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The mechanical properties of cured wood adhesive films were tested in a dry state by means of nanoindentation. These studies have found that the application of adhesives have an effect on the accuracy of the hardness and elastic modulus determination. The highest values of hardness among the tested adhesives at 20 °C have condensation resins: MF (0.64 GPa) and RPF (0.52 GPa). Then the decreasing EPI (0.43 GPa), PUR (0.23 GPa) and PVAc (0.14 GPa) adhesives. The values of the elastic modulus look a little bit different. The highest values among the tested adhesives at 20 °C have EPI (11.97 GPa), followed by MF (10.54 GPa), RPF (7.98 GPa), PVAc (4.71 GPa) and PUR (3.37 GPa). X-ray micro-computed tomography was used to evaluate the adhesive joint by the determination of the voids. It has been proven that this value depends on the type of adhesive, glue quantity and reactivity. The highest values of the void ratio achieve the PUR (17.26%) adhesives, then PVAc (13.97%), RRF (6.88%), MF (1.78%) and EPI (0.03%). The ratio of the gaps increases with the higher joint thickness. A too high proportion of voids may weaken the adhesive joint. Validerad;2023;Nivå 2;2023-01-01 (johcin)

The selective oxidation of cyclooctene with tert-butylhydroperoxide (TBHP) was studied over Cu-containing MOFs at 348 K in liquid toluene. With Cu3(BTC)2, complete conversion was achieved after 120 h. The epoxide selectivity steadily increases to >80%. The conversion is accelerated by a radical initiator and decelerated by a radical inhibitor. A radical-based mechanism is proposed with alkoxy- or polyperoxides being formed as intermediates to the epoxide. The comparison of the cyclooctene conversion with TBHP over Cu3(BTC)2 with FeBTC, the ion-exchanged zeolites Na,Cu-Y and Na,Fe-Y and TS-1 proves that Cu3(BTC)2 is active for radicals generation from TBHP, but less suitable for catalyzing alkene epoxidation. The two recently reported Cu-MOFs [ Cu ( Me - 4 py - trz - ia ) ] ∞ 3 and [ ( Cu 4 ( μ 4 - O ) ( μ 2 - OH ) 2 ( Me 2 trz - pba ) 4 ] ∞ 3 are up to four times more active for cyclooctene oxidation than Cu3(BTC)2. This was attributed to the specific coordination geometry of the catalytically active Cu sites within these materials. Moreover, the liquid-phase conversion of cyclooctene with TBHP is shown to be a sensitive test reaction to evaluate the potential of new solid oxidation catalysts, especially of transition metal-containing MOFs.

The synthesis and characterization of an isomorphous series of copper-containing microporous metal-organic frameworks (MOFs) based on triazolyl isophthalate linkers with the general formula ∞3[Cu4(μ3-OH)2(R1-R2-trz-ia)3(H2O)x] are presented. Through size adjustment of the alkyl substituents R1 and/or R2 at the linker, the impact of linker functionalization on structure-property relationships was studied. Due to the arrangement of the substituents towards the cavities, the porosity (pore fraction 28%–39%), as well as the pore size can be adjusted by the size of the substituents of the triazole ring. Thermal analysis and temperature-dependent PXRD studies reveal a thermal stability of the MOFs up to 230 °C due to increasing framework stability through fine-tuning of the linker substitution pattern. Adsorption of CO2 (298 K) shows a decreasing maximum loading with increasing steric demand of the substituents of the triazole ring. Furthermore, the selective oxidation of cyclohexene with tert-butyl hydroperoxide (TBHP) is studied over the MOFs at 323 K in liquid chloroform. The catalytic activity increases with the steric demand of the substituents. Additionally, these isomorphous MOFs exhibit considerable robustness under oxidizing conditions confirmed by CO2 adsorption studies, as well as by the catalytic selective oxidation experiments.

