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Structural heterogeneity defines the properties of many functional polymers and it is often crucial for their performance and ability to withstand mechanical impact. Such heterogeneity, however, poses a tremendous challenge for characterization of these materials and limits our ability to design them rationally. Herein we present a practical methodology capable of resolving the complex mechanical behavior and tracking mechanical impact in discrete phases of segmented polyurethane—a typical example of a structurally complex polymer. Using direct optical imaging of photoluminescence produced by a small‐molecule organometallic mechano‐responsive sensor we observe in real time how polymer phases dissipate energy, restructure, and breakdown upon mechanical impact. Owing to its simplicity and robustness, this method has potential in describing the evolution of complex soft‐matter systems for which global characterization techniques fall short of providing molecular‐level insight.

Non‐oxidative dehydroaromatization of methane (MDA) is a promising catalytic process for direct valorization of natural gas to liquid hydrocarbons. The application of this reaction in practical technology is hindered by a lack of understanding about the mechanism and nature of the active sites in benchmark zeolite‐based Mo/ZSM‐5 catalysts, which precludes the solution of problems such as rapid catalyst deactivation. By applying spectroscopy and microscopy, it is shown that the active centers in Mo/ZSM‐5 are partially reduced single‐atom Mo sites stabilized by the zeolite framework. By combining a pulse reaction technique with isotope labeling of methane, MDA is shown to be governed by a hydrocarbon pool mechanism in which benzene is derived from secondary reactions of confined polyaromatic carbon species with the initial products of methane activation.

The catalytic Diels–Alder cycloaddition–dehydration (DACD) reaction of furanics with ethylene is a promising route to bio‐derived aromatics. The reaction can be catalyzed by alkali‐metal‐exchanged faujasites. Herein, the results of periodic DFT calculations based on accurate structural models of alkali‐metal‐exchanged zeolites are presented, revealing the fundamental roles that confinement and the nature of the exchangeable cations in zeolite micropores have in the performance of faujasite‐based catalysts in the DACd reaction. Special attention is devoted to analyzing the effect of functional substituents on furanic substrates (furan, 2,5‐dimethylfuran, 2,5‐furandicarboxylic acid) on the catalyst behavior. It is demonstrated that the conventional reactivity theories of the Diels–Alder chemistry based on simplistic single‐site Lewis acidity and substituent effects do not apply if catalytic processes in the multiple‐site confined environment of zeolite nanopores are considered. The nature and cooperativity of the interactions between the multiple exchangeable cations and the substrates determine the reaction energetics of the elementary steps involved in the DACD process.

The [4+2] cycloaddition reaction between 2-pyrone and Me3 Si-C≡P gives the corresponding 2-(trimethylsilyl)-λ3 -phosphinine in good yields as a rather air and moisture stable, colorless oil. Insight into the regioselectivity of the pericyclic reaction was obtained with the help of deuterium-labeling experiments. The silyl-phosphinine acts as a ligand for the preparation of a Cu(I) and the first crystallographically characterized phosphinine-Ag(I) complex. The title compound was further used as a starting material for an alternative preparation of the parent phosphinine C5 H5 P by means of protodesilylation with HCl. C5 H5 P reacts with CuBr⋅S(CH3 )2 to give an infinite Cu(I)Br coordination polymer. DFT calculations shed light on the influence of the -Si(CH3 )3 group on the electronic properties of the aromatic phosphorus heterocycle.

Active sites in carbon-catalyzed phosgene synthesis from gaseous CO and Cl2 have been identified using C60 fullerene as a model catalyst. The carbon atoms distorted from sp2 coordination in non-planar carbon units are concluded to generate active Cl2. Experiments and density functional theory calculations indicate the formation of a surface-bound [C60⋯Cl2] chlorine species with radical character as key intermediate during phosgene formation. It reacts rapidly with physisorbed CO in a two-step Eley-Rideal-type mechanism.

