato A, Akutsu H, Turner SS, Le Pevelen D, Day P, Light ME, Hursthouse MB, Akutagawa T, Nakamura T (2003) Structures and physical properties of BEDT-TTF salts containing channels of protons, Synthetic Metals 135-136 pp. 597-598
Charge transfer salts with stoichiometry ²3-(BEDT-TTF) [M(CO),](18-crown-6 ether)(9HO), where M= Cr, Ga or Fe and x= 2 or 3 are reported. Their structures suggest that proton migration is possible. Variable temperature resistivity measurements on the Cr salt show metallic behaviour down to 180K. Magnetic susceptibility of the Cr salt is paramagnetic down to 1.8 K. Preliminary impedance measurements suggest that the proton conductivities of the Cr and Ga salts are the order of 10 S cm at 300 K. © 2003 Elsevier Science B.V. All rights reserved.
Turner SS, Day P, Gelbrich T, Hursthouse MB (2001) New molecular charge transfer salts of BEDT-TTF, Bis(ethylenedithio) tetrathiafulvalene, with thiocyanato-complex anions: (BEDT-TTF)[Fe(NCS)]·CHCl and (BEDT-TTF)[Cr(NCS)(bipym)]·0.15HO, Journal of Solid State Chemistry 159 (2) pp. 385-390
Two new charge transfer salts of BEDT-TTF, bis (ethylenedithio) tetrathiafulvalene, with thiocyanato-metal complex anions have been synthesized and characterized as (BEDT-TTF)[Fe(NCS)]·CHCl and (BEDT-TTF)[Cr(NCS) (bipym)]·0.15HO, where bipym=2,22-bipyrimidine. The Fe salt, I, crystallizes in the P-1 (No. 2) space group at 150 K with a=10.629(1) Å, b=12.099(1) Å, c=16.062(2) Å, ±=99.61(1)°, ²=90.87(1)°, ³=112.92(1)°, and V=1868.5(6) Å. At 150 K the Cr salt, II, crystallizes in the P-1 (No. 2) space group with a=9.243(2), b=11.781(2), c=22.925(5) Å, ±=93.76(3), ²=101.51(3), ³=105.45(3)°, V=2339.0(8) Å, and Z=2. Both salts exhibit close S···S contacts between the anion and cation components and in II there is no À-stacking between the bipym group and the BEDT-TTF molecules. Both salts are paramagnetic with C=4.926 I and C=1.819 II with small negative Weiss constants of -0.19 and -0.26, respectively. Therefore, the S···S contacts alone do not promote correlated magnetic effects as seen in other thiocyanato salts that also contain À-stacking. Each compound is a semiconductor and has two crystallographically independent BEDT-TTF molecules for which bond length analysis give charges of +0.9±0.1/+0.6±0.1 for I and +0.3±0.1/+0.9±0.1 for II. © 2001 Academic Press.
Akutsu-Sato A, Akutsu H, Yamada J, Nakatsuji S, Turner SS, Day P (2007) Suppression of superconductivity in a molecular charge transfer salt by changing guest molecule: ²3-(BEDT-TTF)[(H O)Fe(CO)](CH CN)(CHN), Journal of Materials Chemistry 17 (24) pp. 2497-2499
SQUID magnetometry and transport measurements combined with crystal structure refinement have been used to examine the variation in superconducting properties (T and Meissner fraction) in the molecular superconductor ²3-(BEDT-TTF)[(HO)Fe(CO )]·CHCN on replacing the CHCN guest molecule with pyridine (CH N). Up to approximately 65% pyridine substitution there is only a small decrease in T and Meissner fraction but above that the superconductivity is suppressed. © The Royal Society of Chemistry 2007.
