Crystal structure, magneto-structural correlation, thermal and electrical studies of an imidazolium halometallate molten salt: (trimim)[FeCl4].

A novel imidazolium halometallate molten salt with formula (trimim)[FeCl4] (trimim: 1,2,3-trimethylimidazolium) was synthetized and studied with structural and physico-chemical characterization. Variable-temperature synchrotron X-ray powder diffraction (SXPD) from 100 to 400 K revealed two structural transitions at 200 and 300 K. Three different crystal structures were determined combining single crystal X-ray diffraction (SCXD), neutron powder diffraction (NPD), and SXPD. From 100 to 200 K, the compound exhibits a monoclinic crystal structure with space group P21/c. At 200 K, the former crystal system and space group are retained, but a disorder in the organic cations is introduced. Above 300 K, the structure transits to the orthorhombic space group Pbcn, retaining the crystallinity up to 400 K. The study of the thermal expansion process in this temperature range showed anisotropically evolving cell parameters with an axial negative thermal expansion. Such an induction occurs immediately after the crystal phase transition due to the translational and reorientational dynamic displacements of the imidazolium cation within the crystal building. Electrochemical impedance spectroscopy (EIS) demonstrated that this motion implies a high and stable solid-state ionic conduction (range from 4 × 10-6 S cm-1 at room temperature to 5.5 × 10-5 S cm-1 at 400 K). In addition, magnetization and heat capacity measurements proved the presence of a three-dimensional antiferromagnetic ordering below 3 K. The magnetic structure, determined by neutron powder diffraction, corresponds to ferromagnetic chains along the a-axis, which are antiferromagnetically coupled to the nearest neighboring chains through an intricate network of superexchange pathways, in agreement with the magnetometry measurements.

Correction: Crystal structure, magneto-structural correlation, thermal and electrical studies of an imidazolium halometallate molten salt: (trimim)[FeCl4].

[This corrects the article DOI: 10.1039/D0RA00245C.].

Ax(H3O)2-xMn5(HPO3)6 (A = Li, Na, K and NH4): open-framework manganese(ii) phosphites templated by mixed cationic species.

Ax(H3O)2-xMn5(HPO3)6 (A = Li, x = 0.55 (1-Li); A = Na, x = 0.72 (2-Na); A = K, x = 0.30 (3-K); A = NH4, x = 0.59 (4-NH4)) phases were synthesized by employing mild hydrothermal conditions. 1-Li was studied by single crystal X-ray diffraction, while sodium, potassium and ammonium containing analogues were obtained as polycrystalline samples and characterized by powder X-ray diffraction. The four compounds were characterized by ICP-Q-MS, thermal analysis and XPS, IR, UV/Vis and EPR spectroscopy. Single crystal data indicate that 1-Li crystallizes in the P3[combining macron]c1 space group with lattice parameters a = 10.3764(1) Å and c = 9.4017(1) Å with Z = 2. The crystal structure of these phases is constituted by a three-dimensional [Mn(ii)5(HPO3)6](2-) anionic skeleton templated by alkali metal and ammonium cations together with protonated water molecules. Such an inorganic framework is formed by layers of edge-sharing MnO6 octahedra placed in the ab plane and joined along the c direction through phosphite pseudotetrahedra. The sheets display 12-membered ring channels parallel to the c-axis, ca. 5 Å in diameter, where the extraframework species display a strong disorder. EPR measurements point to the existence of short range ferromagnetic interactions around 12 K. Magnetic susceptibility and heat capacity measurements show that all the compounds exhibit long range antiferromagnetic order below circa 4 K, with a significant magnetocaloric effect around the Neel temperature.

Dynamically slow solid-to-solid phase transition induced by thermal treatment of DimimFeCl4 magnetic ionic liquid.

The results reported here represent the first direct experimental observations supporting the existence of a solid-to-solid phase transition induced by thermal treatment in magnetic ionic liquids (MILs). The phase transitions of the solid phases of 1,3-dimethylimidazolium tetrachloroferrate, DimimFeCl4, are closely related to its thermal history. Two series of solid-to-solid phase transitions can be described in this MIL: (i) from room temperature (RT) phase II [space group (s.g.) = P21] to phase I-a [s.g. = P212121] via thermal quenching or via fast cooling at T > 2 K min(-1); (ii) from phase I-a to phase I-b [s.g. = P21/c] when the temperature was kept above 180 K for several minutes. The latter involves a slow translational and reorientational dynamical process of both the imidazolium cation and the tetrachloroferrate anion and has been characterized using synchrotron and neutron powder diffraction and DFT (density functional theory) studies. The transition is also related to the modification of the super-exchange pathways of low-temperature phases which show a overall antiferromagnetic behavior. A combination of several experimental methods such as magnetometry, Mössbauer and muon spectroscopy together with polarized and non-polarized neutron powder diffraction has been used in order to characterize the different features observed in these phases.

Anion-π and halide-halide nonbonding interactions in a new ionic liquid based on imidazolium cation with three-dimensional magnetic ordering in the solid state.

