Sustainable catalysts for efficient triazole synthesis: an immobilized triazine-based copper-NNN pincer complex on TiO2.

The multistep synthesis of a hybrid material based on a TiO2 core with an immobilized triazine-based copper(II)-NNN pincer complex is reported. The formation of the material was confirmed by FT-IR spectroscopy and elemental and thermogravimetric analyses, and the loading by copper ions was quantified by ICP/OES analysis. The properties of the hybrid material were further investigated by X-ray photoelectron spectroscopy (XPS), contiuous wave electron spin resonance (CW-ESR), UV-vis spectroscopy, and argon sorption. Efficient and regioselective synthesis of 1,4-disubstituted 1,2,3-triazoles was achieved by employing the hybrid material as a catalyst in a mixture of H2O/EtOH as a green solvent with excellent catalytic activity with a TOF up to 495 h-1 at 50 °C. The reusability of the prepared hybrid material in the catalytic reaction was possible over five consecutive runs without significant loss of catalytic activity. The described method represents an effective way to ensure sustainable use of pincer complexes in catalytic systems by immobilizing them on solid supports, resulting in a hybrid organic-inorganic catalyst platform.

Improving the performance of an anionic MOF by counter cation replacement as electrode material in a full cell setup of a potassium ion capacitor.

Potassium-based energy storage devices are attracting increasing attention as an alternative to lithium and sodium systems. In addition, metal-organic frameworks (MOFs) can be considered as promising electrode materials for this type of device due to their advantageous properties. Herein, the anionic MOF JUMP-1 and its analog with pre-loading of potassium cations, namely JUMP-1(K), were synthesized and characterized. The anionic framework of JUMP-1 is found to be extremely stable towards the exchange of the dimethylammonium cations by potassium ions. These MOFs were tested in composite electrodes in combination with conventional organic electrolytes as anode materials in a potassium-based system, including the full cell assembly of a potassium ion capacitor (KIC). The results show the significant improvement in capacity between the pristine JUMP-1 and the potassium-exchanged analog JUMP-1(K) as electrode materials. KICs containing JUMP-1(K) coupled with activated carbon (AC) display a promising stability over 4000 cycles. According to the results from these studies, the composite MOF electrode with the potassium-exchange analog JUMP-1(K) presents a promising approach, for which the electrochemical performance compared to the pristine anionic MOF is significantly enhanced.

Enhancing Capacity and Stability of Anionic MOFs as Electrode Material by Cation Exchange.

In this study we report on the characterization and use of the anionic metal-organic framework (MOF) JUMP-1, [(Me2NH2)2[Co3(ntb)2(bdc)]] n , alongside with its alkali-metal ion-exchanged analogs JUMP-1(Li) and JUMP-1(Na), as electrode materials for lithium and sodium batteries. Composite electrodes containing these anionic-MOFs were prepared and tested in 1 M lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) in propylene carbonate (PC) and/or 1 M sodium TFSI (NaTFSI) in PC. We showed that the ion-exchanged materials JUMP-1(Li) and JUMP-1(Na) display higher capacities in comparison with the original as-prepared compound JUMP-1 (490 mA∙h∙g-1 vs. 164 mA∙h∙g-1 and 83 mA∙h∙g-1 vs. 73 mA∙h∙g-1 in Li and Na based electrolytes, respectively). Additionally, we showed that the stability of the electrodes containing the ion-exchanged materials is higher than that of JUMP-1, suggesting a form of chemical pre-alkalation works to stabilize them prior to cycling. The results of these studies indicate that the use of designed anionic-MOFs represents a promising strategy for the realization of high performance electrodes suitable for energy storage devices.

Metal-Bonded Redox-Active Triarylamines and Their Interactions: Synthesis, Structure, and Redox Properties of Paddle-Wheel Copper Complexes.

Four new triphenylamine ligands with different substituents in the para position and their corresponding copper(II) complexes are reported. This study includes their structural, spectroscopic, magnetic, and electrochemical properties. The complexes possess a dinuclear copper(II) paddle-wheel core, a building unit that is also common in metal-organic frameworks. Electrochemical measurements demonstrate that the triphenylamine ligands and the corresponding complexes are susceptible to oxidation, resulting in the formation of stable radical cations. The square-wave voltammograms observed for the complexes are similar to those of the ligands, except for a slight shift in potential. Square-wave voltammetry data show that, in the complexes, these oxidations can be described as individual one-electron processes centered on the coordinated ligands. Spectroelectrochemistry reveals that, during the oxidation of the complexes, no difference can be detected for the spectra of successively oxidized species. For the absorption bands of the oxidized species of the ligands and complexes, only a slight shift is observed. ESR spectra for the chemically oxidized complexes indicate ligand-centered radicals. The copper ions of the paddle-wheel core are strongly antiferromagnetic coupled. DFT calculations for the fully oxidized complexes indicate a very weak ferromagnetic coupling between the copper ions and the ligand radicals, whereas a very weak antiferromagnetic coupling is found among the ligand radicals.

