Exploring Salts of Memantine with Inorganic Anions: From Polymorphism and Solid-State Transitions to Potential for Drug Formulations.

This study examines pharmaceutically acceptable inorganic salts of memantine, specifically focusing on hydrogen sulfate, sulfate, and dihydrogen phosphate salts, with the aim of finding alternatives to the commonly used chloride salt in the treatment of Alzheimer's disease. Through comprehensive solid-state characterization, including powder X-ray diffraction, thermal analysis, and solubility testing, we unveil complex polymorphic behaviors, reversible solid-state transitions, and significant differences in solubility and stability among the salts. Notably, the hydrogen sulfate salt emerges as a promising candidate for drug formulations, offering improved solubility, nonhygroscopic nature, and favorable morphological characteristics compared to the existing chloride salt.

Transition Metal-Based Dimeric Metallosurfactants: From Organic-Inorganic Hybrid Structures and Low-Dimensional Magnets to Metallomicelles.

The dimeric (gemini) as well as metallosurfactants exhibit enhanced physicochemical properties compared with conventional surfactants. By uniting the benefits of both, a series of novel dimeric metallosurfactants of the type (12-2-12)[MBr] (M = Co, Ni, Cu and Zn) was successfully prepared by the reaction of the dimeric surfactant bis(,-dimethyl--dodecyl)ethylene-1,2-diammonium dibromide, 12-2-12, and the MBr salt. Structures and magnetic properties of the materials were studied comprehensively in the solid state, while their micellization was explored in solution.

Impact of POM's coordination mode and Mo-hybrid constituents on the binding, stability, and catalytic properties of hybrid (pre)catalysts.

The assembly of MoO and methoxy-substituted salicylaldehyde nicotinoyl hydrazone ligands afforded two classes of hybrid polyoxometalates (POMs). In the Class I architectures, [MoO(HL)(D)][MoO]·CHCOCH (D = CHCOCH or HO, = 0 or 2, and L = ligands bearing the OMe group at position 3, 4 and 5, respectively), the main driving force for self-assembly is the electrostatic interaction between the components. Class II architectures are composed of a POM anion covalently linked to two Mo-complex units through the terminal O or bridging μ-O oxygen atoms, as found in Lindqvist-based hybrids [{MoO(HL)}MoO]·CHCN ( = 0 or 2) and the asymmetrical β-octamolybdate-based hybrid [{MoO(HL)(HL)}{MoO(HL)}MoO]·CHCN·HO.

Direct thermodynamic characterization of solid-state reactions by isothermal calorimetry.

Despite the growing importance of solid-state reactions, their thermodynamic characterization has largely remained unexplored. This is in part due to the lack of methodology for measuring the heat effects related to reactions between solid reactants. We address here this gap and report on the first direct thermodynamic study of chemical reactions between solid reactants by isothermal calorimetry.

Relationships between radionuclides, metals, and sediment properties in sediment of a bay exposed to anthropogenic pressure and mixed sediment sources (Kaštela Bay, Adriatic Sea, Croatia).

Natural and anthropogenic radionuclides, metals, organic matter, sediment grain size, mineral composition, and sediment sources were studied in marine sediment of Kaštela Bay up to a depth of 0.5 m. Deposition of man-modified material into the sea was evidenced in sediment mineral composition.

Supramolecular intermediates in thermo-mechanochemical direct amidations.

We present a solvent-free thermo-mechanochemical approach for the direct coupling of carboxylic acids and amines, which avoids activators and additives. Detailed analysis of the reactions by and monitoring methods led to the observation, isolation, and characterisation of multicomponent crystalline intermediates that precede the formation of amides. We applied our methodology for the quantitative synthesis of the active pharmaceutical ingredient moclobemide.

The Role of Crystalline Intermediates in Mechanochemical Cyclorhodation Reactions Elucidated by in-Situ X-ray Powder Diffraction and Computation.

The occurrence of crystalline intermediates in mechanochemical reactions might be more widespread than previously assumed. For example, a recent study involving the acetate-assisted C-H activation of N-Heterocycles with [Cp*RhCl ] by ball milling revealed the formation of transient cocrystals between the reagents prior to the C-H activation step. However, such crystalline intermediates were only observed through stepwise intervallic ex-situ analysis, and their exact role in the C-H activation process remained unclear.

Structure-Related Evolution of Magnetic Order in Anisidinium Tetrachlorocuprates(II).

Tetrachlorocuprate(II) hybrids of the three anisidine isomers (-, -, and -, or 2-, 3-, and 4-methoxyaniline, respectively) were prepared and studied in the solid state via X-ray diffraction and magnetization measurements. Depending on the position of the methoxy group of the organic cation, and subsequently, the overall cation geometry, a layered, defective layered, and the structure comprising discrete tetrachlorocuprate(II) units were obtained for the -, -, and -anisidinium hybrids, respectively. In the case of layered and defective layered structures, this affords quasi-2D-layered magnets, demonstrating a complex interplay of strong and weak magnetic interactions that lead to the long-range ferromagnetic (FM) order.

