The fluorite-like LiSm4Mo3O15F ceramics: Synthesis and conductivity

Orlova E.; Sorokin T.; Baldin E.; Zakharova E.; Kharitonova E.; N. Lyskov; Yapaskurt V.; Voronkova V.

doi:10.1016/j.jssc.2023.124078

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The fluorite-like LiSm4Mo3O15F ceramics: Synthesis and conductivity

Journal of Solid State Chemistry. 2023. Vol. 324. Article 124078.

Orlova E., Sorokin T., Baldin E., Zakharova E., Kharitonova E., Lyskov N., Yapaskurt V., Voronkova V.

Fluorite-like compounds of the Sm5Mo3O16 composition and, for the first time, their fluorine- and lithium-containing analogues of the LiSm4Mo3O15F composition have been obtained by solid-phase synthesis in vacuum sealed quartz ampoules. The resulting materials were characterized by XRD, differential scanning calorimetry, thermogravimetry, scanning electron microscopy, and impedance spectroscopy. It was found that LiSm4Mo3O15F samples are isostructural to cubic Sm5Mo3O16 compounds with a fluorite-like structure. It is shown that the double replacement of samarium with lithium and oxygen with fluorine leads to the appearance of a reversible phase transition accompanied by a jump in conductivity by 2 orders of magnitude. The conductivity of the LiSm4Mo3O15F compound reaches the value of 10^-3 S/cm at 600 ◦C which is about half an order of magnitude higher than the conductivity of non-fluorinated compounds at this temperature.

Research target: Chemistry

Keywords: Phase transitions solid oxide fuel cells Proton conductivity Rare earth molybdates Fluorine-containing molybdates Oxyfluorides

A 36-Nuclear Wheel-Shaped Heterometallic Cluster: Self-Assembly of Mixed-Valent Pt II /Pt IV and Mn II Centers

Sosunov E., Skabitsky I. V., Churakov A. et al., Crystal Growth & Design 2026 Vol. 26 No. 4 P. 1775–1782

Polynuclear 5d–3d assemblies represent a promising class of systems for exploring the interplay among electronic structure, magnetism, and self-assembly. Here, we report the synthesis and structural characterization of the first heterometallic wheel-shaped Pt–Mn cluster, [PtIV12PtII6Mn18(OAc)72(μ3-O)12]·43C6H6(1), which incorporates 36 metal centers. The giant ring is constructed from alternating PtIIMnII paddlewheel fragments and PtIV2Mn2 oxo-acetate units, bridged ...

Added: September 14, 2026

Effect of the size of the substituents in triptycene (TPC-X) on the magnetic and conducting properties of the layered 2D organic metals (MDABCO+)(C60•−)·(TPC-X), where X = H, Br, and I

Sobov P. A., Kuzmin A. V., Shevchun A. F. et al., Synthetic Metals 2025 Vol. 313 Article 117904

Modification of the neutral triptycene TPC-X molecule by increasing the size of the X substituent at the 9th position from X = H to Br and I affects the magnetic and conducting properties of the (MDABCO+)(C60•−)(TPC-X) salts (1–3, respectively), where MDABCO+ is N-methyldiazabicyclooctanium. These salts feature hexagonal fullerene layers composed of C60•−, which remain undimerized owing to ...

Added: September 14, 2026

Salts of Tetraselenatetracene and Bis(ethylenedithio)tetrathiafulvalene with Metal Hexafluoroacetylacetonate Anions: MnII(hfac)3–, CoII(hfac)2Cl–, and PrIII(hfac)4–

Flakina A. M., Nazarov D., Faraonov M. et al., Crystal Growth & Design 2025 Vol. 25 No. 15 P. 6332–6344

Oxidation of tetraselenatetracene (TSeT) and bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) by p-chloranil in the presence of metal hexafluoroacetylacetonates: MnII(hfac)2, CoII(hfac)2 and PrIII(hfac)3 followed by precipitation of crystals by n-hexane produces (TSeT1.5)+{MnII(hfac)3–} (1), (TSeT1.5)+{PrIII(hfac)4–} (3), (TSeT2)+{CoII(hfac)2Cl–} (4), and (ET3)+{MnII(hfac)3–} (5). Thioindigo dye is introduced into (TSeT1.5)+ (Thioindigo1.5){MnII(hfac)3–} (2) due to the appearance of specific C═O···(Se–Se bond) interactions accompanied by ...