The reaction mechanism of CO2 coupling with C2H4 by homogeneous Ni-complexes bearing bidentate phosphorous ligands was studied by means of density functional theory calculations. The reaction is initiated by sequential coordination of C2H4 and CO2 to the Ni center, followed by a facile coupling step, which results in a stable nickelalactone intermediate. Subsequent decomposition of this intermediate through ß-H transfer is the rate-determining step. Together with the following reductive elimination step to form acrylic acid they represent a strongly kinetically-hampered process. Destabilization of the nickelalactone intermediate in the presence of large bite angle bidentate ligands has only a minor effect on the overall reaction energetics. Modifying the electronic properties of ligands is also not effective to drive the reaction in a catalytic manner. These studies indicate that the coupling reaction has to be enforced through an alternative route. It is predicted here that a base-assisted decomposition of the nickelalactone intermediate represents a favorable reaction channel. The factors affecting the reactivity of this route are investigated. The best reactivity corresponds to the CH3OH-solvated CH3ONa that allows the ß-H transfer step to proceed with a barrier of only 49 kJ¿mol-1. Keywords: ab initio calculations; carbon dioxide; homogeneous catalysis; nickel; reaction mechanisms

5-Hydroxymethylfurfural (HMF) is considered an important building block for future bio-based chemicals. Here, we present an experimental study using different ketoses (fructose, sorbose, tagatose) and aldoses (glucose, mannose, galactose) under aqueous acidic conditions (65gL(-1) substrate, 100-160 degrees C, 33-300mM H2SO4) to gain insights into reaction pathways for hexose dehydration to HMF. Both reaction rates and HMF selectivities were significantly higher for ketoses than for aldoses, which is in line with literature. Screening and kinetic experiments showed that the reactivity of the different ketoses is a function of the hydroxyl group orientation at the C3 and C4 positions. These results, in combination with DFT calculations, point to a dehydration mechanism involving cyclic intermediates. For aldoses, no influence of the hydroxyl group orientation was observed, indicating a different rate-determining step. The combination of the knowledge from the literature and the findings in this work indicates that aldoses require an isomerization to ketose prior to dehydration to obtain high HMF yields.

The isomerization of glucose to fructose in the presence of Sn-containing zeolite BEA (beta polymorph A) was studied by periodic DFT calculations. Focus was placed on the nature of the active site and the reaction mechanism. The reactivities of the perfect lattice SnIV site and the hydroxylated SnOH species are predicted to be similar. The isomerization activity of the latter can be enhanced by creating an extended silanol nest in its vicinity. Besides the increased Lewis acidity and coordinationflexibility of the Sn center, the enhanced reactivity in this case is ascribed to the reaction environment that promotes activation is ascribed to the reaction environment that promotes activation of the confined sugar intermediates through hydrogen bonding. The resulting multidentate activation of the substrate favors the rate-determining hydrogen-shift reaction. These findings suggest the important role of defect lattice sites in Sn-BEA for catalytic glucose isomerization. Sn-BEA for catalytic glucose isomerization.

We present an in situ small- and wide-angle X-ray scattering (SAXS/WAXS) and quick-scanning extended X-ray absorption fine-structure (QEXAFS) spectroscopy study on the crystallization of the metal–organic framework ZIF-7. In combination with DFT calculations, the self-assembly and growth of ZIF-7 microrods together with the chemical function of the crystal growth modulator (diethylamine) are revealed at all relevant length scales, from the atomic to the full crystal size.

A series of faujasite zeolites was modified by extraframework Al (AlEF) with the goal to investigate the influence of such species on the intrinsic Brønsted acidity and catalytic activity towards paraffin cracking. The chemical state of AlEF and zeolite acidity were investigated by 27Al MAS NMR and COads IR spectroscopy, H/D exchange reaction, and propane cracking. Strongly acidic defect-free Y zeolites were obtained by substitution of framework Al by Si with (NH4)2SiF6. In accordance with the next-nearest-neighbor model, the intrinsic acidity of the protons increased with decreasing framework Al density. This increased acidity was evidenced by an increased shift of the OH stretching vibration upon CO adsorption in COads IR spectroscopy and by an increased H/D exchange rate in H/D exchange reactions with perdeuterobenzene. All of the acid sites in these zeolites were of equal strength beyond a certain Si/Al ratio. The increased acidity resulted in an enhanced propane cracking activity. Modification of a model dealuminated Y zeolite by AlEF only resulted in a small fraction of cationic AlEF species, because it was difficult to control the ion exchange process. In comparison, commercial ultrastabilized Y zeolites contained less AlEF and these species were predominantly present in cationic form. The rate of propane cracking strongly correlated to the concentration of Brønsted acid sites perturbed by cationic AlEF species. The results of MQMAS 27Al NMR spectroscopy confirmed the presence of sites perturbed by AlEF and unaffected framework Al sites. Zeolites with higher intrinsic cracking activities contained a higher proportion of perturbed sites. Although COads IR and H/D exchange methods proved to be suitable methods to probe the acidity of Y zeolites free from AlEF, they were less suitable to predict the reactivity if the Brønsted acid sites were affected by cationic AlEF species.