Metal-Bonded Redox-Active Triarylamines and Their Interactions: Synthesis, Structure, and Redox Properties of Paddle-Wheel Copper Complexes.

Invited for this month's cover picture is the group of Professor Winfried Plass at the Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University, Jena (Germany). The cover picture shows a scene illustrating the need to investigate the properties of building blocks for complex systems to enable the basic design of new functional materials. The utilized triphenylamine ligands are constituting parts of the currently investigated "Jena University Magnetic Polymer" (JUMP) series. Read the full text of their Full Paper at 10.1002/open.201800243.

Solvent-dependent selective cation exchange in anionic frameworks based on cobalt(ii) and triphenylamine linkers: reactor-dependent synthesis and sorption properties.

Two cobalt(ii) coordination polymers with anionic networks of formulae {(Me2NH2)2[CoCl(ntb)]}n (JUMP-2) and {(Me2NH2)2[Co5(ntb)4(H2O)3(Me2NH)]}n (previously reported as MIL-144 by Livage et al., Microporous Mesoporous Mater., 2012, 157, 37) have been obtained via a solvothermal reaction of cobalt chloride and 4,4',4''-nitrilotribenzoic acid (H3ntb) in DMF employing two differently-sized reactors, while using the same absolute amount of reactants. Structure analysis revealed that JUMP-2 crystallized in the monoclinic space group P21/n and displays a two-dimensional (2D) network, which by topological analysis was characterized as a layered 3-connected hcb net. The topological analysis of MIL-144 revealed a 3,6-connected net with 3,6T80 topology. The magnetic properties of JUMP-2 are indicative of independent single-ion behavior of the tetrahedral cobalt(ii) ions and showed an out-of-phase signal in the alternating-current (ac) magnetic susceptibility below 2.5 K, whereas for MIL-144 an overall antiferromagnetic interaction within the di- and trinuclear secondary building units is observed and no indication for slow magnetization dynamics. The organic cations in both frameworks could successfully be exchanged with inorganic cations under retention of the respective network structure. In the process of exchange, both compounds displayed cation selectivity based on which solvent was utilized for immersing the solids. JUMP-2 shows a preference for europium(iii) ions in DMF, whereas MIL-144 preferentially takes up lithium ions when ethanol is used. The N2 adsorption isotherms were measured before and after exchange and revealed a considerable improvement in the sorption properties of the exchanged samples.

Specific Surface versus Electrochemically Active Area of the Carbon/Polypyrrole Capacitor: Correlation of Ion Dynamics Studied by an Electrochemical Quartz Crystal Microbalance with BET Surface.

Carbon/polypyrrole (PPy) composites are promising electrode materials for energy storage applications such as lightweight capacitors. Although these materials are composed of relatively inexpensive components, there is a gap of knowledge regarding the correlation between surface, porosity, ion exchange dynamics, and the interplay of the double layer capacitance and pseudocapacitance. In this work we evaluate the specific surface area analyzed by the BET method and the area accessible for ions using electrochemical quartz-crystal microbalance (EQCM) for SWCNT/PPy and carbon black Vulcan XC72-R/PPy composites. The study revealed that the polymer has significant influence on the pore size of the composites. Although the BET surface is low for the polypyrrole, the electrode mass change and thus the electrochemical area are large for the polymer-containing electrodes. This indicates that multiple redox active centers in the charged polymer chain are good ion scavengers. Also, for the composite electrodes, the effective charge storage occurs at the polypyrrole-carbon junctions, which are easy to design/multiply by a proper carbon-to-polymer weight ratio. The specific BET surface and electrochemically accessible surface area are both important parameters in calculation of the electrode capacitance. SWCNTs/PPy showed the highest capacitances normalized to the BET and electrochemical surface as compared to the polymer-carbon black. TEM imaging revealed very homogeneous distribution of the nanosized polymer particles onto the CNTs, which facilitates the synergistic effect of the double layer capacitance (CNTs) and pseudocapacitance (polymer). The trend in the electrode mass change in correlation with the capacitance suggest additional effects such as a solvent co-insertion into the polymer and the contribution of the charge associated with the redox activity of oxygen-containing functional groups on the carbon surface.

A facile, green and efficient surfactant-free method for synthesis of aluminum nanooxides with an extraordinary high surface area.

Nano boehmite with unprecedented high surface area and pore volume (802 m(2) g(-1), 2.35 cm(3) g(-1)) was prepared using a facile, green and efficient surfactant-free synthesis method. The structure of the material is characterized by the presence of plates with varying thicknesses and morphologies. The calcined samples show curved and rolled plates with a nanotube-like appearance.