ACS Appl Mater Interfaces
August 2024
Redox-active metal-organic frameworks (MOFs) are very promising materials due to their potential capabilities for postsynthetic modification aimed at tailoring their application properties. However, the research field related to redox-active MOFs is still relatively underdeveloped, which limits their practical application. We investigated the self-assembly process of Cr(II) ions and isophthalate (m-bdc) linkers, which have been previously demonstrated to yield 0D metal-organic polyhedra.
View Article and Find Full Text PDFNitroxides find application in various areas of chemistry, and a more in-depth understanding of factors controlling their reactivity with metal complexes is warranted to promote further developments. Here, we report on the effect of the metal centre Lewis acidity on both the distribution of the O- and N-centered spin density in 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) and turning TEMPO from the O- to N-radical mode scavenger in metal-TEMPO systems. We use Et(Cl)Zn/TEMPO model reaction system with tuneable reactivity in the solid state and solution.
View Article and Find Full Text PDFDespite various applications of alkylzinc complexes supported by ,-bidentate ligands in chemistry and materials science, the corresponding organozinc amidinates still represent an insufficiently explored area. To gain a more in-depth understanding of factors controlling the structure and stability of alkylzinc amidinates, we selected benzamidinate and ,'-diphenylformamidinate ligands as model ,'-unsubstituted and ,'-diaryl substituted ligands, respectively, to systematically modify the secondary coordination sphere of the Zn center. A series of new alkylzinc amidinates has been synthesized and their molecular structures identified in both the solid state (single-crystal X-ray crystallography) and solution (NMR and FTIR spectroscopy).
View Article and Find Full Text PDFThe distinct research areas related to CO capture and mechanochemistry are both highly attractive in the context of green chemistry. However, merger of these two areas, , mechanochemical CO capture, is still in an early stage of development. Here, the application of biguanidine as an active species for CO capture is investigated using both solution-based and liquid-assisted mechanochemical approaches, which lead to a variety of biguanidinium carbonate and bicarbonate hydrogen-bonded networks.
View Article and Find Full Text PDFIntroduction of photoactive building blocks into mixed-ligand coordination polymers appears to be a promising way to produce new advanced luminescent materials. However, rational design and self-assembly of the multi-component supramolecular systems is challenging from both a conceptual and synthetic perspective. Here, we report exploratory studies that investigate the potential of [Zn(q)][BuZn(OH)] complex (q = deprotonated 8-hydroxyquinoline) as an organozinc precursor as well as a mixed-ligand synthetic strategy for the preparation of new luminescent coordination polymers (CPs).
View Article and Find Full Text PDFMetal-oxo clusters can serve as directional and rigid building units of coordination and noncovalent supramolecular assemblies. Therefore, an in-depth understanding of their multi-faceted chemistry is vital for the development of self-assembled solid-state structures of desired properties. Here we present a comprehensive comparative structural analysis of isostructural benzoate, benzamidate, and new benzamidinate zinc-oxo clusters incorporating the [O,O]-, [O,NH]- and [NH,NH]-anchoring donor centers, respectively.
View Article and Find Full Text PDFUnderstanding the factors governing the formation of supramolecular structures and phase transitions between various forms of molecular crystals is pivotal for developing dynamic, stimuli-responsive materials and polymorph-controlled syntheses. Here, we investigate the pressure-induced dynamic of both the intrinsic molecular structure and the supramolecular network of a predesigned polyhedral oxo-centered zinc cluster incorporating monoanionic N,N'-diphenylformamidinate and featuring N-bonded phenyl groups in close proximity to the primary coordination sphere. We demonstrate that the model oxo cluster is prone to undergoing pressure-induced conformational transformations of the secondary coordination sphere and simultaneous stepwise (initially every second polyhedral molecule undergoes the conformational transformations) and reversible transitions from an ambient phase α to high-pressure phases β and γ, as single-crystal-to-single-crystal events.
View Article and Find Full Text PDFSolution-based syntheses are omnipresent in chemistry but are often associated with obvious disadvantages, and the search for new mild and green synthetic methods continues to be a hot topic. Here, comparative studies in four different reaction media were conducted, that is, the solid-state mechano- and slow-chemistry synthesis, melted phase, and solution protocols, and the impact of the employed solvent-free solid-state versus liquid-phase synthetic approaches was highlighted on a pool of products. A moderately exothermic model reaction system was chosen based on bis(pentafluorophenyl)zinc, (C F ) Zn, and 2,2,6,6-tetramethylpiperidinyl oxide (TEMPO) as a stable nitroxyl radical, anticipating that these reagents may offer a unique landscape for addressing kinetic and thermodynamic aspects of wet and solvent-free solid-state processes.
