New metal-organic frameworks (MOF) with lanthanum(III), cerium(III), neodymium(III), europium(III), gadolinium(III), dysprosium(III), and holmium(III)] and the ligand precursor 1,3,5-tris(4-carboxyphenyl)-2,4,6-trimethylbenzene (H3L) were synthesized under solvothermal conditions. Single crystal x-ray analysis confirmed the formation of three-dimensional frameworks of [LnL(H2O)2]n·xDMF·yH2O for Ln = La, Ce, and Nd. From the nitrogen sorption experiments, the compounds showed permanent porosity with Brunauer-Emmett-Teller (BET) surface areas of about 400 m2/g, and thermal stability up to 500 °C. Further investigations showed that these Ln-MOFs exhibit catalytic activity, paving the way for potential applications within the field of catalysis.
Mesitylene was used as a core in seven new tritopic nitrogen containing linkers. Three of the linkers, each containing three nitrile groups, were obtained through Suzuki, Sonogashira and Heck-type coupling reactions. Next, these were converted to tetrazol-5-yl moieties by the cycloaddition of sodium azide to the nitrile functionalities. The last linker, containing three 1,2,3-triazol-4-yl moieties, was synthesized by the Huisgen cycloaddition of phenyl azide to the corresponding alkyne. The latter was obtained via a Corey–Fuchs reaction sequence from the previously reported formyl derivative. As the proof of concept for their potential in MOF design, one of the nitriles was used to build an Ag-based network.
The synthesis of paracyclophane-based tetrathiafulvalene precursors is described in the context of the importance of these compounds in the field of material chemistry. Pseudo-geminal bis(1,3-dithia-2-thione) was synthesized via the corresponding 1,3-dithiol-2-ylium salt. The latter was obtained by a synthetic procedure that involves 4,15-bis(acetyl)[2.2]paracyclophane, a new compound of interest for many researchers.
Several new di- and tetracarboxylic [2.2]paracyclophane derivatives were obtained via Suzuki coupling between the appropriately brominated [2.2]paracyclophanes and 4-(methoxycarbonyl)phenylboronic acid. The reaction of one of these products, namely pp-bis(4-carboxyphenyl)[2.2]paracylophane (12), with zinc nitrate afforded a 2D coordination polymer comprising zinc-carboxylate paddlewheel clusters linked together by cyclophane cores. The zinc center is five-coordinated in a square-pyramidal geometry, with a DMF oxygen atom at the apex and four carboxylate oxygen atoms in the base.
30 September 2019 in Studia Universitatis Babeș-Bolyai Chemia
The intramolecular interactions in pseudo-geminally substituted [2.2] paracyclophanes induced by chalchogenide halides is reviewed. The subtitution reactions with sulfur dichloride and disulfur dichloride and the addition reactions of selenium dihalides and diselenium dichlorides are highlighted.
Three new Metal-Organic Frameworks, containing mesitylene tribenzoic acid as a linker and zinc (1) or cadmium as metals (2,3), were synthesized through solvothermal reactions, using DMF/ethanol/water as solvents, at temperatures of 80 °C (structures 1 and 3) and 120 °C (structure 2). Following single-crystal X-ray diffraction, it was found that 1 and 3 crystallize in the P21/c and C2/c space groups and form 2D networks, while 2 crystallizes in the Fdd2 space group, forming a 3D network. All three frameworks, upon heating, were found to be stable up to 350 °C. N2 sorption isotherms revealed that 1 displays a BET area of 906 m2/g. Moreover, the porosity of this framework is still present after five cycles of sorption/desorption, with a reduction of 14% of the BET area, down to 784 m2/g, after the fifth cycle. The CO2 loading capacity of 1 was found to be 2.9 mmol/g at 0 °C.