C2 and C3 alkanes are selectively adsorbed from mixtures over the corresponding alkenes on the zeolite imidazolate framework ZIF-7 through a gate-opening mechanism. As a result, the direct production of the pure alkene upon adsorption and the pure alkane upon desorption in packed columns is possible. Herein, a detailed investigation of the step-wise adsorption and separation of alkanes and alkenes is presented, together with a rigorous performance assessment. A molecular picture of the gate-opening mechanism underlying the unprecedented selectivity towards alkane adsorption is proposed based on DFT calculations and a thermodynamic analysis of the adsorption–desorption isotherms.

Sugar it up: Stabilization of the CrCl2 active phase in a thin layer of an ionic liquid covalently grafted to mesoporous silica results in a highly selective catalyst for the dehydration of glucose to 5-hydroxymethylfurfural (HMF) in an aqueous medium. Glucose dehydration in water by using the CrCl2-Im-SBA-15 catalyst leads to a 50¿% HMF selectivity that can be further increased to up to 70¿% by modifying the solvent system.

Figure Presented] Cat waiting in the wings: The transient formation of Cr2+ dimers through coordination to a second molecule of the catalyst promotes the isomerization of glucose to fructose and explains the unique ability of CrCl2 to catalyze the dehydration of glucose to 5-hydroxymethylfurfural (HMF) in ionic-liquid media. The active-site environment during the rate-controlling step resembles that in hexose isomerase enzymes.© 2010 Wiley-VCH Verlag GmbH & Co. KGaA.

The concepts of confinement- and molecular recognition-driven chemical reactivity of cation-exchanged zeolites is illustrated by our recent results from periodic and cluster density functional theory (DFT) calculations. The reactivity of alkali-earth- and alkaline-exchanged low-silica zeolites for selective photo-oxidation of alkenes with molecular oxygen and for N2O4 disproportionation is shown to be mainly due to the specific arrangement and the size of the cations in the zeolite cage. An attempt is made to separate the effects of basicity of the framework, the Lewis acidity of the extra-framework cations and the electrostatic field in the zeolite cage as well as its geometrical properties for the respective reactions. The importance of the favorable adsorption fashion of the reagents controlled by noncovalent interactions with the microporous matrix is shown. The role of the weak interactions with the zeolite walls and the factors, which determine the preference for a particular adsorption mode, are discussed by the example of light alkanes adsorption to Mg- and Ca-exchanged faujasites. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010

The disproportionation of N(2)O(4) into NO(3)(-) and NO(+) on Y zeolites has been studied through periodic DFT calculations to unravel 1) the role of metal cations and the framework oxygen atoms and 2) the relationship between the NO(+) stretching frequency and the basicity of zeolites. We have considered three situations: adsorption on site II cations with and without a cation at site III and adsorption on a site III cation. We observed that cations at sites II and III cooperate to stabilize N(2)O(4) and that the presence of a cation at site III is necessary to allow the disproportionation reaction. The strength of the stabilization is due to the number of stabilizing interactions increasing with the size of the cation and to the Lewis acidity of the alkali cations, which increases as the size of the cations decreases. In the product, NO(3)(-) interacts mainly with the cations and NO(+) with the basic oxygen atoms of the tetrahedral aluminium through its nitrogen atom. As the cation size increases, the NO(3)(-)...cation interaction increases. As a result, the negative charge of the framework is less well screened by the larger cations and the interaction between NO(+) and the basic oxygen atoms becomes stronger. NO(+) appears to be a good probe of zeolite basicity, in agreement with experimental observations.

Both enantiomers of the first atropisomeric phosphinine (1) have been isolated by using analytical HPLC on a chiral stationary phase. The enrichment of one enantiomer and a subsequent investigation into its racemization kinetics revealed a barrier for internal rotation of DeltaG(298)(double dagger) = (109.5+/-0.5) kJ mol(-1), which is in excellent agreement with the theoretically predicted value of DeltaG(298)(double dagger) =116 kJ mol(-1). Further analysis with UV and circular dichroism spectroscopies and density functional theory calculations led to the determination and assignment of the absolute configurations of both enantiomers. These results are the basis for future investigations into this new class of axially chiral phosphinine-based ligands and their possible applications in asymmetric homogeneous catalysis.

