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

?

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

Inorganica Chimica Acta. 2024. Vol. 563. Article 121933.

Flakina A. M., Torunova S. A., Faraonov M., Nazarov D., Kuzmin A. V., Khasanov S., Otsuka A., Yamochi H., Kitagawa H., Konarev D.

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 closely packed 2D layers composed of the {FeIII(CN)2Pc}− anions and cationic layers containing solvent molecules. Since cations cannot partially oxidize Pc in these salts, two S = 1/2 spins are positioned on FeIII and the cations. The χMT values are 0.90 and 0.87 emu⋅K/mol per formula unit at 300 K. Antiferromagnetic coupling of spins is observed in 1 and 2 due to both Fe-Cation coupling of -0.4 and -3.5 cm-1 and Fe-Fe couplings of -3.5 and -7.9 cm-1, respectively. Due to its smaller size, DB-TTF+ forms denser packing and shows stronger exchange coupling. An unusual compound forms when DB-TTF and {FeII(CN)2Pc}2− are oxidized together in acetonitrile: (DB-TTF0)2{Cryptand(K+)}{FeIII(CN)2Pc}− (3) where charges on DB-TTF and Fe are closer to zero and +3, respectively. The {FeIII(CN)2Pc}− anions form layers in 3 among which chains with shorter C,N…C,N contacts between Pc can be outlined. Only weak intermolecular antiferromagnetic coupling is manifested in 3 with estimated zJ value of -1.6 cm-1.

Research target: Chemistry

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

Stress tensor of inhomogeneous flexible polymer chain solutions beyond the ground-state dominance approximation

Budkov Y., Journal of Chemical Physics 2026 Vol. 165 No. 9 Article 094902

We derive the stress tensor of a flexible polymer solution within the Gaussian-chain self-consistent field theory (SCFT) without invoking the ground-state dominance (GSD) approximation. Starting from a covariant formulation of the single-chain partition function in a background metric, we obtain the symmetric stress tensor expressed through the full Edwards propagators. The result contains the local ...

Added: September 2, 2026

“-Ethylene” vs “-ethane”: How minor cation variations drive the self-assembly of structurally different supramolecular diiodine-halometalate hybrid complexes

Novikov A., Polyhedron 2026 Vol. 299 Article 118358

Two new supramolecular halometalate hybrid complexes, (H2bpen){[MCl5](I2)} (M = Sb(III) (1) and Bi(III) (2); bpen – 1,2-Bis(4-pyridyl)ethylene, have been prepared. Despite very close similarity of the nature of cations, they reveal significant structural difference from the (H2bpe){[MCl5](I2)} (bpe – 1,2-bis(4-pyridil)ethane) reported earlier. We discuss these features, along with thermal stability, optical properties as well as Raman spectra ...

Added: September 2, 2026

From Small Data to High Capacity: Symbolic Learning of Sodium-Ion Cathode Materials

Meng K., Vasenko A., Chulkov E. et al., The Journal of Physical Chemistry Letters 2026 Vol. 17 No. 36 P. 10546–10554

Data-driven discovery of sodium-ion cathodes is often limited by small data sets and the poor interpretability of graph neural networks (GNNs). Here, we developed Symbol_ETR, an interpretable framework combining symbolic regression with ensemble learning. By constructing explicit nonlinear descriptors, symbolic regression extra trees regression (Symbol_ETR) achieves a test R2 of 0.90 for average voltage prediction ...

Added: August 29, 2026

Monometallic Ln3+ and heterometallic Ln3+–Cd2+ complexes based on pentafluorophenylacetic acid: efficient control of dimension and luminescent properties

Belousov Y., Кискин М. А., Sidoruk A. et al., Australian Journal of Chemistry 2022 Vol. 75 No. 9 P. 572–580

Four new complexes [Ln(pfaa)3(H2O)2]n (Ln = Eu (1), Tb (2)) and [Ln2Cd2(pfaa)10 (phen)2(EtOH)2]·2MeCN (Ln = Eu (3), Tb (4), phen = 1,10-phenanthroline) based on pentaphorphenylacetic acid (Hpfaa) have been prepared and completely investigated. The structures of compounds 1 and 3 were studied by single crystal X-ray diffraction analysis: the isostructural complexes 1 and 2 represent ...

