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Professor Peter Day FRS was born on 20 August 1938 in Kent (UK) and attended Maidstone Grammar School [...]

Peter Day’s research group reported the first molecular superconductor containing paramagnetic metal ions in 1995, β″-(BEDT-TTF)4(H3O)Fe(C2O4)3·C6H5CN. Subsequent research has produced a multitude of BEDT-TTF-tris(oxalato)metallate salts with a variety of structures and properties, including 32 superconductors to date. We present here the synthesis, crystal structure, and conducting properties of the newest additions to the Day series including the first superconductor incorporating the diamagnetic tris(oxalato)aluminate anion, β″-(BEDT-TTF)4(H3O)Al(C2O4)3·C6H5Br, which has a superconducting Tc of ~2.5 K. β″-(BEDT-TTF)4(H3O)Co(C2O4)3·C6H5Br represents the first example of a β″ phase for the tris(oxalato)cobaltate anion, but this salt does not show superconductivity.

An organic anion, 2-bromoethanesulfonate (BrC2H4SO3−), provides one bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and two bis(ethylenedithio)tetraselenafulvalene (BETS) salts, the compositions of which are β’’-β’’-(BEDT-TTF)2BrC2H4SO3 (1), β’’-β’’-(BETS)2BrC2H4SO3 (2), and θ-(BETS)2BrC2H4SO3 (3), respectively. Compound 1 shows a metal–insulator transition at around 70 K. Compound 2 is isomorphous to 1, and 3 is polymorphic with 2. Compounds 2 and 3 show metallic behavior at least down to 4.2 K. The pressure dependence of the electrical resistivity of 1 is also reported.

Two novel salts containing the anion [Ni(mnt)2]− (mnt = maleonitriledithiolate) have been synthesized. The counter-ions, [Fe(II)(L1 or L2)2], are cationic complexes where L1 and L2 are methylated derivatives of 2,6-bis(pyazolyl)pyridine or pyrazine, which are similar to ligands found in a series of spin-crossover (SCO) complexes. Both salts are characterized by variable temperature single crystal X-ray diffraction and bulk magnetization measurements. Compound 1, [Fe(II)(L1)2][Ni(mnt)2]2 displays an incomplete and gradual SCO up to 300 K, followed by a more rapid increase in the high-spin fraction between 300 and 350 K. Compound 2, [Fe(II)(L2)2][Ni(mnt)2]2.MeNO2, shows a gradual, but more complete SCO response centered at 250 K. For compound 2, the SCO is confirmed by variable temperature Mössbauer spectroscopy. In both cases, the anionic moieties are isolated from each other and so no electrical conductivity is observed.

An organic anion, 2-bromoethanesulfonate (BrC2H4SO3−), provides one bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and two bis(ethylenedithio)tetraselenafulvalene (BETS) salts, the compositions of which are β’’-β’’-(BEDT-TTF)2BrC2H4SO3 (1), β’’-β’’-(BETS)2BrC2H4SO3 (2), and θ-(BETS)2BrC2H4SO3 (3), respectively. Compound 1 shows a metal–insulator transition at around 70 K. Compound 2 is isomorphous to 1, and 3 is polymorphic with 2. Compounds 2 and 3 show metallic behavior at least down to 4.2 K. The pressure dependence of the electrical resistivity of 1 is also reported. [ABSTRACT FROM AUTHOR]

Peter Day’s research group reported the first molecular superconductor containing paramagnetic metal ions in 1995, β″-(BEDT-TTF)4(H3O)Fe(C2O4)3·C6H5CN. Subsequent research has produced a multitude of BEDT-TTF-tris(oxalato)metallate salts with a variety of structures and properties, including 32 superconductors to date. We present here the synthesis, crystal structure, and conducting properties of the newest additions to the Day series including the first superconductor incorporating the diamagnetic tris(oxalato)aluminate anion, β″-(BEDT-TTF)4(H3O)Al(C2O4)3·C6H5Br, which has a superconducting Tc of ~2.5 K. β″-(BEDT-TTF)4(H3O)Co(C2O4)3·C6H5Br represents the first example of a β″ phase for the tris(oxalato)cobaltate anion, but this salt does not show superconductivity. [ABSTRACT FROM AUTHOR]

Two novel salts containing the anion [Ni(mnt)2]- (mnt = maleonitriledithiolate) have been synthesized. The counter-ions, [Fe(II)(L¹ or L²)2], are cationic complexes where L¹ and L² are methylated derivatives of 2,6-bis(pyazolyl)pyridine or pyrazine, which are similar to ligands found in a series of spin-crossover (SCO) complexes. Both salts are characterized by variable temperature single crystal X-ray diffraction and bulk magnetization measurements. Compound 1, [Fe(II)(L¹)2][Ni(mnt)2]2 displays an incomplete and gradual SCO up to 300 K, followed by amore rapid increase in the high-spin fraction between 300 and 350 K. Compound 2, [Fe(II)(L²)2][Ni(mnt)2]2.MeNO2, shows a gradual, but more complete SCO response centered at 250 K. For compound 2, the SCO is confirmed by variable temperature Mössbauer spectroscopy. In both cases, the anionic moieties are isolated from each other and so no electrical conductivity is observed. [ABSTRACT FROM AUTHOR]