A series of donor-functionalized pyrylium salts have been prepared by classical condensation reactions which were further converted into the corresponding thienyl- and pyridyl-substituted polydentate lambda(3)-phosphinines by reaction with P(SiMe(3))(3). Further chemical modification of these phosphorus heterocycles with Hg(OAc)(2) in the presence of methanol resulted in the formation of lambda(5)-phosphinines. The photophysical properties of a selected series of thienyl- and pyridyl-functionalized pyrylium salts, lambda(3)- and lambda(5)-phosphinines, were investigated and the results compared and supported by theoretical calculations on the DFT level. Significant fluorescence was observed for the pyrylium salts and lambda(5)-phosphinines. In contrast, the heteroaromatic substituted lambda(3)-phosphinines show very little emission which is consistent with the low oscillator strength predicted by DFT calculations for this pi-->pi* transition. Furthermore, all three classes of compounds show readily observable phosphorescence in solution, which was determined by time-gated detection at low temperature.

The catalytic reduction of carboxylic acid derivatives has witnessed a rapid development in recent years. These reactions, involving molecular hydrogen as the reducing agent, can be promoted by heterogeneous and homogeneous catalysts. The milestone achievements and recent results by both approaches are discussed in this Review. In particular, we focus on the mechanistic aspects of the catalytic hydrogenation and highlight the bifunctional nature of the mechanism that is preferred for supported metal catalysts as well as homogeneous transition metal complexes.

Structural properties of a series of mordenite and ZSM-5 zeolites with different framework Al distribution modified with oxygenated extraframework Ga, Zn, Al, Cu and Fe complexes were investigated by means of periodic density functional theory calculations. It is demonstrated that mononuclear oxygenated and hydroxylated cationic metal complexes in high-silica zeolites tend to self-organize into binuclear complexes. In the cases of Ga- and Fe-modified zeolites, it is shown that the catalytic activity of the most stable binuclear extraframework cations is much higher than that of the hypothetical very reactive mononuclear counterparts. This is due to a weaker binding of reaction intermediates and easier regeneration of the initial active complexes in the course of the catalytic reaction. The formation of multiple-charged binuclear oxygenated metal species in zeolites is a general phenomenon. It does not require a specific distribution of the equivalent number of negative framework charges that compensate for the positive charge of the cationic complexes. The location and the stability of cationic complexes in zeolite micropores are mainly determined by the coordination properties of the metal centres.

Large zeolite crystals have been used as model systems for the investigation of diffusion and catalytic reactivity phenomena in microporous host materials for at least two decades. However, their potential in assisting the detection of elusive reactive intermediates appears to have been underestimated. Herein, we show that a complementary use of vibrational and optical spectroscopy in combination with theoretical calculations allows for the unambiguous identification of transient carbocationic species generated upon the acid-catalyzed oligomerization of styrene derivatives within zeolite H-ZSM-5. Thanks to the mediated diffusion of the reactant in the large H-ZSM-5 crystals and minimal external surface the reaction intermediates can be accumulated within zeolite micropores in sufficient concentrations to allow their detection by synchrotron-based IR microspectroscopy. The UV/Vis and IR spectra display strong polarization dependence of on the molecular alignment of the dimeric styrene carbocations imposed by the zeolite channels and cages that can be rationalized in terms of the electronic and vibrational transitions of the intrazeolite carbocations. Based on these findings, a molecular-level picture of the macroscopic arrangement of the reaction intermediates confined within microporous zeolite matrices can be devised.

Basic molecular concepts in heterogeneous catalysis are illustrated by recent results from periodic and cluster density functional theory (DFT) calculations. For reactions on platinum surfaces, differences in the activation barriers found for ammonia activation are analysed in terms of bond-order conservation principles. The notion of early and late transition-states is introduced and used to understand the difference between step edges versus terrace activation. Another important concept relates to the stereoselectivity of a catalytic reaction. For immobilized organo-metallic complexes, the ligand-reactant interaction dominates the selectivity. We analyse activation by immobilized salen complexes and show that attachment of the catalytically active complex to the wall of a microporous system can dramatically affect the conformation of the ligand and hence selectivity. In zeolites we find that the match of shape and size of pre-transition-state structures with the zeolite cavity dominates the stereochemistry of the reaction.