Conductive metal-organic frameworks and networks: fact or fantasy?

Electrical conduction is well understood in materials formed from inorganic or organic building blocks, but their combination to produce conductive hybrid frameworks and networks is an emerging and rapidly developing field of research. Self-assembling organic-inorganic compounds offer immense potential for functionalising material properties for a wide scope of applications including solar cells, light emitters, gas sensors and bipolar transparent conductors. The flexibility of combining two distinct material classes into a single solid-state system provides an almost infinite number of chemical and structural possibilities; however, there is currently no systematic approach established for designing new compositions and configurations with targeted electronic or optical properties. We review the current status in the field, in particular, the range of hybrid systems reported to date and the important role of materials modelling in the field. From theoretical arguments, the Mott insulator-to-metal transition should be possible in semiconducting metal-organic frameworks, but has yet to be observed. The question remains as to whether electro-active hybrid materials will evolve from chemical curiosities towards practical applications in the near term.     

Hydrogen physisorption in metal–organic frameworks: concepts and quantum chemical calculations

Storage of hydrogen by physisorption in metal–organic frameworks is reviewed from the perspective of quantum chemistry. Concepts regarding the interaction of hydrogen with metals are revised and the specific features of metal–organic frameworks are explained. The influence of the type of inorganic cluster and hydrogen loading and its relation to hydrogen storage are analysed. Heats of hydrogen adsorption in previous studies are critically discussed and estimations are made regarding the adsorption strength needed for storage applications and how to approach commercial targets.     

Crystal structures of 2-chloropyridine and 2-fluoropyridine: Isostructural crystal packing or not?

Structural Chemistry - In order to investigate how halogen substituents influence the crystal packing of 2-halogenpyridines, the crystal structure of 2-chloropyridine was determined and the crystal...     

Versatile and efficient functionalisation of multiallylic dendronised polymers: can dense packing be reached?

Surface modification of a multiallylic dendronised polymer was performed using hydrosilylation, hydroboration or radical addition of thiols to cover the polymer with various functional moieties; surface congestion is expected to occur when bulky groups are grafted.     

Combinatorial synthesis and characterization of metal-open frameworks in mild and friendly conditions: application to CO₂ adsorption

Combinatorial screening using precipitation methods at room temperature can lead to a great diversity of carboxylate based Metal Organic Frameworks (MOFs) including already known or original porous solids. The investigation of the synthesis of MOFs in different solvent and solvent mixtures includes the use of solvents such as alcohols and tetrahydrofuran (THF) which would greatly facilitate large scale production. We also show the application of Principal Component Analysis (PCA) and clustering techniques on large libraries of XRD diffraction files in order to identify classes of similar phases and peculiar phases. The combinatorial screening of 105 samples in the La/btc system has led to the identification of two phases which are solvent depending. On the La(btc) compound, the CO? adsorption measurements reveal a guest-host interactions as supported by XRD phase transformation upon thermal treatment. The mass transport can be assigned to a "single file diffusion" regime due to the one dimensional channel porous structure associated to small pore size.     

Octahedral and Tetrahedral Coinage Metal Clusters: Is Three‐Dimensional d‐Orbital Aromaticity Viable?

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.     

Conformational control in a bipyridine linked π-conjugated oligomer: cation mediated helix unfolding and refolding

A chiral π-conjugated oligomer having alternate bipyridine and carbazole moieties connected through acetylinic bonds undergoes helical folding in chloroform-acetonitrile (40/60, v/v) as evident by fluorescence and circular dichroism changes. In the presence of transition metal cations such as Zn(2+) defolding of the helical conformation occurs. Upon decomplexation of the cation with EDTA, the helical conformation is regained.     

Theory of chemical bonds in metalloenzymes XII: Electronic and spin structures of metallo–oxo and isoelectronic species and spin crossover phenomena in oxygenation reactions

The broken-symmetry (BS) and multideterminant approaches to atomic oxygen (O), molecular oxygen (O₂) and iron–oxo (Fe(IV)O) core in P450 have elucidated electronic structures of the ground triplet and excited singlet states, which indicate isoelectronic characteristics of the species. The dissociation processes of the O–O and Fe–O double bonds are also examined to clarify the radical character, namely O-atom property responsible for radical mechanism of hydroxylations of alkanes and epoxidation of alkenes. This isolobal analogy has indeed enabled us to propose possible reaction mechanisms of oxygenation reactions by the Fe(IV)O species on the basis of available theoretical and experimental results for O and O₂. Similarly, an isolobal analogy of the σ^* bond among Fe(IV)O, dioxirane, peracids, etc. indicates the common electrophilic property for the oxygenation reactions. The small energy gaps between the high- and low-spin states of the transition structures and intermediates generated in the oxygenation reactions are found to be origins for spin crossover phenomena along the reaction pathways of these reactions.     