Martin L, Turner SS, Day P, Guionneau P, Howard JA, Hibbs DE, Light ME, Hursthouse MB, Uruichi M, Yakushi K (2001) Crystal chemistry and physical properties of superconducting and semiconducting charge transfer salts of the type (BEDT-TTF)(4)[A(I)M(III)(C2O4)3]*PhCN (A(I) = H30,NH4,K; M(III) = Cr, Fe, Co, Al; BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene., Inorg Chem 40 (6) pp. 1363-1371
Synthesis, structure determination by single-crystal X-ray diffraction, and physical properties are reported and compared for superconducting and semiconducting molecular charge-transfer salts with stoichiometry (BEDT-TTF)(4)[A(I)M(III)(C(2)O(4))(3)].PhCN, where A(I) = H(3)O, NH(4), K; M(III) = Cr, Fe, Co, Al; BEDT-TTF = bis(ethylenedithio) tetrathiafulvalene. Attempts to substitute M(III) with Ti, Ru, Rh, or Gd are also described. New compounds with M = Co and Al are prepared and detailed structural comparisons are made across the whole series. Compounds with A = H(3)O(+) and M = Cr, Fe are monoclinic (space group C2/c), at 150, 120 K a = 10.240(1) A, 10.232(12) A; b = 19.965(1) A, 20.04(3) A; c = 34.905(1) A, 34.97(2) A; beta = 93.69(1) degrees, 93.25(11) degrees, respectively, both with Z = 4. These salts are metallic at room temperature, becoming superconducting at 5.5(5) or 8.5(5) K, respectively. A polymorph with A = H(3)O(+) and M = Cr is orthorhombic (Pbcn) with a = 10.371(2) A, b = 19.518(3) A, c = 35.646(3) A, and Z = 4 at 150 K. When A = NH(4)(+), M = Fe, Co, Al, the compounds are also orthorhombic (Pbcn), with a = 10.370(5) A, 10.340(1) A, 10.318(7) A; b = 19.588(12) A, 19.502(1) A, 19.460(4) A; c = 35.790(8) A, 35.768(1) A, 35.808(8) A at 150 K, respectively, with Z = 4. All of the Pbcn phases are semiconducting with activation energies between 0.15 and 0.22 eV. For those compounds which are thought to contain H(3)O(+), Raman spectroscopy or C=C and C-S bond lengths of the BEDT-TTF molecules confirm the presence of H(3)O(+) rather than H(2)O. In the monoclinic compounds the BEDT-TTF molecules adopt a beta' ' packing motif while in the orthorhombic phases (BEDT-TTF)(2) dimers are surrounded by monomers. Raman spectra and bond length analysis for the latter confirm that each molecule of the dimer has a charge of +1 while the remaining donors are neutral. All of the compounds contain approximately hexagonal honeycomb layers of [AM(C(2)O(4))(3)] and PhCN, with the solvent occupying a cavity bounded by [M(C(2)O(4))(3)](3-) and A. In the monoclinic series each layer contains one enantiomeric conformation of the chiral [M(C(2)O(4))(3)](3-) anions with alternate layers having opposite chirality, whereas in the orthorhombic series the enantiomers form chains within each layer. Analysis of the supramolecular organization at the interface between the cation and anion layers shows that this difference is responsible for the two different BEDT-TTF packing
Narduzzo A, Ardavan A, Singleton J, Pardi L, Bercu V, Akutsu-Sato A, Akutsu H, Turner SS, Day P (2004) Electron spin resonance studies of the organic superconductor ²3-(BEDT-TTF)4[(H3O)Fe(C2O 4)3]C6H5CN, Journal De Physique. IV : JP 114 pp. 347-349
We applied magneto-optical techniques to investigate the electron spin resonance (ESR) spectra of single crystal and powder samples of the organic superconductor ²3-(BEDT- TTF)4[(H3O)Fe (C 2O4]C6H5CN. Data were obtained in magnetic fields up to 10 Tesla using both cylindrical and rectangular resonators at 55, 63 and 72 GHz and transmission measurements at 95 and 190 GHz with field modulation. Analysis of the high field-high frequency ESR lines for different field orientations and temperatures allows the determination of the g-value anisotropy and the zero-field splitting parameters for the Fe3+ ions (S = 5/2), showing that they occupy a site with distorted octahedral symmetry. The temperature and frequency dependences of the magneto-optical spectra are used to identify the nature of the interaction between localised Fe spins and between the local moments and the delocalised carriers. © EDP Sciences,.