An isostructural series of 15 structurally flexible microporous silver metal-organic frameworks (MOFs) is presented. The compounds with a dinuclear silver core as secondary building unit (Ag2N4) can be obtained under solvothermal conditions from substituted triazolyl benzoate linkers and AgNO3 or Ag2SO4; they exhibit 2-fold network interpenetration with lvt topology. Besides the crystal structures, the calculated pore size distributions of the microporous MOFs are reported. Simultaneous thermal analyses confirm the stability of the compounds up to 250 °C. Interconnected pores result in a three-dimensional pore structure. Although the porosity of the novel coordination polymers is in the range of only 20-36%, this series can be regarded as a model system for investigation of network flexibility, since the pore diameters and volumes can be gradually adjusted by the substituents of the 3-(1,2,4-triazol-4-yl)-5-benzamidobenzoates. The pore volumes of selected materials are experimentally determined by nitrogen adsorption at 77 K and carbon dioxide adsorption at room temperature. On the basis of the flexible behavior of the linkers a reversible framework transformation of the 2-fold interpenetrated network is observed. The resulting adsorption isotherms with one or two hysteresis loops are interpreted by a gate-opening process. Due to external stimuli, namely, the adsorptive pressure, the materials undergo a phase transition confirming the structural flexibility of the porous coordination polymer.

Pure component sorption isotherms of n-butane, isobutane, 1-butene and isobutene on the metal–organic framework (MOF) 3∞[Cu4(μ4-O)(μ2-OH)2(Me2trz-pba)4] at various temperatures between 283 K and 343 K and pressures up to 300 kPa are presented. The isotherms show a stepwise pore filling which is typical for structurally flexible materials with broad adsorption–desorption hysteresis loops. Gate opening pressures in their endemic characteristic depend on the used hydrocarbon gases. From all investigated gases only the isotherms of 1-butene present a second step at a relative pressure above p/p0 = 0.55. As a consequence, only 1-butene can fully open the framework resulting in a pore volume of 0.54 cm3 g−1. This result is in good agreement with the value of 0.59 cm3 g−1 calculated based on single crystal structure data. The isosteric heat of adsorption was calculated from the experimental isotherms for all C4-isomers. At low loadings the isosteric heat is in a narrow region between 41 and 49 kJ mol−1. Moreover, in situ XRD measurements at different relative hydrocarbon pressures were performed at 298 K for the C4-isomers. The differences in the pressure-depending powder diffraction patterns indicate phase transitions as a result of adsorption. Similar diffraction patterns were observed for all C4-hydrocarbons, except 1-butene, where the second step at higher relative pressure (p/p0 > 0.55) is accompanied by an additional phase transition. This powder pattern resembles that of the as-synthesized MOF material containing solvent molecules in the pore system. The resulting structural changes of the material during guest and pressure induced external stimuli are evidenced by the new coupled XRD adsorption equipment.

For two series of isostructural, heteronuclear 3D coordination polymers containing Co and Zn, i.e., [Co x Zn 1 − x (tdc)(bipy)] and [Co x Zn 1 − x (Me 2 trz– p ba) 2 ], with n Co /n Zn -ratios from 0.00 to 1.00, the epoxidation of cyclooctene with tert -butyl hydroperoxide in liquid toluene at 348 K was studied. In dependence of the Co-content in the material, the catalytic activity steadily increases with the Co-free materials being inactive and the Zn-free materials showing the highest catalytic activity (cyclooctene conversion of 32% and epoxide selectivity of 50%). Although the catalytic conversion occurs at the outer crystallite surface, the results prove that a sensitive tuning of the catalytic properties of coordination polymers and metal-organic frameworks can be achieved by isomorphous substitution with redox active elements.

Synthesis and solid-state NMR characterization of two isomorphous series of zinc and cobalt coordination networks with 1,2,4-triazolyl benzoate ligands are reported. Both series consist of 3D diamondoid networks with four-fold interpenetration. Solid-state NMR identifies the metal coordination of the ligands, and assignment of all (1)H and (13)C shifts was enabled by the combination of (13)C editing, FSLG-HETCOR spectra, and 2D (1)H-(1)H back-to-back (BABA) spectra with results from NMR-CASTEP calculations. The incorporation of Co(2+) replacing Zn(2+) ions in the MOF over the full range of concentrations has significant influences on the NMR spectra. A uniform distribution of metal ions is documented based on the analysis of (1)H T1 relaxation time measurements.