Added: September 14, 2026

Complex of copper(II) hexafluoroacetylacetonate with photochromic spiropyran in the merocyanine form: Field-induced slow magnetic relaxation and quantum coherence for Cu(II) (S = 1/2) and photoswitching of spiropyran ligand

Osipov N., Faraonov M., Yakushev I. A. et al., Dalton Transactions 2025 Vol. 54 No. 32 P. 12180–12188

The interaction of photochromic 8-methoxy-1′,3′,3′-trimethyl-6-nitro-spiro[chromene-2,2′-indole] (MNSP) spiropyran with copper(II) hexafluoroacetylacetonate yields a deep red–violet solution due to a coordination-induced transition of MNSP from its closed form to the colored, open merocyanine (MC) form. The crystal structure of {CuII(hfac)2·MNSP} (1) shows coordination of two oxygen atoms in MNSP to CuII, forming a distorted octahedral geometry with ...

Added: September 14, 2026

Complexes of d‐ and f‐metal Ions with Redox‐Active and Highly Symmetric Truxenone Ligand: Effect of Cations and Coordination on Distortions of Radical Anions and Singlet–Triplet Transition in Dianions

Krivenko K., Shestakov A., Faraonov M. et al., European Journal of Inorganic Chemistry 2025 Vol. 28 No. 14 Article e202400760

Truxenone (Tr) with high C3h symmetry forms crystalline radical anion and dianion salts. The {Bu3MeP+}(Tr⋅−) (1) and {Cp*2Co+)}(Tr⋅−)⋅2 C6H4Cl2 (2) show intense low‐energy absorption up to 2000 nm. Calculations predict Jahn–Teller distortions for Tr⋅−, which are enhanced by the asymmetric approach of cations to Tr⋅−, leading to C=O bond length alternation and EPR signal asymmetry in 2. ...

Added: September 14, 2026

Complexes (TBA+){(TMI-NPS)2·LnIIII4}− (Ln = Dy, Tb) with two axial photochromic spiropyran ligands: photoswitching and zero-field SIM behaviour with a high magnetization blocking barrier for the Dy complex

Osipov N., Faraonov M., Kuzmin A. V. et al., Inorganic Chemistry Frontiers 2025 Vol. 12 No. 5 P. 2092–2102

Two photochromic spiropyran molecules (1,3,3-trimethylindolino-β-naphthopyrylospiran, TMI-NPS) react in the open form with LnIII iodides (Ln = Dy, Tb) to form in the presence of TBAI crystalline (TBA+){(TMI-NPS)2·LnIIII4}−·0.5C6H4Cl2 (1 and 2, respectively). Two TMI-NPS ligands are coordinated to lanthanides (Ln) by oxygen atoms at the axial position, and four iodide anions located at the equatorial position ...

Added: September 14, 2026

Macrocycle- and metal-centered reduction of cobalt trithiadodecaazahexaphyrin (Hhp). Metal-to-ligand charge transfer in {(Co(I)2Co(II)O){Hhp(•4-))}(2-)

Nazarov D., Kuzmin A. V., Islyaikin M. et al., New Journal of Chemistry 2025 Vol. 49 No. 5 P. 1631–1639

Reduction of free-base trithiadodecaazahexaphyrin, H3Hhp, by potassium graphite in the presence of cobalt(II) acetylacetonate and cryptand[2.2.2] produces {Cryptand[2.2.2](K+)}2{(CoI2CoIIO)2+(Hhp˙4−)}2−·2C6H4Cl2 (1). Co atoms in Co3O have square-planar geometry with short Co–N and Co–O bonds of 1.852–1.898(3) Å length. A nearly planar shape of Hhp macrocycles in 1 with equal Nmeso–C bonds indicates the aromatic character of Hhp˙4−. ...

Added: September 14, 2026

Coordination complexes of iron(II) phthalocyanine with cationic, anionic and neutral ligands

Romanenko N., Faraonov M., Kuzmin A. V. et al., Journal of Porphyrins and Phthalocyanines 2024 Vol. 28 No. 09n10 P. A–k

A series of coordination complexes of iron(II) phthalocyanine (FeIIPc) with anionic, cationic and neutral ligands has been obtained in crystalline form. The salt of FeIIPc with MDABCO[Formula: see text] cations (MDABCO[Formula: see text][FeI(Pc[Formula: see text]][Formula: see text]⋅(I[Formula: see text]⋅2TPC⋅2C6H4Cl2 (1) contains FeIIPc reduced to [FeI(Pc[Formula: see text]][Formula: see text], and the FeI ion coordinates two ...

