Uncovering Factors Controlling Reactivity of Metal-TEMPO Reaction Systems in the Solid State and Solution.

Nitroxides 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. Among various products, a unique Lewis acid-base adduct of Cl2Zn with the N-ethylated TEMPO was isolated and structurally characterised, and the so-called solid-state 'slow chemistry' reaction led to a higher yield of the N-alkylated product. The revealed structure-activity/selectivity correlations are exceptional yet are entirely rationalised by the mechanistic underpinning supported by theoretical calculations of studied model systems. This work lays a foundation and mechanistic blueprint for future metal/nitroxide systems exploration.

Stepwise Stress-Induced Transformations of Metal-Organic Polyhedral Cluster-Based Assemblies: Where Conformational and Supramolecular Features Meet.

Understanding 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 ß and γ, as single-crystal-to-single-crystal events. The observed phase transitions illustrate the key role of an interplay between the low-energy conformation perturbations and cooperative intra- and intermolecular noncovalent interactions.

From a Well-Defined Organozinc Precursor to Diverse Luminescent Coordination Polymers Based on Zn(II)-Quinolinate Building Units Interconnected by Mixed Ligand Systems.

Introduction 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)2]2[tBuZn(OH)]2 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). As a result we present three new 2D mixed-ligand Zn(II)-quinolinate coordination polymers which are based on various zinc quinolinate secondary building units interconnected by two different organic linker types, i.e., deprotonated 4,4'-oxybisbenzoic acid (H2obc) as a flexible dicarboxylate linker and/or selected bipyridines (bipy). Remarkably, using the title organozinc precursors in a combination with H2obc and 4,4'-bipyridine, a novel molecular zinc quinolinate building unit, [Zn4(q)6(bipy)2(obc)2], was obtained which self-assembled into a chain-type hydrogen-bonded network. The application of the organometallic precursor allowed for its direct reaction with the selected ligands at ambient temperature, avoiding the use of both solvothermal conditions and additional base reagents. In turn, the reaction involving Zn(NO3)2, as a classical inorganic precursor, in a combination with H2obc and bipy led to a novel 1D coordination polymer [Zn2(q)2(NO3)2(bipy)]. While the presence of H2obc was essential for the formation of this coordination polymer, this ditopic linker was not incorporated into the isolated product, which indicates its templating behavior. The reported compounds were characterized by single-crystal and powder X-ray diffraction, elemental analysis as well as UV-Vis and photoluminescence spectroscopy.

Moisture Resistance, Thermal Stability and Fire Behavior of Unsaturated Polyester Resin Modified with L-histidinium Dihydrogen Phosphate-Phosphoric Acid.

In 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). Reaction to small flames was studied by horizontal burning (HB) test, while fire behavior and smoke emission were investigated with the cone calorimeter (CC) and smoke density chamber. Further, the analysis of volatile products was conducted (TGA/FT-IR). It was observed that the addition of LHP resulted in the formation of carbonaceous char inhibiting the thermal decomposition, burning rate and smoke emission. The most promising results were obtained for the UP containing 30 wt. % of LHP, for which the highest reduction in maximum values of heat release rate (200 kW/m2) and total smoke release (3535 m2/m2) compared to unmodified polymer (792 kW/m2 and 6895 m2/m2) were recorded. However, some important disadvantage with respect to water resistance was observed.

Solvent Templating and Structural Dynamics of Fluorinated 2D Cu-Carboxylate MOFs Derived from the Diffusion-Controlled Process.

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.

Rational Design of Noncovalent Diamondoid Microporous Materials for Low-Energy Separation of C6-Hydrocarbons.

Selective 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 C6-hydrocarbons with kinetic diameters in the range of 4.3-6.3 Å. This strategy is based on a Cambridge Structural Database search of diamondoid NPMs with a low packing factor, leading to the selection of an oxidotetrazinc cluster based diamondoid NPM network named DiaMM-1 containing tetrahedral voids of 336 Å3 (tetrahedron insphere diameter of 5.8 Å accessible through 8.2 Å triangular windows) suitable for this separation. Based on this result the fluorinated analogue DiaMM-2 was designed and synthesized. DiaMM-1 and DiaMM-2 exhibit permanent porosity and high thermal stability. The optimal combination of molecular crystal softness, pore size, and decoration of pore surface of DiaMM-1,-2 leads to high adsorbate diffusivity and low adsorption energy, allowing fast separation of hexane isomers and benzene/cyclohexane mixtures at low temperature.