Syntheses and comprehensive characterization of two closely related series of isomorphous metal-organic frameworks (MOFs) based on triazolyl isophthalate linkers with the general formula ∞(3)[M2(R(1)-R(2)-trz-ia)2] (M = Cu, Zn) are presented. Using solvothermal synthesis and synthesis of microcrystalline materials on the gram scale by refluxing a solution of the starting materials, 11 MOFs are readily available for a systematic investigation of structure-property relationships. The networks of the two series are assigned to rutile (rtl) (1-4) and α-PbO2 (apo) (5-9) topology, respectively. Due to the orientation of the triazole substituents toward the cavities, both the pore volume and the pore diameter can be adjusted by choice of the alkyl substituents. Compounds 1-9 exhibit pronounced microporosity with calculated porosities of 31-53% and show thermal stability up to 390 °C as confirmed by simultaneous thermal analysis. Systematic investigation of adsorption properties by CO2 (298 K) and N2 (77 K) adsorption studies reveal remarkable network flexibility induced by alkyl substituents on the linker. Fine-tuning of the gate opening pressure and of the hysteresis shape is possible by adjusting the substitution pattern and by choice of the metal ion.

An isomorphous series of 10 microporous copper-based metal-organic frameworks (MOFs) with the general formulas (∞)(3)[{Cu(3)(μ(3)-OH)(X)}(4){Cu(2)(H(2)O)(2)}(3)(H-R-trz-ia)(12)] (R = H, CH(3), Ph; X(2-) = SO(4)(2-), SeO(4)(2-), 2 NO(3)(2-) (1-8)) and (∞)(3)[{Cu(3)(μ(3)-OH)(X)}(8){Cu(2)(H(2)O)(2)}(6)(H-3py-trz-ia)(24)Cu(6)]X(3) (R = 3py; X(2-) = SO(4)(2-), SeO(4)(2-) (9, 10)) is presented together with the closely related compounds (∞)(3)[Cu(6)(μ(4)-O)(μ(3)-OH)(2)(H-Metrz-ia)(4)][Cu(H(2)O)(6)](NO(3))(2)·10H(2)O (11) and (∞)(3)[Cu(2)(H-3py-trz-ia)(2)(H(2)O)(3)] (12(Cu)), which are obtained under similar reaction conditions. The porosity of the series of cubic MOFs with twf-d topology reaches up to 66%. While the diameters of the spherical pores remain unaffected, adsorption measurements show that the pore volume can be fine-tuned by the substituents of the triazolyl isophthalate ligand and choice of the respective copper salt, that is, copper sulfate, selenate, or nitrate.

The syntheses and crystal structures of a mononuclear cadmium complex and five novel coordination polymers based on 1,2,4-triazolyl benzoates are presented. The compounds (∞)(3)[Cd(H-Me-trz-pba)(2)] (2), (∞)(3)[Cd(Me-3py-trz-pba)(2)] (4), and (∞)(3)[Zn(H-Me-trz-pba)(2)] (6) can be obtained by solvothermal synthesis or simple heating of the starting materials in appropriate solvents, and are also accessible by thermal conversion of the complex [Cd(H-Me-trz-pba)(2)(H(2)O)(4)] (1), the one-dimensional (1D) coordination polymer (∞)(1)[Cd(Me-3py-trz-pba)(2)(H(2)O)(2)]·H(2)O (3), and the porous three-dimensional (3D) framework (∞)(3)[Zn(H-Me-trz-pba)2]·4H(2)O (5), respectively. The driving force for these conversions is the formation of thermally stable, nonporous, crystalline 3D coordination polymers. The structural transformations are accompanied by the loss of water and reveal significant changes of the coordination spheres of the metal ions caused by a rearrangement of the triazolyl benzoate ligands. Compounds 2, 4, 5, and 6 exhibit 4- and 5-fold interpenetration of diamondoid networks (dia) and are thermally stable up to 380 °C.

Two new binuclear silver(I) complexes of 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine (PDT) and 3,5,6-tris(2-pyridyl)-1,2,4-triazine (TPT) ligands, [Ag2(PDT)2(NO3)2], 1, and [Ag2(TPT)2(NO3)2], 2, have been synthesized and characterized by elemental analysis, IR and 1H NMR spectroscopy, and also studied by thermal and electrochemical analysis as well as by X-ray crystallography. The individual dinuclear complexes in 1 are extended into a one-dimensional layered structure by weak Ag···CPDT (η3) interactions. The interesting features of the Ag(I) complexes are the different coordination modes of the ligands. The supramolecular features in these complexes are controlled by weak directional intra and intermolecular interactions.

