RESUMEN
Invited for the cover of this issue is Sergiusz Lulinski and his co-workers from Warsaw University of Technology and University of Warsaw. The image depicts a journey through the interior of the porous Covalent Organic Framework containing phosphorus and boron centres with carbon dioxygen trapped inside an imagined cave. Read the full text of the article at 10.1002/chem.202001960.
RESUMEN
Two covalent organic frameworks comprising Lewis basic PIII centers and Lewis acidic boron atoms were prepared by poly-condensation reactions of newly obtained tris(4-diisopropoxyborylphenyl)phosphine with 2,3,6,7,10,11-hexahydroxytriphenylene and 2,3,6,7-tetrahydroxy-9,10-dimethylanthracene. Obtained materials exhibit significant sorption of dihydrogen (100â cm3 g-1 at 1â bar at 77â K), methane (20â cm3 g-1 at 1â bar at 273â K) and carbon dioxide (50â cm3 g-1 at 1â bar at 273â K). They were exploited as solid-state ligands for coordination of Pd0 centers. Alternatively, in a bottom-up approach, boronated phosphine was treated with Pd2 dba3 and poly-condensated, yielding hybrid materials where the polymer networks are formed by means of covalent boronate linkages and coordination P-Pd bonds. In addition, the analogous materials based on phosphine oxide were synthesized. The DFT calculations on framework-guest interactions revealed that the behavior of adjacent boron and phosphorus/phosphine oxide centers is reminiscent of that found in Frustrated Lewis Pairs and may improve sorption of selected molecules.
RESUMEN
The layered 2D MOFs, owing to their enhanced flexibility and tunability, have recently emerged as a promising alternative to the 3D microporous MOFs in the quest for novel responsive functional materials. However, maintaining the simultaneous control over self-assembly of molecular building blocks as well as ordered stacking of MOF layers poses a significant synthetic challenge. We report on the controlled 2D MOF formation based on a case study of solvent-templated growth of a series of 2D Cu(II)-carboxylate MOFs varying in stacking modes and distances using a diffusion-controlled MOF deposition approach in various solvent mixtures. Moreover, we demonstrate the structural dynamics of the developed 2D MOFs involving both in-plane and out-of-plane movements of the individual 2D layers triggered by solvent exchange, which allowed for selective postsynthetic transformations between the developed 2D MOFs. We also investigated the gas adsorption properties of the developed MOFs, which demonstrates a remarkable crystal size effect on the N2 adsorption capacity using a model 2D MOF system.
RESUMEN
Lithium tetrakis(4-boronatoaryl)borates were subjected to polycondensation reactions with selected polyhydroxyl monomers such as 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) and 2,3,6,7-tetrahydroxy-9,10-dimethylanthracene (THDMA). Obtained boronate-type ionic porous polymers TAB1-4 were characterized by PXRD, 6Li and 11B magic-angle spinning nuclear magnetic resonance (MAS NMR), FT-IR, SEM, and TGA. They exhibit relatively good sorption of H2 (up to 75 cm3/g STP), whereas N2 uptake at 77 K for lower pressure range is relatively poor (up to 50 cm3/g STP below P/P0 = 0.8). In addition, the effect of elongation of aryl arms in the tetraarylborate core on the materials' properties was studied. Thus, it was found that replacement of the 4-boronatophenyl with 4-boronatobiphenylyl group has a negative impact on the sorption characteristics.
RESUMEN
The conversion of 2,4,6-tris(4'-bromophenyl)-1,3,5-triazine to the respective triboronic acid was successfully accomplished by a simple triple Br/Li exchange followed by boronation. Further dehydrative condensation reactions with 2,3,6,7,10,11-hexahydroxytriphenylene or 2,3,6,7-tetrahydroxy-9,10-dilalkylanthracenes (R = Me, Et) resulted in materials featuring good porosity and sorption properties with the nitrogen uptake exceeding 500 cm3/g (STP) and SBET up to 1267 m2/g (T = 77.2 K). In addition, simple dehydration of this compound was employed for the preparation of a hybrid 2D COF composed of triazine, boroxine, and benzene rings. The formation of materials was confirmed by the IR analysis and NMR studies on water-decomposed samples. All obtained COFs exhibit high thermal stability with decomposition temperatures in the range of 400-600 °C. They also show quite different morphology ranging from regular 0.5-4 µm spherical and ellipsoidal clusters to 5-12 µm bent rodlike particles. The PXRD studies supported by periodic DFT modeling in Crystal09 package revealed the formation of crystalline 2D honeycomb-type lattices with eclipsed stacking models. In addition, the differences between boroxine-triazine material and related COF-1 and CTF-1 structures were investigated by comparing layer interaction energies, work function values as well as atomic charges and electrostatic potential maps plotted on the electron density surfaces. It demonstrates that the interactions between layers are enhanced by the stacking of triazine and boroxine rings. Finally, we have investigated the upper limit to space accessible volume using a procrystal electron density approach.