Added: September 14, 2026

Binuclear Coordination Assemblies of Metal Tetraphenylporphyrins (M = Mn, Fe, and In) with Anionic Thioindigo Bridges as Promising Magnetic Systems with Tunable Properties

Nazarov D., Faraonov M., Nations S. et al., Inorganic Chemistry 2024 Vol. 63 No. 48 P. 22677–22687

A series of hybrids comprising two metal (Mn, Fe, and In) tetraphenylporphyrins axially substituted with anionic bidentate trans-thioindigo ligands (TI) were obtained. Substitution of the axial chloride anion by an oxygen atom of the dye forms short M–O bonds. Crystalline binuclear assemblies (TI•–)·{[MnIITPP]0·[MnIIITPP]+}·xC6H4Cl2 (x = 2 for 1 or 1 for 2) and (TI2–){[MIIITPP]+}2·xC6H4Cl2 (M ...

Added: September 14, 2026

Effect of nuclearity and reduction state of the central ligand on magnetic properties of hexaazatrinaphthylene-based cobalt(ii) and iron(ii) complexes: from extremely weak to record-breaking antiferromagnetic exchange interaction

Mikhailenko M., Ivanov V. V., Faraonov M. et al., Inorganic Chemistry Frontiers 2024 Vol. 11 No. 21 P. 7563–7575

A series of hexaazatrinaphthylene (HATNA) and hexaazatrianthracene (HATA) complexes with high-spin four-coordinate cobalt(II) (S = 3/2) and iron(II) (S = 2) ions were synthesized. These compounds vary in charge of the central hexaazatriphenylene (HAT) ligand (L) and the number of coordinated metal atoms. The occupancy of the three coordinating sites on the HAT ligands greatly ...

Added: September 14, 2026

Single-Ion Magnetism of the [DyIII(hfac)4]− Anions in the Crystalline Semiconductor {TSeT1.5}●+[DyIII(hfac)4]− Containing Weakly Dimerized Stacks of Tetraselenatetracene

Flakina A. M., Nazarov D., Faraonov M. et al., International Journal of Molecular Sciences 2024 Vol. 25 No. 15 Article 8068

The oxidation of tetraselenatetracene (TSeT) by tetracyanoquinodimethane in the presence of dysprosium(III) tris(hexafluoroacetylacetonate), DyIII(hfac)3, produces black crystals of {TSeT1.5}●+[DyIII(hfac)4]− (1) salt, which combines conducting and magnetic sublattices. It contains one-dimensional stacks composed of partially oxidized TSeT molecules (formal averaged charge is +2/3). Dimers and monomers can be outlined within these stacks with charge and spin ...

Added: September 14, 2026

Coordination vs. oxidative rearrangement of photochromic spiropyrans upon reacting with FeIIICl3 and FeIIIBr3

Osipov N., Faraonov M., Kuzmin A. V. et al., New Journal of Chemistry 2024 Vol. 48 No. 30 P. 13526–13537

Photochromic 1,3,3-trimethylindolino-β-naphthopyrylospiran (TMI–NPS) and 1,3,3-trimethylindolinonaphthospirooxazine (TMI–NSO) spiropyrans transform into the open merocyanine (MC) form, which exhibits a red-violet color upon reacting with one equivalent of anhydrous FeIIICl3 or FeIIIBr3 in o-dichlorobenzene. Slow mixing with n-hexane precipitates black crystals of the coordination complexes: (TMI–NPS)·FeIIICl3 (1), (TMI–NPS)·FeIIIBr3·2C6H4Cl2 (2) and (TMI–NSO)·FeX3·0.5C6H4Cl2 (where X = Cl for 3 and ...

Added: September 14, 2026

Expanded Porphyrin exhibiting offcentered out-of-plane coordination to Dysprosium

Nazarov D., Labella J., Kuzmin A. V. et al., CCS CHEMISTRY 2024 Vol. 6 No. 7 P. 1731–1738

The complexation of high-spin lanthanides to porphyrinoids is a powerful strategy for the development of advanced molecular magnets. In this context, the use of expanded porphyrinoids remains elusive since their coordination chemistry is challenging to control. Herein, taking inspiration from on-surface chemistry, we explored the coordination of Dy3+ to a six-membered porphyrinoid, namely, the hemihexaphyrazine ...