Due to their network flexibility, metal-organic frameworks (MOFs) may respond to external stimuli such as guest molecules, heat, pressure, humidity and so on by a dynamical transformation of their structure. In this work we present experimental studies by means of nitrogen and argon physisorption at cryogenic temperature concerning the influence of handling and storage on the recently synthesized highly flexible copper-based MOF ∞ 3 [ ( Cu 4 ( μ 4 -O ) ( μ 2 -OH ) 2 ( Me 2 trz p ba ) 4 ] . Unusual adsorption isotherms with up to three distinct steps in the adsorbed volume have been found substantiating once more: (i) the high sensitivity of flexible network structures for environmental influences, (ii) the high diversity of physisorption isotherm types for flexible materials including isotherms with several steps and large hysteresis loops, and last but not least (iii) that theoretical methods assuming inert solids cannot be applied to highly flexible materials for calculating pore sizes and other solid state parameters.

Synthesis and crystal structure of a novel copper-based MOF material are presented. The tetragonal crystal structure of [ ∞ 3 ( Cu 4 ( μ 4 -O ) ( μ 2 -OH ) 2 ( Me 2 trz p ba ) 4 ] possesses a calculated solvent-accessible pore volume of 57%. Besides the preparation of single crystals, synthesis routes to microcrystalline materials are reported. While PXRD measurements ensure the phase purity of the as-synthesized material, TD-PXRD measurements and coupled DTA–TG–MS analysis confirm the stability of the network up to 230 °C. The pore volume of the microcrystalline material determined by nitrogen adsorption at 77 K depends on the synthetic conditions applied. After synthesis in DMF/H2O/MeOH the pores are blocked for nitrogen, whereas they are accessible for nitrogen after synthesis in H2O/EtOH and subsequent MeOH Soxhleth extraction. The corresponding experimental pore volume was determined by nitrogen adsorption to be V Pore = 0.58 cm 3 g - 1 . In order to characterize the new material and to show its adsorption potential, comprehensive adsorption studies with different adsorptives such as nitrogen, argon, carbon dioxide, methanol and methane at different temperatures were carried out. Unusual adsorption–desorption isotherms with one or two hysteresis loops are found – a remarkable feature of the new flexible MOF material.

The crystal structures of five new Co(II), Zn(II), and Cd(II) coordination polymers based on pyridine-substituted triazolyl carboxylates are reported. The two isomorphous compounds (∞)³[M(Me-3py-pba)₂] (M = Zn, Co) possess {6⁶} topology (dia). In order to obtain heteronuclear compounds, we synthesized Co(II)-substituted Zn(II) and Cd(II) coordination polymers. At T = 5 K, the powder samples of the diamagnetically diluted Co(II)/Zn(II) and Co(II)/Cd(II) systems [Co/(Zn,Cd) ≈ 0.01] show intense electron paramagnetic resonance spectra, which were analyzed with an effective spin of S' = ½. The g tensor as well as the ⁵⁹Co hyperfine tensor A(Co) are strongly anisotropic. The g tensor components are used to gain information about the symmetry of the Co(II) coordination sphere and covalency effects. Differential thermal analysis/thermogravimetry-mass spectrometry and temperature-dependent powder X-ray diffraction studies reveal high thermal stability of the three-dimensional coordination polymers up to 390 °C.

The magnetic properties of the dinuclear and tetranuclear nickel(II) tetrazolato complexes [Ni2L(RCN4)][BPh4] (R = H (4), Me (5), Ph (6)) and [(Ni2L)2(1,4-(CN4)2-C6H4)][BPh4]2 (7), where (L)2– represents a 24-membered macrocyclic N6S2 supporting ligand, are reported. Analysis of temperature-dependent magnetic susceptibility measurements over the temperature range from 2 to 300 K revealed the presence of weak ferromagnetic exchange interactions between the NiII ions in the binuclear [Ni2L(μ-L′)]+ subunits with magnetic exchange coupling constant values of J1 = 13.5 cm–1 for 4, J1 = 20.0 cm–1 for 5, J1 = 19.2 cm–1 for 6, and J1 = 15.2 cm–1 for 7 (H = –2JS1S2). The exchange coupling J2 across the bistetrazolato bridge in 7 is less than 0.1 cm–1, which suggests that no significant interdimer coupling occurs in this compound. The synthesis and crystal structure of the new complex 7·2MeCN is also reported.

