From non-conductive MOF to proton-conducting metal-HOFs: a new class of reversible transformations induced by solvent-free mechanochemistry.

Proton-conducting materials play an important role as solid electrolytes in electrochemical devices for energy storage and conversion, including proton exchange membrane fuel cells. Metal-organic frameworks (MOFs), covalent-organic frameworks (COFs) and more recently hydrogen-bonded organic frameworks (HOFs) have emerged as useful crystalline platforms for proton transport that provide high conductivity and enable insight into conduction pathways. Here, we present two new HOFs with high conductivity, reaching 2 × 10-2 S cm-1 at 60 °C and 75% relative humidity, obtained in reactions that represent a new class of reversible transformations of solids. The reactions are induced by solvent-free mechanochemistry and involve breaking of coordination linkages in a MOF and formation of extended hydrogen-bonded networks of metal-HOFs (MHOFs). This unprecedented class of MOF-to-MHOF transformations has been demonstrated using a non-conductive MOF (JUK-1) and formamidinium or methylammonium thiocyanates as solid reactants. Structural details of the solid-state reactions are revealed by powder X-ray diffraction and Rietveld refinements for the MHOF products. None of the attempts using conventional methods were successful in obtaining the MHOFs, emphasizing a unique role of mechanochemical stimuli in the reactivity of supramolecular polymer solids, including crystalline MOFs and HOFs. The reversible nature of non-covalent interactions in such materials may be utilized for the development of healable polymer systems.

From crystal phase mixture to pure metal-organic frameworks - Tuning pore and structure properties.

In this study, a sonochemical route for the preparation of a new Hf-MIL-140A metal-organic framework from a mixture of UiO-66/MIL-140A is presented. The sonochemical synthesis route not only allows the phase-pure MIL-140A structure to be obtained but also induces structural defects in the MIL-140A structure. The synergic effect between the sonochemical irradiation and the presence of a highly acidic environment results in the generation of slit-like defects in the crystal structure, which increases specific surface area and pore volume. The BET-specific surface area in the case of sonochemically derived Zr-MIL-140A reaches 653.3 m2/g, which is 1.5 times higher than that obtained during conventional synthesis. The developed Hf-MIL-140A structure is isostructural to Zr-MIL-140A, which was confirmed by synchrotron X-ray powder diffraction (SR-XRD) and by continuous rotation electron diffraction (cRED) analysis. The obtained MOF materials have high thermal and chemical stability, which makes them promising candidates for applications such as gas adsorption, radioactive waste removal, catalysis, and drug delivery.

New Organic-Inorganic Hybrid Compounds Based on Sodium Peroxidomolybdates (VI) and Derivatives of Pyridine Acids: Structure Determination and Catalytic Properties.

Two organic-inorganic hybrids based on sodium peroxidomolybdates(VI) and 3,5-dicarboxylic pyridine acid (Na-35dcpa) or N-oxide isonicotinic acid (Na-isoO) have been synthesized and characterized. All compounds contain inorganic parts: a pentagonal bipyramid with molybdenum center, and an organic part containing 3,5-dicarboxylic pyridine acid or N-oxide isonicotinic acid moieties. The type of organic part used in the synthesis influences the crystal structure of obtained compounds. This aspect can be interesting for crystal engineering. Crystal structures were determined using powder X-ray diffraction or single crystal diffraction for compounds Na-35dcpa and Na-isoO, respectively. Elemental analysis was used to check the purity of the obtained compounds, while X-ray Powder Diffraction (XRPD) vs. temp. was applied to verify their stability. Moreover, all the compounds were examined by Infrared (IR) spectroscopy. Their catalytic activity was tested in the Baeyer-Villiger (BV) oxidation of cyclohexanone to ε-caprolactone in the oxygen-aldehyde system. The highest catalytic activity in the BV oxidation was observed for Na-35dcpa. The compounds were also tested for biological activity on human normal cells (fibroblasts) and colon cancer cell lines (HT-29, LoVo, SW 620, HCT 116). All compounds were cytotoxic against tumor cells with metastatic characteristics, which makes them interesting and promising candidates for further investigations of specific anticancer mechanisms.

Solid-State Study of the Structure, Dynamics, and Thermal Processes of Safinamide Mesylate─A New Generation Drug for the Treatment of Neurodegenerative Diseases.

Safinamide mesylate (SM), the pure active pharmaceutical ingredient (API) recently used in Parkinson disease treatment, recrystallized employing water-ethanol mixture of solvents (vol/vol 1:9) gives a different crystallographic form compared to SM in Xadago tablets. Pure SM crystallizes as a hemihydrate in the monoclinic system with the P21 space group. Its crystal and molecular structure were determined by means of cryo X-ray crystallography at 100 K. SM in the Xadago tablet exists in anhydrous form in the orthorhombic crystallographic system with the P212121 space group. The water migration and thermal processes in the crystal lattice were monitored by solid-state NMR spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. SM in Xadago in the high-humidity environment undergoes phase transformation to the P21 form which can be easily reversed just by heating up to 80 °C. For the commercial form of the API, there is also a reversible thermal transformation observed between Z' = 1 ↔ Z' = 3 crystallographic forms in the 0-20 °C temperature range. Analysis of molecular motion in the crystal lattice proves that the observed conformational polymorphism is forced by intramolecular dynamics. All above-mentioned processes were analyzed and described employing the NMR crystallography approach with the support of advanced theoretical calculations.