Straightforward Synthesis of Single-Crystalline and Redox-Active Cr(II)-carboxylate MOFs.

We report on a facile and environmentally friendly synthetic approach for single-crystalline chromium(II) carboxylate metal-organic frameworks (i.e., Cr3(BTC)2·3H2O (1) and Cr(hfipbb)·H2O (2) at room temperature in water. Both MOFs can be easily dehydrated, affording single-crystalline materials with open Cr(II) sites. In addition, the redox activity and porosity of the resulting Cr(II) MOFs were examined.

Synthesis and Structure of Alkylzinc 3,5-Diphenylpyrazolates: Dramatic Influence of Steric and Solvent Effects.

The 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.

Factors controlling the structure of alkylzinc amidinates: on the role of N-substituents.

Despite various applications of alkylzinc complexes supported by N,N-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 N,N'-diphenylformamidinate ligands as model N,N'-unsubstituted and N,N'-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). The results indicate that [RZnL]x-type amidinate moieties are essentially unstable and tend to undergo Schlenk equilibria-mediated ligand scrambling leading to more thermodynamically stable non-stoichiometric [R2Zn3L4]- and [R3Zn4L5]-type complexes. This process is significantly influenced by the secondary coordination sphere noncovalent interactions as well as the steric hindrance provided by both zinc-bounded alkyl groups and the N-substituents.

Mechanochemical vs Wet Approach for Directing CO2 Capture toward Various Carbonate and Bicarbonate Networks.

The distinct research areas related to CO2 capture and mechanochemistry are both highly attractive in the context of green chemistry. However, merger of these two areas, i.e., mechanochemical CO2 capture, is still in an early stage of development. Here, the application of biguanidine as an active species for CO2 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. We demonstrate that in solution, the formation of the carbonate vs bicarbonate networks can be directed by the organic solvent, while, remarkably, in the liquid-assisted mechanochemical synthesis employing the same solvents as additives, the selectivity in network formation is inversed. In general, our findings support the view of mechanochemistry not only as a sustainable alternative but rather as a complementary strategy to solution-based synthesis.

Effect of the proximal secondary sphere on the self-assembly of tetrahedral zinc-oxo clusters.

Metal-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. We demonstrated that the NH groups in the proximal secondary coordination sphere are prone to the formation of intermolecular hydrogen bonds, which affects the packing of clusters in the crystal structure. Coordination sphere engineering can lead to the rational design of new catalytic sites and novel molecular building units of supramolecular assemblies.

Vegetable Fillers and Rapeseed Oil-Based Polyol as Natural Raw Materials for the Production of Rigid Polyurethane Foams.

The 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. The influence of the used raw materials on the foaming process, structure, and properties of foams was investigated using a FOAMAT analyzer and a wide selection of characterization techniques. The introduction of renewable raw materials limited reactivity of the system, which reduced maximum temperature of the foaming process. Moreover, foams prepared using renewable raw materials were characterized by a more regular cell structure, a higher share of closed cells, lower apparent density, lower compressive strength and glass transition temperature, low friability (<2%), low water absorption (<1%), high dimensional stability (<±0.5%) and increased thermal stability. The proper selection and preparation of the renewable raw materials and the rational development of the polyurethane recipe composition allow for the preparation of environmentally-friendly foam products with beneficial application properties considering the demands of the circular economy in the synthesis of rigid foams.

A Case Study on the Desired Selectivity in Solid-State Mechano- and Slow-Chemistry, Melt, and Solution Methodologies.