Coldea AI, Bangura AF, Ardavan A, Singleton J, Akutsu-Sato A, Akutsu H, Turner SS, Day P (2004) Fermi-surface topology and the effects of intrinsic disorder in a class of charge-transfer salts containing magnetic ions: ²3-(BEDT-TTF) [HO)M(CO)]Y (M=Ga, Cr, Fe; Y=CHN), Physical Review B - Condensed Matter and Materials Physics 69 (8) pp. 851121-8511211
We report high-field magnetotransport measurements on ²3 -(BEDT-TTF)[(HO)M(CO) ]Y, where M =Ga, Cr, and Fe and Y=CHN. We observe similar Shubnikov-de Haas oscillations in all compounds, attributable to four quasi-two-dimensional Fermi-surface pockets, the largest of which corresponds to a cross-sectional area H8.5% of the Brillouin zone. The cross-sectional areas of the pockets are in agreement with the expectations for a compensated semimetal, and the corresponding effective masses are
Turner SS, Pevelen DL, Day P, Prout K (2000) TTF based charge transfer salts of [Cr(NCS)4(phen)]-: Bulk magnetic order and crystal structures of the TTF, TMTTF (tetramethyltetrathiafulvalene) and TMTSF (tetramethyltetraselenafulvalene) derivatives, Journal of the Chemical Society, Dalton Transactions (16) pp. 2739-2744
A series of new charge transfer salts of electron donors based on tetrathiafulvalene, TTF, with the anion [Cr(NCS)4(phen)]~ (phen = 1,10-phenanthroline) have been prepared. Single crystal X-ray diffraction provided structures for salts with donors TTF, TMTTF, tetramethyltetrathiafulvalene, and TMTSF, tetramethyltetraselenafulvalene. The salts were found to be [TTF][Cr(NCS)(phen)] at 293 K, [TMTTF][Cr(NCS)(phen)]-CHCl2 at 250 K and rrMTSF][Cr(NCS)(phen)]2-0.5CHCl at 293 K. For the TMTSF compound the solvent is disordered at 293 K so the structure was also solved at 120 K when the solvent becomes ordered. All of the salts have multiple S ïS or S ïSe close contacts between the anions and cations. The TTF salt is a bulk ferrimagnet with Tc = 9 K and is an insulator whereas the TMTTF salt is an antiferromagnetic (TN = 3.0 K) insulator. Both have close atomic interactions of the phen-donor n-stacking type, but the TMTTF salt also contains close anion-anion contacts and dimerised cations whereas the TTF salt consists of stacks of alternating cations and anions. The TMTSF salt is a paramagnetic semiconductor and does not display n stacking but has close inter-donor Se ïSe contacts and isolated anions which afford the magnetic and transport properties. © The Royal Society of Chemistry 2000.
Chmel NP, Howson SE, Allan LEN, Barker J, Clarkson GJ, Turner SS, Scott P (2010) Organic-soluble optically pure anionic metal complexes PPh(4)[M(III)(S,S-EDDS)]center dot 2H(2)O (M = Fe, Co, Cr), DALTON TRANSACTIONS 39 (11) pp. 2919-2927 ROYAL SOC CHEMISTRY
Akutsu H, Yamada J-I, Nakatsuji S, Turner SS (2007) An anionic weak acceptor 2-aminomethylsulfo-3,5,6-trichloro-1, 4-benzoquinone and its BEDT-TTF-based charge-transfer salts, SOLID STATE COMMUNICATIONS 144 (3-4) pp. 144-147 PERGAMON-ELSEVIER SCIENCE LTD
Coldea AI, Bangura AF, Ardavan A, Singleton J, Akutsu-Sato A, Akutsu H, Turner SS, Day P (2004) The role of magnetic ions on the magnetotransport properties of the charge-transfer salts ²3-BEDT-TTF[(HO) M(CO)]CHN where M=Ga, Cr or Fe, Journal of Magnetism and Magnetic Materials 272-276 pp. 1062-1064
We report high-field magnetotransport measurements on ²3-BEDT- TTF[(HO)M(CO)]C HN, where M=Ga, Cr or Fe . In spite of the differing M ions, these compounds have very similar Fermi surfaces. We observe four distinct Shubnikov-de Haas frequencies, corresponding to four Fermi-surface pockets; the frequencies exhibit the additive relationship expected for a compensated semimetal. The compounds show paramagnetic behaviour and no superconductivity down to 0.5 K, in contrast to other materials of the same family with different solvent molecules. © 2003 Elsevier B.V. All rights reserved.