Added: August 26, 2026

Understanding the electric double layer at electrode–electrolyte interfaces, Part III: crystallographic-face dependence of silver capacitance in aqueous NaF solutions

Mazur D., Petr E. Brandyshev, Doronin S. et al., Electrochimica Acta 2026 Vol. 577 Article 149729

The electric double layer (EDL) at a single-crystal metal surface is controlled not only by the electrolyte composition and the electrode potential, but also by the atomic structure of the surface itself. This makes the Ag(hkl)/NaF interface a stringent test for continuum theories of the EDL. In the third part of our series, we examine ...

Added: August 20, 2026

Hall effect in electrolyte solutions: Self-consistent Debye–Hückel–Onsager theory

Budkov Y., Kalikin N., Journal of Chemical Physics 2026 Vol. 165 Article 064506

A self-consistent statistical-mechanical theory of the Hall effect in electrolyte solutions is developed by extending the self-consistent Debye–Hückel–Onsager (SCDHO) framework to crossed electric and magnetic fields. The theory incorporates non-local ionic charge distributions via Slater-type form factors, regularizing the Coulomb interaction at short range, and accounts for dielectric friction through ion-specific coefficients, employing experimental values ...

Added: August 12, 2026

Charge-controlled binding, alloy synergy, and the copper anomaly in Au–Ag–Cu dimers to clusters: DFT-derived design rules for targeted drug delivery

Obijiofor O., Alexander S. Novikov, New Journal of Chemistry 2026 Vol. 50 No. 33 P. 13931–13957

The rational design of coinage metal nanocarriers requires a mechanistic understanding of metal-drug binding and predictive descriptors that translate molecular interactions into design rules. Using DFT (B3LYP-D3BJ/def2-TZVP, SMD water), we systematically investigated the binding of 5-fluorouracil (5-FU) and levodopa (l-DOPA) to neutral and cationic homo- and heteronuclear dimers of Au, Ag, and Cu (Au2, Ag2, ...

Added: August 12, 2026

Surface-sulfonated Al₂O₃, CeO₂, and TiO₂ as functional fillers for Nafion-type gel polymer electrolytes for lithium metal batteries

Voropaeva D., S. Novikova, I. Stenina et al., Solid State Ionics 2026 Vol. 445 Article 117288

Composite gel polymer electrolytes based on a perfluorinated sulfonic acid cation-exchange MF-4SC membrane containing surface-sulfonated nanoparticles of aluminum oxide, cerium (IV) oxide, and titanium oxide (sAl2O3, sCeO2, and sTiO2, respectively) were prepared by casting from a dispersion in N,N-dimethylformamide and plasticized with a 1,3-dioxolane/1,2-dimethoxyethane mixture. The influence of the filler nature on ionic conductivity, solvent uptake, activation energy, lithium ...

Added: July 30, 2026

Long-range machine-learning potentials with environment-dependent charges enable predicting LO-TO splitting and dielectric constants

Korogod D., Shapeev A., Ivan S. Novikov, Physical Review B: Condensed Matter and Materials Physics 2026 Vol. 114 No. 2 Article 024104

We present two models with explicit long-range electrostatics in the form of Coulomb interactions. Both models include point charges depending on their local atomic environments, and the second model also conserves a total charge of an atomic system. We combine the proposed long-range models with the local moment tensor potential (MTP) and demonstrate that they ...

Added: July 22, 2026

A Way to Create Mn-Containing GdFe3(BO3)4 and the Dopant Effect on Its Magnetic Properties

Moshkina E., Molokeev M., Zolotov A. et al., Journal of Alloys and Compounds 2026 Vol. 1077 Article 189412

A wide series of substitutions in a subsystem of small radii cations M = Al, Cr, Fe, Ga, Sc is possible in rare-earth borates ReM3(BO3)4 with the huntite structure. However, the existence of these compounds where M = Mn still raises doubts. The study presents a synthetic approach developed in the framework of the flux method allowing for the required ...

Added: June 29, 2026

Incorporating Scientific Knowledge into Neural Network Density Functionals

Schneider M., Zaripov D., Dokin R. et al., Journal of Chemical Theory and Computation 2026 Vol. 22 No. 9 P. 4405–4414

Density functional theory (DFT) is the workhorse of modern reactions and materials modeling. While the exact functional remains unknown, many approximations to it have been constructed either by hand-crafting functional forms to satisfy exact constraints or by machine learning. In this work, we show how both of these approaches can be fused to build both ...

