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Cationic Mn(III) complexes with 3,5‐Hal‐sal2323 (Hal=diCl, diBr, BrCl) ligands containing electroactive TCNQ anions as counterions have been synthesized: [Mn(3,5‐diCl‐sal2323)](TCNQ)2 (1), [Mn(3,5‐diBr‐sal2323)]2(TCNQ)3⋅6CH3CN (2), and [Mn(3,5‐Br,Cl‐sal2323)]2(TCNQ)3⋅6CH3CN (3). The crystal structures, magnetic and conducting properties of the obtained compounds have been investigated. In 1, an incomplete spin transition from the low‐spin (LS) state at 100 K to the high‐spin (HS) state upon heating to 400 K is observed. Isostructural complexes 2 and 3 contain 6 molecules of solvated acetonitrile, which is lost upon heating, accompanied by the crystal structure transformation. As a result, desolvated complexes jump to the HS state. The temperature dependences of resistivity 2 and 3 show resistivity jumps associated with the loss of lattice solvent. [ABSTRACT FROM AUTHOR]

We present herein the synthesis, crystal structure, and electric and magnetic properties of the spin‐crossover salt [Mn(5‐Cl‐sal‐N‐1,5,8,12)]TCNQ1.5⋅2 CH3CN (I), where 5‐Cl‐sal‐N‐1,5,8,12=N,N′‐bis(3‐(2‐oxy‐5‐chlorobenzylideneamino)propyl)‐ethylenediamine, containing distinct conductive and magnetic blocks along with acetonitrile solvent molecules. The MnIII complex with a Schiff‐base ligand, [Mn(5‐Cl‐sal‐N‐1,5,8,12)]+, acts as the magnetic unit, and the π‐electron acceptor 7,7,8,8‐tetracyanoquinodimethane (TCNQ−) is the conducting unit. The title compound (I) exhibits semiconducting behavior with room temperature conductivity σRT≈1×10−4 ohm−1 cm−1 and activation energy Δ ≈0.20 eV. In the temperature range 73–123 K, it experiences a hysteretic phase transition accompanied by a crossover between the low‐spin S=1 and high‐spin S=2 states of MnIII and changes in bond lengths within the MnN4O2 octahedra. The pronounced shrinkage of the basal Mn−N bonds in I at the spin crossover suggests that the dx2-y2 orbital is occupied/deoccupied in this transition. Interestingly, the bromo isomorphic counterpart [Mn(5‐Br‐sal‐N‐1,5,8,12)]TCNQ1.5⋅2 CH3CN (II) of the title compound evidences no spin‐crossover phenomena and remains in the high‐spin state in the temperature range 2–300 K. Comparison of the chloro and bromo compounds allows the thermal and spin‐crossover contributions to the overall variation in bond lengths to be distinguished. The difference in magnetic behavior of these two salts has been ascribed to intermolecular supramolecular effects on the spin transition. Discrete hydrogen bonding exists between cations and cations and anions in both compounds. However, the hydrogen bonding in the crystals of II is much stronger than in I. The relatively close packing arrangement of the [Mn(5‐Br‐sal‐N‐1,5,8,12)]+ cations probably precludes their spin transformation. [ABSTRACT FROM AUTHOR]

Four new superconducting and metallic salts of the family of organic molecular conductors (BEDT-TTF)4AI[FeIII(C2O4)3]G [A = H3O+; G = 2-chloropyridine (1), 2-bromopyridine (2), 3-chloropyridine (3), and 3-bromopyridine (4); BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene] have been prepared, and their crystal structures, electronic structures, transport properties, and magnetotransport properties have been studied. All of the crystals obtained belong to the monoclinic group of the family with β''-type packing of the conducting BEDT-TTF layers. Crystals 1 and 2 are superconductors with Tc = 2.4-4.0 and 4.3 K, respectively, and possess structural phase transitions from monoclinic to triclinic symmetry at temperatures of 190-215 K, whereas 3 and 4 retain monoclinic symmetry at 90-300 K and do not show a superconducting transition above 0.5 K. Shubnikov-de Haas (SdH) oscillations were found in crystals of 1, 2, and 4. The structures and conducting properties of 1-4 are compared with those of the known monoclinic phases of the family containing FeIII ions and different monohalobenzenes and pyridine as "guest" solvent molecules (G). [ABSTRACT FROM AUTHOR]

Submicron thin films of Bi2Te2,7Se0,3 solid solution is synthesized by thermal vacuum evaporation. The films are then subjected to after-growth vacuum annealing and characterized using X-ray diffraction and confocal laser microscopy techniques. Electron transport in the synthesized films is studied over the temperature range of 1.4-300 K at magnetic fields up to 8 T. Electron localization due to electron-electron interaction, along with weak anti-localization effect at weak magnetic fields and temperatures below 8 K is observed. The latter effect is commonly encountered in thin films of topological insulators grown by molecular beam epitaxy and has therefore been ascribed to the manifestation of the topological surface states. Finally, phase coherence length is estimated. [ABSTRACT FROM AUTHOR]

New metallic triclinic ( 1) and monoclinic ( 2) crystals of the (BEDT-TTF)4AI[MIII(C2O4)3]G family of organic molecular conductors have been prepared: α-'pseudo-κ'-(BEDT-TTF)4K x(H3O)1- x[GaIII(C2O4)3] ·1,2-C6H4Br2 ( x ≈ 0.45) ( 1) and β″-(BEDT-TTF)4K x(H3O)1- x[GaIII(C2O4)3] ·PhBr ( x ≈ 0.33) ( 2). The triclinic crystals belong to a quite rare type of bilayered radical ion salts and contain alternating BEDT-TTF layers with two distinct packing motifs (α- and 'pseudo-κ'). The monoclinic crystals contain one kind of BEDT-TTF radical cation layers. The crystal structure, transport, and magnetotransport properties of 1 and 2 have been studied. The Shubnikov-de Haas (SdH) oscillations were found in both phases. The structure and properties of 1 and 2 are compared with another similar phase with M = FeIII. [ABSTRACT FROM AUTHOR]