Akutsu H, Yamada JI, Nakatsuji S, Turner SS (2014) Crystal structure of PPh4[Fe(NO)2Cl2], X-ray Structure Analysis Online 30 (10) pp. 49-50
© The Japan Society for Analytical Chemistry.The title compound, (C24H20P)(FeN2O2Cl2), was prepared by adapting of literature methods. It crystallizes in the tetragonal space group P4. The structure consists of one P(C6H5)4 cation and one Fe(NO)2Cl2 anion. The anion has one ordered NO group and one ordered Cl ligand. The other two ligands are disordered, such that one half of NO and a half of Cl are located at each position.
Rombaut G, Turner SS, Le Pévelen D, Mathonière C, Day P, Prout K (2001) An unusual phase transition in the crystal structure and physical properties of (TTF)[MO(CN)]·4HO, where TTF = tetrathiafulvalene, Journal of the Chemical Society, Dalton Transactions (22) pp. 3244-3249
At 270 K, the charge transfer salt(TTF)[Mo(CN)]·4H O,I, crystallizes in the triclinic space group P1? with a = 9.9094(2), b = 10.6781(2), c = 23.6086(7) Å, a = 75.7910(8), ² = 88.6010(9), ³ = 78.5250(8)°, V = 2372.5(1) Å and Z = 2. At 120 K, the space group is unchanged with a = 9.7990(7), b = 10.6630(5), c = 22.9940(2) Å, a = 79.981(4), ² = 89.798(4), ³ = 79.013(4)°, V = 2321.5 Å and Z = 2. On comparing the two sets of data, we see significant changes in the cell parameters, most notably in the angle a. Variable temperature crystallographic studies indicate a first order phase transition accompanied by hysteresis, which corresponds to a change in the transport properties.I is a semiconductor and the high temperature activation energy of 0.06 eV changes sharply to 0.15 eV below 236 K. Bulk magnetic susceptibility and ESR measurements indicate that the TTF molecules are antiferromagnetically coupled. The temperature dependence of the EPR spectrum changes from 300-200 K, in approximate agreement with the transport and structural results. The optical spectrum of (TTF)[Mo(CN)]·4HO consists of several broad bands assigned to TTF charged molecules, to [Mo(CN)] and to charge transfer from the donors to the acceptor in the near infra-red range. Preliminary magnetic susceptibility measurements under light irradiation with a multi-line (752.5-799.3 nm) laser were also performed, but no photomagnetic effect was noted.
Akutsu H, Sato K, Yamashita S, Yamada J-I, Nakatsuji S, Turner SS (2008) The first organic paramagnetic metal containing the aminoxyl radical, Journal of Materials Chemistry 18 (28) pp. 3313-3315
We have prepared an organic magnetic anion, PROXYL-4-CONHCH
SO

(1). The electrocrystallisation of BEDT-TTF with PPh
1 gave the first purely organic paramagnetic metal, ²3-(BEDT-TTF)
(1). The salt shows a broad metal-insulator transition at approximately 210 K. © The Royal Society of Chemistry 2008.

Turner SS, Le Pévelen D, Day P (2003) Interaction between cation and anion sublattices in molecular charge transfer salts: Structural conditions for ferrimagnetism, Synthetic Metals 133-134 pp. 497-500
Many molecular charge transfer salts with organo-chalcogen donors and transition-metal complex anions have been synthesised in recent years in an effort to find lattices that combine conductivity with long range magnetic order, but in most cases interaction between the donor and anion sublattices is very weak. We have approached this issue by selecting anions that contain S or Se atoms capable of forming close non-bonding contacts with the donor molecules, and which also contain aromatic rings to form À-À contacts. In this way new ferrimagnets have been synthesised and characterised, with general formula D[M(NCX)B] where D is TTF or BEDT-TTF; M = Cr, Fe; X = S, Se; B = 1,10-phenantholine, isoquinoline. We have demonstrated that cation-anion SïS and ÀïÀ contacts are necessary. © 2002 Elsevier Science B.V. All rights reserved.