An optimised synthesis of 3,4,5-trisubstituted 1,2,4-triazoles, that can be used as linkers for metal organic frameworks (MOFs), is described. The substituents in 3- and 5-position of the triazole have a significant impact on the torsion angles between the aromatic rings and therefore influence on solubility and coordination behaviour of these ligands.

A bitopic ligand, 4-(3,5-dimethylpyrazol-4-yl)-1,2,4-triazole (Hpz-tr) (1), containing two different heterocyclic moieties was employed for the design of copper(II)-molybdate solids under hydrothermal conditions. In the multicomponent Cu(II)/Hpz-tr/Mo(VI) system, a diverse set of coordination hybrids, [Cu(Hpz-tr)2SO4]·3H2O (2), [Cu(Hpz-tr)Mo3O10] (3), [Cu4(OH)4(Hpz-tr)4Mo8O26]·6H2O (4), [Cu(Hpz-tr)2Mo4O13] (5), and [Mo2O6(Hpz-tr)]·H2O (6), was prepared and characterized. A systematic investigation of these systems in the form of a ternary crystallization diagram approach was utilized to show the influence of the molar ratios of starting reagents, the metal (Cu(II) and Mo(VI)) sources, the temperature, etc., on the reaction products outcome. Complexes 2-4 dominate throughout a wide crystallization range of the composition triangle, while the other two compounds 5 and 6 crystallize as minor phases in a narrow concentration range. In the crystal structures of 2-6, the organic ligand behaves as a short [N-N]-triazole linker between metal centers Cu···Cu in 2-4, Cu···Mo in 5, and Mo···Mo in 6, while the pyrazolyl function remains uncoordinated. This is the reason for the exceptional formation of low-dimensional coordination motifs: 1D for 2, 4, and 6 and 2D for 3 and 5. In all cases, the pyrazolyl group is involved in H bonding (H-donor/H-acceptor) and is responsible for π-π stacking, thus connecting the chain and layer structures in more complicated H-bonding architectures. These compounds possess moderate thermal stability up to 250-300 °C. The magnetic measurements were performed for 2-4, revealing in all three cases antiferromagnetic exchange interactions between neighboring Cu(II) centers and long-range order with a net moment below Tc of 13 K for compound 4.

Spectroscopic techniques are a powerful tool for structure determination, especially if single-crystal material is unavailable. (113)Cd solid-state NMR is easy to measure and is a highly sensitive probe because the coordination number, the nature of coordinating groups, and the geometry around the metal ion is reflected by the isotropic chemical shift and the chemical-shift anisotropy. Here, a detailed investigation of a series of 27 cadmium coordination polymers by (113)Cd solid-state NMR is reported. The results obtained demonstrate that (113)Cd NMR is a very sensitive tool to characterize the cadmium environment, also in non-single-crystal materials. Furthermore, this method allows the observation of guest-induced phase transitions supporting understanding of the structural flexibility of coordination frameworks.

The isomorphous title complexes, dichlorido[4-(3,5-dimethyl-4H-1,2,4-triazol-4-yl)benzoic acid-kappaN(1)]zinc(II) dihydrate, [ZnCl(2)(C(11)H(11)N(3)O(2))(2)].2H(2)O, and dibromido[4-(3,5-dimethyl-4H-1,2,4-triazol-4-yl)benzoic acid-kappaN(1)]zinc(II) dihydrate, [ZnBr(2)(C(11)H(11)N(3)O(2))(2)].2H(2)O, were synthesized and crystallized by slow evaporation of the solvent from a solution of the ligand and either zinc chloride or zinc bromide, respectively, in water/ethanol. The Zn(II) ions occupy twofold axes in the noncentrosymmetric orthorhombic space group Fdd2. The metal ion is approximately tetrahedrally coordinated by two monodentate triazole groups of the ligands and additionally by two halide ions. The water molecules incorporate the complexes into a three-dimensional framework made up by hydrogen bonds. Furthermore, each complex possesses two hydrogen-bond-donor sites represented by the carboxy groups and two acceptor sites at the noncoordinating N atoms of the triazoles.