Newly-Obtained Two Organic-Inorganic Hybrid Compounds Based on Potassium Peroxidomolybdate and Dicarboxypyridinic Acid: Structure Determination, Catalytic Properties, and Cytotoxic Effects of Eight Peroxidomolybdates in Colon and Hepatic Cancer Cells.

Two new organic-inorganic hybrid compounds containing dicarboxylic pyridine acids have been obtained and characterized. Both compounds are potassium oxidodiperoxidomolybdates with 2,6-dicarboxylicpyridine acid or 3,5-dicarboxylicpyridine acid moieties, respectively. The chemical formula for the first one is C14H7K3Mo2N2O18 denoted as K26dcpa, the second C7H4K1Mo1N1O11.5-K35dcpa. Their crystal structures were determined using single crystal (K26dcpa) or XRPD-X-ray powder diffraction techniques (K35dcpa). The purity of the compounds was confirmed by elemental analysis. Their thermal stability was determined with the use of non-ambient XRPD. In addition, they were examined by IR spectroscopy methods and catalytic activity studies were performed for them. Catalytic tests in the Baeyer-Villiger reaction and biological activity have been performed for eight compounds: K26dcpa, K35dcpa, and six peroxidomolybdates previously obtained by our group. The anti-proliferative activity of peroxidomolybdenum compounds after 24 h of incubation was studied in vitro against three selected human tumor cell lines (SW620, LoVo, HEP G2) and normal human cells (fibroblasts). The data were expressed as IC50 values. The structure of the investigated oxodiperoxomolybdenum compounds was shown to have influence on the biological activity and catalytic properties. It has been shown that the newly-obtained compound, K35dcpa, is a very efficient catalyst in the Baeyer-Villiger reaction. The best biological activity results were obtained for Na-picO (previously obtained by us), which is a very effective anti-cancer agent towards SW 620 colorectal adenocarcinoma cells.

Synthesis, crystal structure solution and characterization of two organic-inorganic hybrid layered materials based on metal sulfates and 1,4-phenylenediamine.

Two organic-inorganic hybrid layered materials, namely poly[(µ-1,4-diaminobenzene-κ2N:N')[µ3-sulfato(VI)-κ4O:O':O'',O''']manganese], [Mn(SO4)(C6H8N2)]n, 1, and poly[(µ-1,4-diaminobenzene-κ2N:N')[µ3-sulfato(VI)-κ4O:O':O'',O''']copper], [Cu(SO4)(C6H8N2)]n, 2, have been synthesized using 1,4-phenylenediamine (PPD) as an organic template and component (linker). Both materials form three-dimensional frameworks. The crystal structures were determined using data from powder X-ray diffraction measurements. The purity and morphology of the compounds were studied by elemental analyses and SEM investigations, and their thermal stabilities were determined by thermogravimetric and nonambient powder X-ray diffraction measurements, which indicated that 1 is stable up to 537 K and 2 is stable up to 437 K.

1D coordination polymer (OPD)2CoIISO4 showing SMM behaviour and multiple relaxation modes.

A novel one-dimensional CoII coordination polymer (OPD)2CoIISO4 was formed from alternating tetrahedral sulphate anions, Co centers and molecules of 1,2-phenylenediamine (OPD). The thermal stability of the structure was confirmed up to ∼230 °C using thermogravimetry and non-ambient powder X-ray diffraction in air. The distorted pseudo-octahedral coordination sphere of CoII ions promotes strong magnetic anisotropy. Therefore (OPD)2CoIISO4 was subjected to thorough characterization with ab initio and DFT calculations along with dc magnetic measurements both of which point to strong easy-axis anisotropy (D/kB≈-87 K, E/kB≈ 23 K). The analysis of ac susceptibility revealed field assisted magnetic relaxation in two field regimes: a low field one with one relaxation time and a high field one where three relaxation times were distinguished. The main role in relaxations of the fastest process (τ1) was attributed to the direct and Raman processes.

Magnetic percolation in CN-bridged ferrimagnetic coordination polymers.

A series of diluted molecular magnets {[MnII(H2O)2]2[MIV(CN)8]·4H2O}n (M = Nb/Mo) exhibiting a ferrimagnetic phase have been synthesized and investigated to demonstrate the first example of site percolation in magnetic coordination polymers. It is the first case of a magnetic percolation study with selective site substitution, where magnetic ions of only one type are replaced by their diamagnetic analogues leaving the other magnetic sublattice untouched. By modifying the molecular field model the NbIV concentration dependence of the magnetic ordering temperature was reproduced and the percolation threshold was determined.