View Article and Find Full Text PDFRigid polyurethane foams were obtained using two types of renewable raw materials: bio-polyols and a cellulose filler (ARBOCEL P 4000 X, JRS Rettenmaier, Rosenberg, Germany). A polyurethane system containing 40 wt.% of rapeseed oil-based polyols was modified with the cellulose filler in amounts of 1, 2, and 3 php (per hundred polyols).
View Article and Find Full Text PDFThe reported study concerns the introduction of renewable raw materials into the formulation of rigid polyurethane foams in the quest for the sustainable development of polymer composites. In this study, rigid polyurethane foam composites were prepared using 75 wt.% of rapeseed oil-based polyol and 15 parts per hundred parts of polyol (php) of natural fillers such as chokeberry pomace, raspberry seeds, as well as hazelnut and walnut shells.
View Article and Find Full Text PDFIn this paper, the fire behavior of unsaturated polyester resin (UP) modified with L-histidinium dihydrogen phosphate-phosphoric acid (LHP), being a novel intumescent fire retardant (IFR), was investigated. Thermal and thermomechanical properties of the UP with different amounts of LHP (from 10 to 30 wt. %) were determined by thermogravimetric analysis (TG) as well as dynamic mechanical thermal analysis (DMTA).
View Article and Find Full Text PDFEquimolar reactions of Et2Zn with 3,5-dimethylpyrazole (H-pzMe2), 3,5-di-iso-propylpyrazole (H-pziPr2), 3,5-di-tert-butylpyrazole (H-pztBu2) and indazole (H-ind) were investigated in toluene or tetrahydrofuran (as a coordinating solvent). A series of diverse ethylzinc pyrazolates and indazolates were identified using advanced NMR spectroscopy and the single crystal X-ray diffraction techniques. The NMR experiments indicate that dimeric moieties of the general formula [EtZn(pz)]2 or [Et2Zn2(pz)2(THF)] are favoured in solution.
View Article and Find Full Text PDFThe 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.
View Article and Find Full Text PDFFrom the green chemistry perspective, molecular solid-state transformations conducted under mild conditions are of great interest and desirability. However, research in this area lacked popularity in the previous century, and thus progressed slowly. In particular, the application of radical reactions in solid-state chemistry has been hampered by several long-standing challenges that are intrinsically associated with the apparent unpredictable nature of radical chemistry.
View Article and Find Full Text PDFSelective separation of gases/vapors with similar physicochemical properties involves energetically costly distillation processes. Alternative separation processes based on shape-selective molecular sieving, taking place on porous frameworks (or membranes), are less energy demanding but require an optimal balance between selectivity and diffusion kinetics (permeability). Herein, we report a rational strategy to select an optimal soft noncovalent microporous material (NPM) suitable for the low-energy separation of C-hydrocarbons with kinetic diameters in the range of 4.
View Article and Find Full Text PDFWe report on a facile and environmentally friendly synthetic approach for single-crystalline chromium(II) carboxylate metal-organic frameworks (i.e., Cr(BTC)·3HO (1) and Cr(hfipbb)·HO (2) at room temperature in water.
View Article and Find Full Text PDFHerein, we show how the inherent light-induced redox properties of semiconducting nanocrystals (NCs) can be utilized for the photo-driven reversible modulation of dynamic supramolecular systems formed at their interfaces that, on their own, do not respond to light. This was achieved by the unprecedented combination of photoactive zinc oxide NCs (ZnO NCs) with a host-guest chemistry of cucurbit[8]uril (CB[8]) providing a route to the semiconductor-assisted light modulation of supramolecular assemblies (SALSA), here mediated by the photo-generation of viologen radical cations (MV˙) at the NC corona and their further dimerization enhanced by CB[8] macrocycles. The reported SALSA strategy was successfully applied for light-controlled reversible assembly processes at NC interfaces enabling light-triggered release of guest molecules from surface confined discrete CB[8] host-guest complexes.
View Article and Find Full Text PDFThe controlled hydrolysis of an ethylzinc guanidinate complex affording an alkylzinc cluster containing a [ZnO] supertetrahedron core stabilized by the guanidinate ligands is described. Accompanying investigations on the reactivity of this unprecedented cluster toward alcohols resulted in the formation of a mononuclear zinc alkoxide supported by the guanidinate ligands.
View Article and Find Full Text PDFThe reaction of R2Zn (R = Et, (t)Bu) with 3,5-diphenylpyrazole results in the formation of three structurally diverse alkylzinc pyrazolates: a novel dinuclear tetrahydrofuran solvate, an unprecedented trimeric structure, and a spiro trinuclear aggregate. Structural analysis of the resulting complexes provides a new look at the aggregation and stabilization of alkylzinc species.
View Article and Find Full Text PDF