We present the first magnetic phase of an ionic liquid with anion-π interactions, which displays a three-dimensional (3D) magnetic ordering below the Néel temperature, TN = 7.7 K. In this material, called Dimim[FeBr4], an exhaustive and systematic study involving structural and physical characterization (synchrotron X-ray, neutron powder diffraction, direct current and alternating current magnetic susceptibility, magnetization, heat capacity, Raman and Mössbauer measurements) as well as first-principles analysis (density functional theory (DFT) simulation) was performed. The crystal structure, solved by Patterson-function direct methods, reveals a monoclinic phase (P21 symmetry) at room temperature with a = 6.745(3) Å, b = 14.364(3) Å, c = 6.759(3) Å, and ß = 90.80(2)°. Its framework, projected along the b direction, is characterized by layers of cations [Dimim](+) and anions [FeBr4](-) that change the orientation from layer to layer, with Fe···Fe distances larger than 6.7 Å. Magnetization measurements show the presence of 3D antiferromagnetic ordering below TN with the existence of a noticeable magneto-crystalline anisotropy. From low-temperature neutron diffraction data, it can be observed that the existence of antiferromagnetic order is originated by the antiparallel ordering of ferromagnetic layers of [FeBr4](-) metal complex along the b direction. The magnetic unit cell is the same as the chemical one, and the magnetic moments are aligned along the c direction. The DFT calculations reflect the fact that the spin density of the iron ions spreads over the bromine atoms. In addition, the projected density of states (PDOS) of the imidazolium with the bromines of a [FeBr4](-) metal complex confirms the existence of the anion-π interaction. Magneto-structural correlations give no evidence for direct iron-iron interactions, corroborating that the 3D magnetic ordering takes place via superexchange coupling, the Fe-Br···Br-Fe interplane interaction being defined as the main exchange pathway.

Enhancement of the luminescent properties of a new red-emitting phosphor, Mn2(HPO3)F2, by Zn substitution.

The Mn(2)(HPO(3))F(2) phase has been synthesized as single crystals by using mild hydrothermal conditions. The compound crystallizes in the orthorhombic Pnma space group, with unit cell parameters of a = 7.5607(8), b = 10.2342(7), and c = 5.5156(4) Å, with Z = 4. The crystal structure consists of a three-dimensional framework formed by alternating (010) layers of [MnO(3)F(3)] octahedra linked up by three connected [HPO(3)] tetrahedra. Luminescence measurements were performed at different temperatures between 10 and 150 K. The 10 K emission spectrum of the octahedrally coordinated Mn(II) cation exhibits a broad band centered at around 615 nm corresponding to the (4)T(1) → (6)A(1) transition. In order to explore the effect of the Mn(II) concentration and the possibility of enhancing the luminescence properties of the Mn(II) cation in Mn(2)(HPO(3))F(2), different intermediate composition members of the finite solid solution with the general formula (Mn(x)Zn(1-x))(2)(HPO(3))F(2) were prepared and their luminescent properties studied. The magnetic and specific heat behavior of M(2)(HPO(3))F(2) (M = Mn, Fe) have also been investigated. The compounds exhibit a global antiferromagnetic ordering with a spin canting phenomenon detected at approximately 30 K. The specific heat measurements show sharp λ-type peaks at 29.7 and 33.5 K for manganese and iron compounds, respectively. The total magnetic entropy is consistent with spin S = 5/2 and S = 2 of Mn(II) and Fe(II) cations.

Structural, thermal, spectroscopic, specific-heat, and magnetic studies of (C5H18N3)[Fe3(HPO3)6].3H2O: a new organically templated iron(III) phosphite with a pillared structure formed by the interpenetration of two subnets.

A new open framework iron(III) phosphite with formula (C5H18N3)[Fe3(HPO3)6].3H2O has been prepared by hydrothermal synthesis with N-(2-aminoethyl)-1,3-propanediamine as a templating agent. The crystal structure was solved from single-crystal X-ray diffraction data in the trigonal space group R. The unit cell parameters are a= 8.803(1) A and c= 25.292(2) A with Z = 3. The complex pillared structure can be described as two interpenetrating subnets, one organic, [(C5H18N3).3H2O]3+, and one inorganic, [Fe3(HPO3)6]3-. In the inorganic subnet, the pillars are formed by FeO6 trimers linked by vertex sharing phosphite groups, while in the cationic subnet the organic molecules act like pillars. With increasing temperature, the flexibility of the structure allows contraction due to dehydration followed by thermal expansion before reaching the thermal stability limit. The Dq and Racah parameters calculated for (C5H18N3)[Fe3(HPO3)6].3H2O are Dq = 965, B = 1080, and C = 2472 cm(-1). Mössbauer spectroscopy confirms the trivalent oxidation state of iron cations and the crystallographic multiplicities of their sites. The ESR spectra show isotropic signals with a g-value of 2.00(1). Specific-heat measurements show a three-dimensional (lambda-type) peak at a critical temperature Tc = 32 K. The value of the entropy at saturation is 46 J/mol K, very near the expected value of 44.7 J/mol K for the iron(III) cations with S = 5/2. Magnetic measurements indicate a three-dimensional antiferromagnetic ordering below 32 K and a reorientation of spins below 15 K with an incomplete cancellation of spins due to triangular interactions inherent to the structure.