Structural Insights into Layered Tetrahalocuprates(II) Based on Small Unsaturated and Cyclic Primary Ammonium Cations.

Layered hybrid halometallates represent a promising class of multifunctional materials, yet with many open challenges regarding the interaction between building blocks. In this work, we present a synthetic and analytical methodology for the efficient synthesis and structural analysis of a series of novel tetrahalocuprate(II) hybrids based on small alkylammonium cations. Observed robustness in geometrical motifs provided a platform for crystal structure determination, even from the complex laboratory powder diffraction data.

Diamondoid ether clusters in helium nanodroplets.

Diamondoid ethers were introduced into superfluid helium nanodroplets and the resulting clusters were analyzed by time-of-flight mass spectrometry. Clusters of higher abundances (magic number clusters) were identified and the corresponding potential cluster geometries were obtained from GFN2-xTB and DFT computations. We found that the studied diamondoid ethers readily self-assemble in helium nanodroplets and that London dispersion attraction between hydrocarbon subunits acts as a driving force for cluster formation.

Impedance Spectroscopy as a Powerful Tool for Researching Molybdenum-Based Materials with Schiff Base Hydrazones.

Molybdenum coordination complexes are widely applied due to their biological and pharmacological potential, as well as their performance in different catalytic processes. Parent dioxidomolybdenum Schiff base complexes were prepared via the reaction of [MoO(acac)] with a hydrazone Schiff-base tetradentate ligand. A new hydrazone-Schiff base (HL) and its corresponding mononuclear and polynuclear dioxidomolybdenum(VI) complex were synthesized and characterized by spectroscopic methods and elemental analyses, and their thermal behavior was investigated by thermogravimetry.

Ligand-Modulated Nuclearity and Geometry in Nickel(II) Hydrazone Complexes: From Mononuclear Complexes to Acetato- and/or Phenoxido-Bridged Clusters.

The propensity of 4-hydroxybenzhydrazone-related ligands derived from 3-methoxysalicylaldehyde (HL), 4-methoxysalicylaldehyde (HL), and salicylaldehyde (HL) to act as chelating and/or bridging ligands in Ni(II) complexes was investigated. Three clusters of different nuclearities, [Ni(L)(OAc)(MeOH)]∙2MeOH∙MeCN (∙2MeOH∙MeCN), [Ni(HL)(L)(OAc)(MeOH)]∙4.7MeOH (∙4.

Cocrystal Formation Precedes the Mechanochemically Acetate-Assisted C-H Activation with [Cp*RhCl ].

This work reports the experimentally studied mechanochemical formation of rhodacycles by ball milling pyridine- and quinoline-derived substrates and [Cp*RhCl ] in the presence of NaOAc. Ex-situ analysis of the mechanochemical reactions using powder X-ray diffraction (PXRD), solid-state UV-vis spectroscopy and ATR-FTIR spectroscopy revealed the formation of unexpected cocrystals between the substrates and the rhodium dimer prior to the C-H activation step. This sequence of events differs from the generally accepted steps in solution in which cleavage of [Cp*RhCl ] is initiated by acetate ions.

Magnetoelectric Multiferroicity and Magnetic Anisotropy in Guanidinium Copper(II) Formate Crystal.

Hybrid metal-organic compounds as relatively new and prosperous magnetoelectric multiferroics provide opportunities to improve the polarization, magnetization and magneto-electric coupling at the same time, which usually have some limitations in the common type-I and type-II multiferroics. In this work we investigate the crystal of guanidinium copper (II) formate [C(NH2)3]Cu(HCOO)3 and give novel insights concerning the structure, magnetic, electric and magneto-electric behaviour of this interesting material. Detailed analysis of crystal structure at 100 K is given.

(3,5-Di-methyl-adamantan-1-yl)ammonium methane-sulfonate (memanti-nium mesylate): synthesis, structure and solid-state properties.

The asymmetric unit of the title compound, CHN·CHOS, consists of three (3,5-di-methyl-adamantan-1-yl)ammonium cations, CHN, and three methane-sulfonate anions, CHOS. In the crystal, the cations and anions associate N-H⋯O hydrogen bonds into layers, parallel to the (001) plane, which include large supra-molecular hydrogen-bonded rings.

A unique fluoride nanocontainer: porous molecular capsules can accommodate an unusually high number of "rather labile" fluoride anions.

The present work refers to the challenging issue of fluoride anion recognition/binding in water by taking advantage of the unique possibilities offered by the porous molecular nanocontainers of the {Mo132} Keplerate type allowing the study of a variety of new phenomena. Reaction of the highly reactive carbonate-type capsule with aqueous HF results in the release of carbon dioxide and integration of an unprecedentedly large number of fluoride anions--partly as coordinated ligands at both the pentagonal units and the linkers, partly as a disordered water/fluoride assembly inside the cavity. The internal assembly and some of the fluoride ligands are easily released, which provides interesting options for future studies regarding coordination chemistry and catalysis under confined conditions.