Added: September 14, 2026

Perchlorinated vanadyl tetrapyrazinoporphyrazine: spectral, redox and magnetic properties

Finogenov D. N., Faraonov M., Kopylova A. et al., New Journal of Chemistry 2024 Vol. 48 No. 22 P. 10067–10073

Perchlorinated vanadyl tetrapyrazinoporphyrazine and its reduced form obtained by reduction by potassium graphite in the presence of cryptand in o-dichlorobenzene have been synthetized. The reaction leads to the formation of a crystalline anionic salt cryptand(K+)2[(TPyzPzCl84−)VIVO]2− (1), where reduction is ring-centered and results in [TPyzPzCl84−] tetraanions. This causes a difference between shorter and longer bond lengths ...

Added: September 14, 2026

Monomers and dimers of fullerenes in the radical anion salts with dyes, (astrophloxine+)2(C60˙−)2 and (astrophloxine+)2(C70−)2: suppression of the C60˙− dimerization by π-stacking

Sobov P. A., Faraonov M., Khasanov S. et al., New Journal of Chemistry 2024 Vol. 48 No. 22 P. 10002–10009

Radical anion salts of fullerenes have been obtained through the reaction of Cs·C60 and Cs·C70 with cationic dye (astrophloxine+)(I−) yielding crystalline salts (astrophloxine+)2(C60˙−)2·C6H4Cl2·C6H14 (1) and (astrophloxine+)2(C70−)2 (2). Salt 1 contains C60˙− radical anions arranged in 3D packing among which pairs of types I and II can be outlined. Strong antiferromagnetic coupling of spins is observed ...

Added: September 14, 2026

Coordination complexes of reduced organic dye isoviolanthrone with transition metals and lanthanides [Mn(II), Dy(III), Gd(III), Nd(III)]

Romanenko N., Faraonov M., Khasanov S. et al., Polyhedron 2024 Vol. 253 Article 116930

The reduction of a vat dye isoviolanthrone to the dianion state in the presence of metal-containing compounds yields binuclear coordination complexes. Two manganese(II) acetylacetonate units coordinate to isoviolanthrone2− (L) in {(K+)cryptand}2{[MnII(acac)2]2⋅L}2– (1) with an average Mn–O bond length of 2.022(2) Å. Dysprosium(III)- or gadolinium(III)-2,2,6,6-tetramethyl-3,5-heptanedionate (TMHD) units form {(K+)cryptand}2{[MIII(TMHD)3]2⋅L}2− (M = DyIII for 2 and GdIII ...

Added: September 14, 2026

Bis(ethylenedithio)tetrathiafulvalene and dibenzotetrathiafulvalene salts with dicyanoiron(III) phthalocyanine anions

Flakina A. M., Torunova S. A., Faraonov M. et al., Inorganica Chimica Acta 2024 Vol. 563 Article 121933

Electrooxidation of bis(ethylenedithio)tetrathiafulvelene (BEDT-TTF) and dibenzotetrathiafulvelene (DB-TTF) in the presence of dicyanoiron(II) phthalocyanine dianions in form of the {Cryptand(K+)}2{FeII(CN)2Pc}2− salt has been studied in o-dichlorobenzene and acetonitrile solutions (where Cryptand is cryptand[2.2.2]). Initially iron(II) is oxidized to iron(III) and after that tetrathiafulvelenes are oxidized forming crystalline salts (BEDT-TTF•+){FeIII(CN)2Pc}−⋅C6H4Cl2 (1) and (DB-TTF•+){FeIII(CN)2Pc}−⋅C6H4Cl2 (2). Both salts contain ...

Added: September 14, 2026

Tuning the magnetic coupling between manganese porphyrins in the 2MnIITPP⋅L assemblies, where L is 6,13-pentacenequinone, isoviolanthrone2− and {MnII(triazole−)2Pc}2−. Key role of a linker (L) in magnetic exchange

Nazarov D., Faraonov M., Kuzmin A. V. et al., Dyes and Pigments 2024 Vol. 223 P. 111926

Coordination architectures involving high-spin S = 5/2 manganese (II) tetraphenylporphyrins (MnIITPP) and a series of π-conjugated linkers have been obtained. Different molecules (isoviolanthrone, 6,13-pentacenequinone, 1,2,4-triazole anions coordinated to manganese (II) phthalocyanine [(MnII(triazole−)2Pc)]2−) in either dianion or neutral states were used as linkers in these architectures. Complexes [cryptand(K+)]2⋅[(isoviolanthrone2−)⋅{MnIITPP}2]2−⋅5C6H4Cl2 (1) and [(6,13-pentacenequinone0)⋅{MnIITPP}2]0⋅2C6H4Cl2 (2) are formed as a ...