Akutsu H, Yamada JI, Nakatsuji S, Turner SS (2013) One-dimensional anionic metal-organic chain generated from(Tetraphenylphosphonium)2benzoquinonediiminedisulfonate and CuI, X-ray Structure Analysis Online 29 (10) pp. 41-42
The title compound, (C24H20P)2(C6H4N2O6S2)CuI.0.34H2O, was obtained by the slow evaporation of a solvent from an acetonitrile solution containing a mixture of (PPh4)2N,N'-disulfobenzoquinonediimine and CuI. The structure consists of a one-dimensional metal-organic framework of the dianion and CuI. The anionic chains are surrounded by relatively large counter-cations, and are thus well isolated from each other.
Rashid S, Turner SS, Day P, Light ME, Hursthouse MB, Firth S, Clark RJH (2001) The first molecular charge transfer salt containing proton channels, Chemical Communications (16) pp. 1462-1463 Royal Society of Chemistry
We report the first molecular charge transfer salt containing channels of H
O
/H
O within its lattice; it is formulated ²3-(BEDT-TTF)
[(H
O)Cr(C
O
)
]
[(H
O)
(18-crown-6)]·5H
O [BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene], deduced from the crystal structure and C=C and C-S bond lengths and Raman stretching frequencies.
2,6-Bis(pyrazol-1-yl)pyridine (L1) and 2,2:62,23-terpyridine (L2) are popular ligands for use in a wide range of applications in coordination chemistry. Both ligands are capable of forming metal complexes with highly interesting and potentially exploitable properties: luminescence, catalytic redox activity and magnetic spin crossover (SCO). SCO materials have received attention because of the potential for incorporation into commercially relevant technologies such as sensors and information storage media. This review explores the potential of ?back to back? L1 SCO polymers using reported examples, and looks towards the larger L2 chemical library, covering the coordination chemistry with a focus on magnetic properties. In principle, polymeric coordination materials are easier to process and may offer an easier route to tuning properties that are dependent on the electronic environment. It is the intention of this review to highlight the potential of these materials, with the goal of promoting the development of multifunctional SCO hybrids.
Akutsu Hiroki, Ishihara Keita, Ito Soich, Nishiyama Fumiyoshi, Yamada Jun-ichi, Nakatsuji Shin'ichi, Turner Scott, Nakazawa Yasuhiro (2017) Anion polarity-induced self-doping in a purely organic paramagnetic conductor, ±2-±2-(BEDT-TTF)2(PO-CONH- m -C6H4SO3)·H2O where BEDT-TTF is bis(ethylenedithio)tetrathiafulvalene and PO is the radical 2,2,5,5-Tetramethyl-3-pyrrolin-1-oxyl, Polyhedron 136 pp. 23-29 Elsevier
A new BEDT-TTF-based salt with an organic free radical, ±2-±2-(BEDT-TTF)2(PO-CONH-m-C6H4SO3)·H2O, has been prepared. The crystal structure consists of alternating donor and anion/water layers propagated along the c axis. The anisotropic radical anions form a head-to-head arrangement, which provides a permanent dipole moment. The effect on the nearest donor layer has been estimated to be 4.0 V. The salt has two crystallographically independent donor layers (A and B), one of which (A) is surrounded by the negative ends of the anion layer dipole whereas the B layers are bordered by the positive ends of the dipole. This structural feature suggests that layers A and B have different Fermi levels. To eliminate the imbalance, self-doping occurs whereby electron density is transferred from layer A to B. The temperature dependence of the magnetic susceptibility has 11.1% of extra Curie spins, from which a doping ratio of 12.7% has been estimated.
