RESUMEN
The structural properties of the iron mixed-valence complex ( n-C3H7)4N[FeIIFeIII(dto)3] (dto = dithiooxalato, C2O2S2) have been investigated by single-crystal X-ray diffraction (SCXRD) at low temperatures. ( n-C3H7)4N[FeIIFeIII(dto)3] has two-dimensional (2D) honeycomb layers consisting of alternating FeII and FeIII arrays bonded by bis-bidentate dithiooxalato ligands. Upon cooling, a superlattice structure with q = (1/3, 1/3, 0) was observed below 260 K, which corresponds to an order-disorder transition of the ( n-C3H7)4N+ ions between the honeycomb layers. The charge-transfer phase transition (CTPT) occurs at TC↑1/2 â¼ 120 K and TC↓1/2 â¼ 90 K upon heating and cooling, respectively, with an electron transfer between the FeII and FeIII ions, accompanied by a spin-state change, FeII ( S = 2; HS)-O2C2S2-FeIII ( S = 1/2; LS) â FeIII ( S = 5/2; HS)-O2C2S2-FeII ( S = 0; LS). During the CTPT, the intersheet [FeIIFeIII(dto)3] distance decreased monotonously upon cooling, and an abrupt structural contraction was observed in the hexagonal 2D network. The volume contraction during the CTPT was quite small (â¼0.7%), and differences in the structural distortions at the FeS6 and FeO6 sites were not found in the vicinity of the CTPT. We also calculated the orbital energies and the occupied spin states for the [Fe(O2C2S2)3] and [Fe(S2C2O2)3] octahedra in the vicinity of the CTPT by density functional theory (DFT). Because the local symmetry around the two coordinating iron ions is already lowered to trigonal symmetry, the CTPT did not cause any further deformation. This symmetry invariance resulted in an absence of orbital contributions to the total entropy change (Δ S) in the CTPT, which is in agreement with the previous heat capacity measurements. [Nakamoto, T; Miyazaki, Y; Itoi, M; Ono, Y; Kojima, N; Sorai, M. Heat Capacity of the Mixed-Valence Complex {[( n-C3H7)4N][FeIIFeIII(dto)3]}∞, Phase Transition because of Electron Transfer, and a Change in Spin-State of the Whole System. Angew. Chem., Int. Ed. 2001, 40, 4716-4719.].
RESUMEN
The local structure within the Co-Fe atomic array of the photoswitchable coordination polymer magnet, K0.3Co[Fe(CN)6]0.77·nH2O, is directly observed during charge transfer induced spin transition (CTIST), a solid-solid phase change, using high-resolution transmission electron microscopy (HRTEM). Along with the low-spin (LS) or thermally quenched high-spin (HS) states normally observed in CTIST solids at low temperature, slow cooling of K0.3Co[Fe(CN)6]0.77·nH2O results in an intermediate phase containing both HS and LS domains with short coherence length. By mapping individual metal-metal distances, the nanometer-scale HS domains are directly visualized within the LS array. Temperature-dependent analyses allow monitoring of HS domain coarsening along the warming branch of the CTIST, providing direct visualization of the elastic process and insight into the mechanism of phase propagation. Normally sensitive to electron beam damage, the low-temperature TEM measurements of the porous coordination polymer are enabled by using appropriate ionic liquids instead of usual conductive thin-film coatings, an approach that should find general utility in related classes of materials.
RESUMEN
We investigated the superconductivity of (TMTTF)2TaF6 (TMTTF: tetramethyl-tetrathiafulvalene) by conducting resistivity measurements under high pressure up to 8 GPa. A cubic anvil cell (CAC) pressure generator, which can produce hydrostatic high-pressure, was used for this study. Since the generalized temperature-pressure (T-P) diagram of (TMTCF)2X (C = Se, S, X: monovalent anion) based on (TMTTF)2PF6 (TCO = 70 K and spin-Peierls: SP, TSP = 15 K) was proposed by Jérome, exploring superconductivity states using high-pressure measurement beyond 4 GPa has been required to confirm the universality of the electron-correlation variation under pressure in (TMTTF)2X (TMTTF)2TaF6, which has the largest octahedral-symmetry counter anion TaF6 in the (TMTTF)2X series, possesses the highest charge-ordering (CO) transition temperature (TCO = 175 K) in (TMTTF)2X and demonstrates an anti-ferromagnetic transition (TAF = 9 K) at ambient pressure. A superconducting state in (TMTTF)2TaF6 emerged after a metal-insulator transition was suppressed with increasing external pressure. We discovered a superconducting state in 5 ≤ P ≤ 6 GPa from Tc = 2.1 K to 2.8 K, whose pressure range is one-third narrower than that of X = SbF6 (5.4 ≤ P ≤ 9 GPa). In addition, when the pressures with maximum SC temperatures are compared between the PF6 and the TaF6 salts, we found that (TMTTF)2TaF6 has a 0.75 GPa on the negative pressure side in the T-P phase diagram of (TMTTF)2PF6.
RESUMEN
Iron mixed-valence complex, (n-C(3)H(7))(4)N[Fe(II)Fe(III)(dto)(3)](dto = C(2)O(2)S(2)), shows a spin entropy-driven phase transition called charge transfer phase transition in [Fe(II)Fe(III)(dto)(3)](-)(infinity) around 120 K and a ferromagnetic transition at 7 K. These phase transitions remarkably depend on the hexagonal ring size in the two-dimensional honeycomb network structure of [Fe(II)Fe(III)(dto)(3)](-)(infinity). In order to control the magnetic properties and the electronic state in the dto-bridged iron mixed-valence system by means of photoirradiation, we have synthesized a photosensitive organic-inorganic hybrid system, (SP)[Fe(II)Fe(III)(dto)(3)](SP = spiropyran), and investigated the photoinduced effect on the magnetic properties. Upon UV irradiation at 350 nm, a broad absorption band between 500 and 600 nm appears and continuously increases with the photoirradiation time, which implies that the UV irradiation changes the structure of spiropyran from the closed form to the open one in solid state. The photochromism in spiropyran changes the ferromagnetic transition temperature from 5 to 22 K and the coercive force from 1400 to 6000 Oe at 2 K. In this process, the concerted phenomenon coupled with the charge transfer phase transition in [Fe(II)Fe(III)(dto)(3)](-)(infinity) and the photoisomerization of spiropyran is realized.