Brønsted/Lewis acid synergy in dealuminated HY zeolite: a combined solid-state NMR and theoretical calculation study

The Br?nsted/Lewis acid synergy in dealuminated HY zeolite has been studied using solid-state NMR and density function theory (DFT) calculation. The 1H double quantum magic-angle spinning (DQ-MAS) NMR results have revealed, for the first time, the detailed spatial proximities of Lewis and Br?nsted acid sites. The results from 13C NMR of adsorbed acetone as well as DFT calculation demonstrated that the Br?nsted/Lewis acid synergy considerably enhanced the Br?nsted acid strength of dealuminated HY zeolite. Two types of Br?nsted acid sites (with enhanced acidity) in close proximity to extra-framework aluminum (EFAL) species were identified in the dealuminated HY zeolite. The NMR and DFT calculation results further revealed the detailed structures of EFAL species and the mechanism of Br?nsted/Lewis acid synergy. Extra-framework Al(OH)3 and Al(OH)2+ species in the supercage cage and Al(OH)2+ species in the sodalite cage are the preferred Lewis acid sites. Moreover, it is the coordination of the EFAL species to the oxygen atom nearest the framework aluminum that leads to the enhanced acidity of dealuminated HY zeolite though there is no direct interaction (such as the hydrogen-bonding) between the EFAL species and the Br?nsted acid sites. All these findings are expected to be important in understanding the roles of Lewis acid and its synergy with the Br?nsted acid in numerous zeolite-mediated hydrocarbon reactions.     

Liquids intermediate between "molecular" and "ionic" liquids: liquid ion pairs?

Ionic liquids comprised of tetradecyltrihexyl- and tetrabutyl-phosphonium cations paired with chloride or sulfonyl amide anions exhibit properties that reflect strong ion association, including comparatively low viscosity as well as a degree of volatility, and hence exemplify an interesting intermediate state between true ionic and true molecular liquids.     

Adsorption complexes ‘zeolite–cationic surfactant’: properties and surface activity in a polymer composite material based on ultra-high-molecular-weight polyethylene

We investigated the adsorption of the cationic surfactant cetyltrimethylammonium bromide (CTAB) to zeolite from premicellar and micellar solutions, as well as some properties of the organically modified zeolite surface and the nature of its interfacial interaction with ultra-high-molecular-weight polyethylene (UHMWPE) in a UHMWPE-based polymer composite material (PCM). The formation mechanism of mono- and bimolecular adsorption layers of cetyltrimethylammonium cation and bromide anion to the clinoptilolite (Cli) surface was proposed, and the thermodynamic and kinetic characteristics of adsorption were determined. The surface texture of organically modified zeolite was studied by instrumental methods; the thermal stability limits of CTAB adsorption layers to zeolite surface and their decomposition behavior in inert and oxidizing media were established. The evaluation of the deformation and strength properties, the study of the supramolecular structure, and the calculation of the thermodynamic and kinetic parameters of the PCM crystallization process revealed that the filing with organically modified Cli increases the UHMWPE surface activity and improves their compatibility.     

Binding of proteins to the minor groove of DNA: What are the structural and energetic determinants for kinking a basepair step?

The structural and energetic determinants for kinking a basepair step by minor groove-insertion of the protein side chains of PurR, LacI, LEF-1, IHF, Sac7d, and Sso7d, have been calculated by molecular dynamics/potential of mean force simulations. The structural determinants of the kinked structures are: two contiguous furanose rings achieve different conformations, in the region of C3'endo (A-DNA) and C2'endo (B-DNA); the chi torsion angle always takes values characteristic of the C2'endo conformation of B-DNA, independently of sugar puckering; and protein side chain insertion increases slide (from negative to positive values), rise, and roll, and decreases twist. The energetic determinants of DNA kinking are: the conformational transition of the sugar-phosphate backbone is not energetically demanding; the relative importance of the interbase parameters in the free energy penalty is slide, followed by twist and rise, and concluding with shift and roll; and the characteristic increase of roll and decrease of twist, upon side chain insertion, tends to stabilize the process of DNA kinking.     

Diet and metabolic syndrome: where does resistant starch fit in?