Added: June 26, 2026

Electrodeposition and electrochromic properties of hydrated mixed oxides MoxW1-xO3·2H2O films

Laurinavichyute V., Levin E. E., Mironkova A. A. et al., Surfaces and Interfaces 2026 Vol. 81 Article 108389

In this work we characterize mixed Mo-W acidic deposition solutions with Mo content ranging from 0 to 100 mol.% by Raman and UV–Vis spectroscopy. The obtained distribution diagram of mixed isopolyanions allows one to explain the observed change in film deposition rate with increase in Mo content. It was found that the initial decrease in ...

Added: June 24, 2026

Сольватация и электрохимические свойства тетрасульфофталоцианината кобальта в водно-диметилформамидных растворителях

Кованова М. А., Кузьмина И. А., Постнов А. С. et al., Журнал физической химии 2023 Т. 97 № 3 С. 386–391

В настоящей работе изучено влияние состава и свойств смешанного растворителя вода – N,N-диметилформамид (χDMF = 0.0–1.0 мол. доли) на изменения в сольватном состоянии 3(4),10(11),17(18),24(25)-тетрасульфофталоцианината кобальта (CoTSPc). Определена область электрохимической устойчивости электролитной системы CoTSPc–DMF при 25.0°C. Методы исследования: метод межфазного распределения вещества, электронная спектроскопия поглощения, циклическая вольтамперометрия. ...

Added: September 16, 2025

The influence of methoxy- group position on thermal stability and properties of novel isomeric 4-[(methoxy)phenoxy] phthalonitriles and phthalocyanine complexes based on them

Erzunov D., Rassolova A., Botnar A. et al., Dyes and Pigments 2023 Vol. 219 Article 111600

Isomeric 4-[(methoxy)phenoxy]phthadinitriles were obtained and characterized in this work. The compounds showed high thermal stability, which is directly related to their structure. These features were revealed and described using X-ray diffraction analysis. For m-substituted structures during packing, the largest contribution was found from intermolecular interactions of the π-stacking type between nitrile fragments. In the packing ...

Added: September 16, 2025

Column chromatography separation of lanthanide(III) bisphthalocyaninate and phthalocyanine ligand

Botnar A. A., Tikhomirova T. V., Vashurin A., Mendeleev Communications 2023 Vol. 33 No. 5 P. 729–731

During the synthesis of double-decker f-metal phthalocyanine complexes Ln(Pc)2 free phthalocyanine ligands can be also formed, however, routine column chromatography is not effective for their separation. The preliminary reduction of the complexes with hydrazine hydrate affords the low mobile forms, which can be re-oxidized in the chromatography columns after the free ligand is eluted. ...

Added: September 16, 2025

Electrocatalytic Properties of Water-Soluble Nickel(II) and Copper(II) Phthalocyaninates in the Oxidation of Hydroxide Ions

Kovanova M. A., Derbeneva P. D., Postnov A. S. et al., Russian Journal of Electrochemistry 2024 Vol. 60 No. 6 P. 429–434

The electrochemical and electrocatalytic behavior of gold electrodes modified with tetra-4-sulfophthalocyaninates of nickel(II) (NiPc) and copper(II) (CuPc) is studied in aqueous alkaline solutions using cyclic voltammetry. The electrocatalytic activity of phthalocyaninates of these metals in the oxidation of hydroxide ions to form molecular oxygen is assessed and compared with the literature data. ...

Added: September 16, 2025

The role of spacer heteroatomic fragment in spectroscopic and luminescent behaviour of phenyl-substituted phthalocyanine complexes

Erzunov D., Alekseeva A., Sarvin I. et al., Journal of Porphyrins and Phthalocyanines 2024 Vol. 28 No. 09n10 P. 701–709

Peripheral phenyl-substituted metal phthalocyanines with thio and oxa substitution in the spacer bridge fragment were obtained in the work. Spectroscopic properties were studied for the obtained complexes, and the main patterns of behavior and characteristics change depending on the solvent and the nature of the spacer atom. It is shown that the replacement of an oxygen ...

Added: September 16, 2025