Added: September 14, 2026

Slow magnetic relaxation in a complex of photochromic spiropyran in merocyanine form and cobalt(II) hexafluoroacetylacetonate

Osipov N. G., Faraonov M., Yakushev I. et al., Dalton Transactions 2024

The interaction between photochromic 8-methoxy-1′,3′,3′-trimethyl-6-nitro-spiro[chromene-2,2′-indole] (MNSP) and cobalt(II) hexafluoroacetylacetonate yields a deep red-violet solution due to the coordination-induced transition of MNSP from a colorless closed state to a colored open merocyanine (MC) form. The resulting complex {CoII(hfac)2·MNSP} (1) is obtained as crystals, and its structure at 250 K shows the coordination of two oxygen atoms ...

Added: September 14, 2026

2,2-Diaryl-1,3,2-dioxaborines based on curcumin: synthesis, photophysical properties and preliminary biological studies

Nazarov Alexey A., Dudarova N., Zhidkova O. et al., Journal of Photochemistry and Photobiology A: Chemistry 2026 Vol. 483 Article 117654

Сyclocondensation of phenyl, ortho-bromophenyl, para-phenylphenyl, para-methoxycarbonylphenyl, para-tolyl and para-methoxyphenyl boronic acid with curcumin in the presence of K3PO4 upon refluxing in 1,4-dioxane for 24 h leads to the formation of curcumin-based 2,2-diaryl-1,3,2-dioxaborines in good yields. The absorption-emission spectra of the synthesized fluorescent conjugates and 1,3,2-dioxaborine with para-biphenyl boronic substituent demonstrated the highest quantum yield. Among the compounds studied, conjugate curcumin with para-methoxycarbonylphenyl boronic substituent ...

Added: September 9, 2026

Degree-based topological co-indices for QSPR modelling of benzenoid hydrocarbons: a comparative computational study

Chemical Papers 2026

Benzenoid hydrocarbons are structurally regular aromatic compounds, which makes them well suited for quantitative structure–property relationship (QSPR) studies. This study presents a QSPR analysis of nineteen benzenoid hydrocarbon species using degree-based topological co-indices. We developed a Python program to compute eleven degree-based topological co-indices from molecular graphs and evaluated their ability to explain variations in ...

Added: September 8, 2026

Bridging experiment and molecular dynamics: Mefenamic acid confinement in nanocrystalline cellulose aerogels under scCO2 conditions

Gurina D., Fashchevsky K. A., Oparin R. D. et al., Surfaces and Interfaces 2026 Vol. 98 Article 110545

In this work, we combine experimental characterization and molecular dynamics (MD) simulations to elucidate the molecular mechanisms governing the impregnation of mefenamic acid (MFA) into nanocrystalline cellulose (NCC) aerogels. NCC aerogels were impregnated with MFA in scCO2, and low-temperature nitrogen adsorption revealed a concentration-dependent decrease in surface area, pore volume, and pore size, with an ...

Added: September 8, 2026

Anharmonic coherent dynamics of the soft phonon mode of a PbTe crystal

Melnikov A., Selivanov Y. G., Chekalin S., Physical Review B: Condensed Matter and Materials Physics 2023 Vol. 108 P. 224309

We investigate the ultrafast optical response of PbTe to an intense single-cycle terahertz pulse, resonant with the soft transverse optical (TO) phonon mode of the crystal. We detect multifrequency oscillations of the reflectance anisotropy, which we associate with nonlinear motion of the TO phonon oscillator excited directly by the terahertz pulse. Our observation of monotonically ...

Added: July 24, 2025

Structure and conductivity of lithium-doped fluorite-like molybdates Nd5Mo3O16

Orlova E. I., Trukhacheva M. P., Sorokin T. A. et al., Crystallography reports 2024 Vol. 69 No. 2 P. 199–205

Rare-earth molybdenum-containing oxides of the nominal composition LixNd5-xMo3O6±δ (x = 0, 0.05, 0.15, 0.25) with a fluorite-related structure have been obtained for the first time as single crystals grown from flux and by solid-phase synthesis in air in the form of polycrystalline samples. The new phases are characterized using X-ray diffraction analysis, simultaneous thermal analysis, ...

Added: May 24, 2024