Spectroscopic Evidence for Ligand Substitution Reactions at the Solid-Liquid Interface of a Sub-micrometer Gold(I) Carbene Complex.

Colloidal coordination compounds in the sub-micrometer range were synthesized from a chloro gold(I) carbene complex via the anti-solvent procedure and stabilized by a surfactant shell of Tween 20. This compound was successfully applied as model system to monitor heterogeneous multiphase ligand substitution reactions at the solid-liquid interface.

Mesoporous carbon-containing voltammetric biosensor for determination of tyramine in food products.

A voltammetric biosensor based on tyrosinase (TYR) was developed for determination of tyramine. Carbon material (multi-walled carbon nanotubes or mesoporous carbon CMK-3-type), polycationic polymer-i.e., poly(diallyldimethylammonium chloride) (PDDA), and Nafion were incorporated into titania dioxide sol (TiO2) to create an immobilization matrix. The features of the formed matrix were studied by scanning electron microscopy (SEM) and cyclic voltammetry (CV). The analytical performance of the developed biosensor was evaluated with respect to linear range, sensitivity, limit of detection, long-term stability, repeatability, and reproducibility. The biosensor exhibited electrocatalytic activity toward tyramine oxidation within a linear range from 6 to 130 µM, high sensitivity of 486 µA mM(-1) cm(-2), and limit of detection of 1.5 µM. The apparent Michaelis-Menten constant was calculated to be 66.0 µM indicating a high biological affinity of the developed biosensor for tyramine. Furthermore, its usefulness in determination of tyramine in food product samples was also verified. Graphical abstract Different food samples were analyzed to determine tyramine using biosensor based on tyrosinase.

Ground to conduct: mechanochemical synthesis of a metal-organic framework with high proton conductivity.

We report a high proton-conducting material prepared for the first time by economical and environmentally-friendly mechanochemistry. Structural elucidation of the material from powder X-ray diffraction data reveals the details of the solid-state reaction. The reaction represents a new synthetic strategy towards materials related to fuel cell technology.

Fine refinement of solid state structure of racemic form of phospho-tyrosine employing NMR Crystallography approach.

We present step by step facets important in NMR Crystallography strategy employing O-phospho-dl-tyrosine as model sample. The significance of three major techniques being components of this approach: solid state NMR (SS NMR), X-ray diffraction of powdered sample (PXRD) and theoretical calculations (Gauge Invariant Projector Augmented Wave; GIPAW) is discussed. Each experimental technique provides different set of structural constraints. From the PXRD measurement the size of the unit cell, space group and roughly refined molecular structure are established. SS NMR provides information about content of crystallographic asymmetric unit, local geometry, molecular motion in the crystal lattice and hydrogen bonding pattern. GIPAW calculations are employed for validation of quality of elucidation and fine refinement of structure. Crystal and molecular structure of O-phospho-dl-tyrosine solved by NMR Crystallography is deposited at Cambridge Crystallographic Data Center under number CCDC 1005924.

Bis(4-methylanilinium) and bis(4-iodoanilinium) pentamolybdates from laboratory X-ray powder data and total energy minimization.

The crystal structures of poly[bis(4-methylanilinium) [tetra-µ3-oxido-hexa-µ2-oxido-hexaoxidopentamolybdenum(VI)]], {(C7H10N)2[Mo5O16]}n, (I), and poly[bis(4-iodoanilinium) [tetra-µ3-oxido-hexa-µ2-oxido-hexaoxidopentamolybdenum(VI)]], {(C6H7IN)2[Mo5O16]}n, (II), were determined from laboratory X-ray powder diffraction data using the direct-space parallel-tempering approach and refined by total energy minimization in the solid state. Both compounds adopt layered structures, in which layers of the inorganic {[Mo5O16](2-)}n polyanion alternate with layers of the organoammonium cations parallel to the (100) plane. The asymmetric units contain three Mo atoms (one situated on a twofold axis, Wyckoff position 4e), eight O atoms and one organic cation. Despite the fact that the structure determinations are based on powder diffraction data, due to the total energy minimization approach applied the Mo-O bond lengths can formally be assigned to one of the three groups, reflecting different types of O-atom placement within the polyanion. The cations form relatively strong N-H...O hydrogen bonds, anchoring one end of the organic molecules to both terminal and shared O atoms. The interactions involving the opposite end of the benzene rings are much weaker and include C-H...O and C-H...π bonds in (I) and an I...O halogen bond in (II). Mutual rotation of the benzene rings in both structures leads to the formation of a C-H...H-C dihydrogen bond, with H-atom separations of 1.95 Šin (I) and 2.12 Šin (II). Differential scanning calorimetry measurements show that the interactions between the inorganic and organic layers are stronger in (I) than in (II).