Akutsu H, Ishihara K, Yamada J, Nakatsuji S, Turner S, Nakazawa Y (2016) A strongly polarized organic conductor, CRYSTENGCOMM 18 (42) pp. 8151-8154 ROYAL SOC CHEMISTRY
The electrically conducting salt a-(BEDT-TTF)2(PO-CON(CH3)CH2SO3)·3H2O crystallized in the polar space group, Pna21. 2D conducting BEDT-TTF layers and anion layers alternate along the crystallographic c axis. In the crystal, permanent dipoles of all anions point along the c axis, providing a net crystal dipole moment.
We have prepared two dmit-based salts with a stable organic radical-substituted ammonium cation, (PO-CONH-C2H4N(CH3)3)[Ni(dmit)2]2·CH3CN and (PO-CONH-C2H4N(CH3)3)[Pd(dmit)2]2 where PO is 2,2,5,5-Tetramethyl-3-pyrrolin-1-oxyl and dmit is 2-Thioxo-1,3-dithiol-4,5-dithiolate. The salts are not isostructural but have similar structural features in the anion and cation packing arrangements. The acceptor layers of both salts consist of tetramers, which gather to form 2D conducting layers. Magnetic susceptibility measurements indicate that the Ni salt is a Mott insulator and the Pd salt is a band insulator, which has been confirmed by band structure calculations. The cationic layers of both salts have a previously unreported polar structure, in which the cation dipoles order as š˜š˜ along the acceptors stacking direction to provide dipole moments. The dipole moments of nearest neighbor cation layers are inverted in both salts, indicating no net dipole moments for the whole crystals. The magnetic network of the [Ni(dmit)2] layer of the Ni salt is two-dimensional so that the magnetic susceptibility would be expected to obey the 1D or 2D Heisenberg model that has a broad maximum around T H ¸. However, the magnetic susceptibility after subtraction of the contribution from the PO radical has no broad maximum. Instead, it shows Curie?Weiss behavior with C = 0.378 emu·K/mol and ¸ = ?35.8 K. The magnetic susceptibility of the Pd salt obeys a Curie?Weiss model with C = 0.329 emu·K·mol?1 and ¸ = ?0.88 K.
Akutsu H, Hashimoto R, Yamada J, Nakatsuji S, Turner Scott, Nakazawa Y (2018) Structure and properties of a BEDT-TTF-based organic conductor with a ferrocene-based magnetic anion octamethylferrocenedisulfonate, European Journal of Inorganic Chemistry 2018 (27) pp. 3249-3252 Wiley
The structure and properties of a new semiconducting
BEDT-TTF-based charge-transfer salt containing the magnetic
monoanion octamethylferrocenedisulfonate (?O3SC5(
CH3)4Fe+C5(CH3)4-SO3
? (ofds)), a-(BEDT-TTF)5(ofds)2 is
described (BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene). The
salt is a semiconductor with rRT = 5.6 ´ 103 W·cm and Ea = 0.11 eV.
There are two types of spins not only on the ferrocenyl parts but also
the 2D donor layers. The former and latter spins obey Curie-Weiss
(C = 0.721 emu K mol-1and q = -5.5 K) and 2D Heisenberg (J2DH = -
80.3 K) models, respectively.
Akutsu H, Ito S, Kadoya T, Yamada J, Nakatsuji S, Turner Scott, Nakazawa Y (2018) A new Ni(dmit)2-based organic magnetic charge-transfer salt, (m-PO-CONH- N-methylpyridinium)[Ni(dmit)2]·CH3CN, Inorganica Chimica Acta 482 pp. 654-658 Elsevier
A new Ni(dmit)2-based organic magnetic charge-transfer (CT) salt, (m-PO-CONH-N-methylpyridinium)[Ni(dmit)2]·CH3CN, where PO = 2,2,5,5-Tetramethyl-3-pyrrolin-1-oxyl free radical and dmit = 2-Thioxo-1,3-dithiole-4,5-dithiolate, was obtained, the crystal structure and magnetic properties of which are reported. Magnetic susceptibility of the CT salt obeys a combination of 1D ferromagnetic (1DF) Heisenberg (J1DF = +0.26 K) and Singlet-Triplet (ST) models (JST = -51.2 K) with mean field (MF) approximation (JMF = -6.7 K), suggesting that spins on the PO radicals form 1D ferromagnetic chains and spins on the Ni(dmit)2 monoanions forms spin dimers at low temperature, the latter of which was also confirmed by band calculations.