Solution-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, (C6 F5 )2 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. In a toluene solution two distinct paramagnetic Lewis acid-base adducts (C6 F5 )2 Zn(η1 -TEMPO) (1) and (C6 F5 )2 Zn(η1 -TEMPO)2 (2) equilibrated, but only 2 was affordable by crystallization. In turn, crystallization from the melt was the only method yielding single crystals of 1. Moreover, the solid-state approaches were stoichiometry sensitive and allowed for the selective synthesis of both adducts by simple stoichiometric control over the substrates. Density functional theory (DFT) calculations were carried out to examine selected structural and thermodynamic features of the adducts 1 and 2. Compound 2 is a unique non-redox active metal complex supported by two nitroxide radicals, and the magnetic studies revealed weak-to-moderate intramolecular antiferromagnetic interactions between the two coordinated TEMPO molecules.

Polyurethane Composite Foams Synthesized Using Bio-Polyols and Cellulose Filler.

Rigid 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). The cellulose was incorporated into the polyol premix as filler dispersion in a petrochemical polyol made using calenders. The cellulose filler was examined in terms of the degree of crystallinity using the powder X-ray diffraction PXRD -and the presence of bonds by means of the fourier transform infrared spectroscopy FT-IR. It was found that the addition of the cellulose filler increased the number of cells in the foams in both cross-sections-parallel and perpendicular to the direction of the foam growth-while reducing the sizes of those cells. Additionally, the foams had closed cell contents of more than 90% and initial thermal conductivity coefficients of 24.8 mW/m∙K. The insulation materials were dimensionally stable, especially at temperatures close to 0 °C, which qualifies them for use as insulation at low temperatures.

Structural diversity of ethylzinc derivatives of 3,5-substituted pyrazoles.

Equimolar 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. Nevertheless, these types of complexes are kinetically labile and tend to undergo ligand scrambling reactions according to the Schlenk equilibrium. For example, the alkyl substituents in the pzMe2 and pziPr2 ligands do not appear to be a strong determinant of the dimeric moieties and the composition of the isolated complexes by crystallisation from the parent reaction mixture varies between spiro-type tri- and tetranuclear aggregates, [Et2Zn3(pz)4(THF)x] (x = 0 or 2) and [Et2Zn4(pz)6(THF)2], respectively. The nonstoichiometric formula of these organozinc derivatives is likely related to both the Schlenk-type equilibria and solubility of the respective moieties. In turn, the high steric demands of the 3,5-di-tert-butylpyrazolate ligand promote the dimeric form in solution and the solid state. Interestingly, the ethylzinc indazolate complex also does not undergo a redistribution reaction and yields a dimer.

Mechanochemical and slow-chemistry radical transformations: a case of diorganozinc compounds and TEMPO.

From 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. We present a comparative study of model mechanochemical, slow-chemistry and solution radical reactions between TEMPO and homoleptic organozinc compounds (i.e., di-tert-butylzinc and diphenylzinc). In the case of the tBu2Zn/TEMPO reaction system only a dimeric diamagnetic complex [tBuZn(µ-TEMPO*)]2 is obtained in yields slightly varying with the method chosen. In contrast, when TEMPO is mixed with diphenylzinc in a 2 : 1 molar ratio a novel paramagnetic Lewis acid-base adduct [[Ph2Zn(η1-TEMPO)]·TEMPO] is isolated in high yields regardless of the applied methodology. This adduct is also formed in the slow-chemistry process when TEMPO is gently mixed with Ph2Zn in a 1 : 1 molar ratio and left for two weeks at ambient temperature. Within the next week the reaction mixture gives in high yield a diamagnetic dinuclear compound [PhZn(µ-TEMPO*)][PhZn(µ2-η1:η1-TEMPO*)] and biphenyl. The analogous reaction conducted in toluene results in a much lower conversion rate. The reported results open up a new horizon in molecular solid-state radical transformations.

From ethylzinc guanidinate to [Zn10O4]-supertetrahedron.

The controlled hydrolysis of an ethylzinc guanidinate complex affording an alkylzinc cluster containing a [Zn10O4]12+ 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.

Photo-induced interfacial electron transfer of ZnO nanocrystals to control supramolecular assembly in water.

Herein, 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.