The newly synthesized Zn(4)O-based MOF (3)(∞)[Zn(4)(μ(4)-O){(Metrz-pba)(2)mPh}(3)]·8 DMF (1·8 DMF) of rare tungsten carbide (acs) topology exhibits a porosity of 43% and remarkably high thermal stability up to 430 °C. Single crystal X-ray structure analyses could be performed using as-synthesized as well as desolvated crystals. Besides the solvothermal synthesis of single crystals a scalable synthesis of microcrystalline material of the MOF is reported. Combined TG-MS and solid state NMR measurements reveal the presence of mobile DMF molecules in the pore system of the framework. Adsorption measurements confirm that the pore structure is fully accessible for nitrogen molecules at 77 K. The adsorptive pore volume of 0.41 cm(3) g(-1) correlates well with the pore volume of 0.43 cm(3) g(-1) estimated from the single crystal structure.

As a basis for the evaluation of hydrogen storage by physisorption, adsorption isotherms of H2 were experimentally determined for several porous materials at 77 K and 298 K at pressures up to 15 MPa. Activated carbons and MOFs were studied as the most promising materials for this purpose. A noble focus was given on how to determine whether a material is feasible for hydrogen storage or not, dealing with an assessment method and the pitfalls and problems of determining the viability. For a quantitative evaluation of the feasibility of sorptive hydrogen storage in a general analysis, it is suggested to compare the stored amount in a theoretical tank filled with adsorbents to the amount of hydrogen stored in the same tank without adsorbents. According to our results, an “ideal” sorbent for hydrogen storage at 77 K is calculated to exhibit a specific surface area of >2580 m2 g−1 and a micropore volume of >1.58 cm3 g−1.

International audience; The concentration and temperature dependence of the self-diffusion of benzene adsorbed in the metal-organic framework MOF-5 (IRMOF-1) is studied by pulsed field gradient (PFG) NMR spectroscopy. When increasing the loading from 10 to 20 molecules per unit cell of MOF-5, the experimental diffusion data drop by a factor of about 3 while current molecular dynamic (MD) simulations predict slightly increasing diffusion coefficients for this range of loadings. The observation is rationalized using the recently predicted clustering of adsorbate molecules in microporous systems for temperatures well below the adsorbate critical temperature. Necessary improvements of molecular simulation models for predicting diffusivities under such conditions are discussed.

A series of molybdenum(VI) oxide-organic solids were prepared by hydrothermal reactions employing N-donor tectons, which combine two 1,2,4-triazol-4-yl sites separated by representative aliphatic spacers (ethylene, tr(2)eth; 1,3-propylene, tr(2)pr; trans-1,4-cyclohexanediyl, tr(2)cy; diamondoid 1,3-adamantanediyl, tr(2)ad; 1,6- and 4,9-diamantanediyls, 1,6-tr(2)dia and 4,9-tr(2)dia) and heterofunctional 5-[4-(1,2,4-triazol-4-yl)phenyl]tetrazole (trtz). In all the compounds the 1,2,4-triazol-4-yl group acts as a short-distance N(1),N(2)-bridge between two Mo ions (Mo-N 2.36-2.50 A). The 3D framework structure is based upon pseudo-4(1) helices ([Mo(4)O(12)(tr(2)eth)(2)] 1, [Mo(2)O(6)(tr(2)cy)] 3) or sinusoidal chains ([Mo(2)O(6)(tr(2)pr)] 2, [Mo(2)O(6)(tr(2)ad)].6H(2)O 4, [Mo(2)O(6)(4,9-tr(2)dia)].0.5H(2)O 5) of vertex-sharing MoO(4)N(2) octahedra, while the bitopic organic ligands manifest a dual role as connectors for two adjacent octahedra and as links between separate 1D inorganic subtopologies. For linear, lengthy tectons tr(2)cy and 4,9-tr(2)dia two identical frameworks interpenetrate. In [MoO(3)(trtz)] 7, the 4(1) helices aggregate into 3D tetragonal framework (five-fold interpenetrated) by hydrogen bonding between the tetrazole groups. The 2D structure of [Mo(4)O(12)(1,6-tr(2)dia)].2H(2)O 6 is influenced by the very bulky aliphatic portion of the ligands, which connect chains of edge-shared octahedra MoO(5)N (Mo-N 2.346(2), 2.456(2) A).