Attwood Max Julian David, Akutsu Hiroki, Martin Lee, Cruickshank Dyanne, Turner Scott S (2018) Above Room Temperature Spin Crossover in Thioamide-Functionalised 2,6-bis(pyrazol-1-yl)pyridine Iron(II) Complexes, Dalton Transactions (48) pp. 90-98 Royal Society of Chemistry
This work describes the synthesis of two novel functionalised 2,6-bis(pyrazol-1-yl)pyridine (bpp) ligands, namely 2,6-bis(pyrazol-1-yl)pyridine-4-carbothioamide (bppCSNH2) and N-methyl-2,6-bis(pyrazol-1-yl)pyridine-4-carbothioamide (bppCSNHMe). The corresponding solvated or non-solvated Fe(II) salts, [Fe(bppCSNH2)2]X2 and [Fe(bppCSNHMe)2]X2 (X = BF4- or ClO4-) were synthesised and their properties measured by SQUID magnetometry, Evans NMR, differential scanning calorimetry and single crystal X-ray diffraction. In the solid state [Fe(bppCSNH2)2]2+ salts persist in the low spin state below 350 K. The structure of [Fe(bppCSNH2)2](BF4)2.2MeNO2 shows a network of intermolecular interactions responsible for the low spin state stabilisation, relative to the prototypical [Fe(bpp)2]2+ spin crossover (SCO) salts. By contrast the complexes of bppCSNHMe both display abrupt SCO above 300 K. [Fe(bppCSNHMe)2](BF4)2.MeNO2 requires solvent loss before SCO can be observed centred at 332 K. The non-solvated [Fe(bppCSNHMe)2](ClO4)2 shows SCO centred at 325 K. Analysis of solvated and non-solvated crystal structures suggests that cooperativity is facilitated by thioamide-group interactions with neighbouring pyrazolyl and pyridyl moieties.
Attwood Max, Akutsu Hiroki, Martin Lee, Cruickshank Dyanne, Turner Scott S. (2019) Above room temperature spin crossover in thioamide-functionalised 2,6-bis(pyrazol-1-yl)pyridine iron(ii) complexes, Dalton Transactions 48 (1) pp. 90-98 Royal Society of Chemistry
This work describes the synthesis of two novel functionalised 2,6-bis(pyrazol-1-yl)pyridine (bpp) ligands, namely 2,6-bis(pyrazol-1-yl)pyridine-4-carbothioamide (bppCSNH2) and N-methyl-2,6-bis(pyrazol-1-yl)pyridine-4-carbothioamide (bppCSNHMe). The corresponding solvated or non-solvated Fe(II) salts, [Fe(bppCSNH2)2]X2 and [Fe(bppCSNHMe)2]X2 (X = BF4? or ClO4?) were synthesised and their properties measured by SQUID magnetometry, Evans NMR, differential scanning calorimetry and single crystal X-ray diffraction. In the solid state [Fe(bppCSNH2)2]2+ salts persist in the low spin state below 350 K. The structure of [Fe(bppCSNH2)2](BF4)2·2MeNO2 shows a network of intermolecular interactions responsible for the low spin state stabilisation, relative to the prototypical [Fe(bpp)2]2+ spin crossover (SCO) salts. By contrast the complexes of bppCSNHMe both display abrupt SCO above 300 K. [Fe(bppCSNHMe)2](BF4)2·MeNO2 requires solvent loss before SCO can be observed centred at 332 K. The non-solvated [Fe(bppCSNHMe)2](ClO4)2 shows SCO centred at 325 K. Analysis of solvated and non-solvated crystal structures suggests that cooperativity is facilitated by thioamide-group interactions with neighbouring pyrazolyl and pyridyl moieties.