Porous capsules with a large number of active sites: nucleation/growth under confined conditions.

This work deals with the generation of large numbers of active sites and with ensuing nucleation/ growth processes on the inside wall of the cavity of porous nanocapsules of the type (pentagon)12(linker)30≡{(Mo(VI))Mo(VI)5}12{Mo(V)2(ligand)}30. A first example refers to sulfur dioxide capture through displacement of acetate ligands, while the grafted sulfite ligands are able to trap {MoO3H}(+) units thereby forming unusual {(O2SO)3MoO3H}(5-) assemblies. A second example relates to the generation of open coordination sites through release of carbon dioxide upon mild acidification of a carbonate-type capsule.

Supramolecular stabilization of metastable tautomers in solution and the solid state.

This work presents a successful application of a recently reported supramolecular strategy for stabilization of metastable tautomers in cocrystals to monocomponent, non-heterocyclic, tautomeric solids. Quantum-chemical computations and solution studies show that the investigated Schiff base molecule, derived from 3-methoxysalicylaldehyde and 2-amino-3-hydroxypyridine (ap), is far more stable as the enol tautomer. In the solid state, however, in all three obtained polymorphic forms it exists solely as the keto tautomer, in each case stabilized by an unexpected hydrogen-bonding pattern.

Desmotropy, polymorphism, and solid-state proton transfer: four solid forms of an aromatic o-hydroxy Schiff base.

The Schiff base derived from salicylaldehyde and 2-amino-3-hydroxypyridine affords a diversity of solid forms, two polymorphic pairs of the enol-imino (D1 a and D1 b) and keto-amino (D2 a and D2 b) desmotropes. The isolated phases, identified by IR spectroscopy, X-ray crystallography, and (13)C cross-polarization/magnetic angle spinning (CP/MAS) NMR spectroscopy, display essentially planar molecular conformations characterized by strong intramolecular hydrogen bonds of the O-H⋅⋅⋅N (D1) or N-H⋅⋅⋅O (D2) type. A change in the position of the proton within this O⋅⋅⋅H⋅⋅⋅N system is accompanied by substantially different molecular conformations and, subsequently, by divergent supramolecular architectures.

Vanadium-induced formation of thiadiazole and thiazoline compounds. Mononuclear and dinuclear oxovanadium(v) complexes with open-chain and cyclized thiosemicarbazone ligands.

Reactions of the salicylaldehyde 4-phenylthiosemicarbazone (H(2)L) with selected vanadium(iv) and vanadium(v) precursors ([VO(acac)(2)], [VO(OAc)(2)], VOSO(4), [V(2)O(4)(acac)(2)]) were investigated under aerobic conditions in different alcohols (methanol, ethanol, propanol). In all examined cases mononuclear alkoxo vanadium(v) complexes [VOL(OR)] (1) (OR = OMe, OEt, OPr) were isolated as major products. On prolonged standing, mother liquids afforded dinuclear vanadium(v) complexes [V(2)O(3)(L(cycl))(2)(OR)(2)] (3) (OR = OMe, OEt, OPr), where L(cycl)(-) represents 1,3,4-thiadiazole ligand, formed by vanadium-induced oxidative cyclization of H(2)L.

Synthesis and characterisation of thiosemicarbazonato molybdenum(VI) complexes and their in vitro antitumor activity.

New dioxomolybdenum(VI) complexes were obtained by the reaction of [MoO2(acac)2] with thiosemicarbazone ligands derived from 3-thiosemicarbazide and 4-(diethylamino)salicylaldehyde (H2L1), 2-hydroxy-3-methoxybenzaldehyde (H2L2) or 2-hydroxy-1-naphthaldehyde (H2L3). In all complexes thiosemicarbazonato ligands are coordinated to molybdenum as tridentate ONS-donors. Octahedral coordination of each molybdenum atom is completed by methanol molecule (in 1a-3a) or by oxygen atom of Mo=O unit from the neighbouring molecule (in 1-3).

Characterization and treatment of the phosphoric gypsum transport water.

This paper presents a new treatment procedure applied on phosphogypsum transport water. Untreated transport water is highly acidic (pH 1.79), having fluoride content of 1540 mg/L and elevated values of phosphates (215 mg/L) and heavy metals (Fe=25.

Two thiosemicarbazones derived from salicylaldehyde: very specific hydrogen-bonding interactions of the N-H...S=C type.

The molecular structures of two salicylaldehyde thiosemicarbazone derivatives, namely salicylaldehyde 4-phenylthiosemicarbazone, C(14)H(13)N(3)OS, (I), and 4-methoxysalicylaldehyde 4-phenylthiosemicarbazone, C(15)H(15)N(3)O(2)S, (II), both of potential pharmacological interest, are found in the keto (thione) tautomeric form. The first compound represents a second triclinic polymorph of composition beta-C(14)H(13)N(3)OS. Although both polymorphs crystallize in the same space group (P1), the alpha-polymorph [Seena, Kurup & Suresh (2008).