Metabolic syndrome is a term linking the clinical profiles of some of the world's major health problems today: obesity, heart disease, and diabetes. It is predicated on dietary patterns, and particularly on the delivery of fuel. The effects may be seen first in the development of abdominal obesity and insulin resistance leading to Type 2 diabetes mellitus and coronary heart disease. This review examines the role resistant starch might play in the prevention and management of these conditions. Beginning with a definition of resistant starch, a critical review of the scientific literature is presented. Current knowledge suggests that resistant starch in the diet may assist in the prevention and management of conditions associated with the metabolic syndrome via its potential effects on delaying the delivery of glucose as fuel with subsequent fat utilization and appetite control benefits. There is still a great deal of research to be undertaken in this area, but it is clearly warranted, given the position of starches in the global food supply and the potential impact on population health.     

Local structure distortion and spin Hamiltonian parameters for Cr4+ ions in Cr4+:α-Al2O3 crystals

The relations between the spin Hamiltonian (SH) parameters and crystal structure of Cr⁴⁺:α-Al₂O₃ crystals have been established. On the basis of this, the SH parameters including zero-field splitting parameter D and Zeeman g-factors (g_|| and g_⊥) for Cr⁴⁺ ions in Cr⁴⁺:α-Al₂O₃ crystals, taking into account the spin–spin (SS), spin-other-orbit (SOO) and orbit–orbit (OO) magnetic interactions in addition to the spin–orbit (SO) magnetic interaction, are theoretically investigated using complete diagonalization method (CDM). The theoretical results are in excellent agreement with the experimental ones when the upper three O^2? ions rotate 0.94° toward [1 1 1] axis and the lower three O^2? ions rotate 0.92° toward it. Hence, the local structure distortion effect plays an important role in explaining the spectroscopic properties of Cr⁴⁺ ions in Cr⁴⁺:α-Al₂O₃ crystals. This study shows that for Cr⁴⁺:α-Al₂O₃ the contributions arising from SS, SOO, and OO interactions to the zero-field splitting (ZFS) parameter D are appreciable, whereas those to g_|| and g_⊥ are quite small.     

Determining Preexponential Factor in Model-Free Kinetic Methods: How and Why?

The kinetics of thermally stimulated processes in the condensed phase is commonly analyzed by model-free techniques such as isoconversional methods. Oftentimes, this type of analysis is unjustifiably limited to probing the activation energy alone, whereas the preexponential factor remains unexplored. This article calls attention to the importance of determining the preexponential factor as an integral part of model-free kinetic analysis. The use of the compensation effect provides an efficient way of evaluating the preexponential factor for both single- and multi-step kinetics. Many effects observed experimentally as the reaction temperature shifts usually involve changes in both activation energy and preexponential factor and, thus, are better understood by combining both parameters into the rate constant. A technique for establishing the temperature dependence of the rate constant by utilizing the isoconversional values of the activation energy and preexponential factor is explained. It is stressed that that the experimental effects that involve changes in the preexponential factor can be traced to the activation entropy changes that may help in obtaining deeper insights into the process kinetics. The arguments are illustrated by experimental examples.     

Applications of cellular automata: attractors and fractals in analytical chemistry?

A cellular automaton is a discrete dynamic system of simple construction, yet capable of exhibiting complex self-organizing behavior. A cellular automaton can be used to model differential systems by assuming that time and space are quantized, and that the dependent variable takes on a finite set of possible values. Cellular-automaton behavior falls into four distinct universality classes, analogous to (1) limit points, (2) limit cycles, (3) chaotic attractors (fractals), and (4) 'universal computers'. The behavior of members of each of these four classes is explored in the context of digital spectral filtering. The utility of class 2 behavior in experimental data analysis is demonstrated with a laboratory example.     

Phosphate and Vanadate in Biological Systems: Chemical Relatives or More?

Structural and functional analogies between acid phosphatases and vanadium haloperoxidases are reflected in the conservation of the amino acid residues contributing to the active sites of these enzymes. This has interesting consequences for the research on both enzyme systems. A first example is the newly proposed structure for the active site of human glucose-6-phosphatase: The picture shows parts of six of the nine transmembrane helices as well as the amino acids (black ovals) that presumably participate in the formation of the active site.     

Chemistry of 4-alkylaryloxenium ion "precursors": sound and fury signifying something?

Quinol esters 2b, 2c, and 3b and sulfonamide 4c were investigated as possible precursors to 4-alkylaryloxenium ions, reactive intermediates that have not been previously detected. These compounds exhibit a variety of interesting reactions, but with one possible exception, they do not generate oxenium ions. The 4-isopropyl ester 2b predominantly undergoes ordinary acid- and base-catalyzed ester hydrolysis. The 4-tert-butyl ester 2c decomposes under both acidic and neutral conditions to generate tert-butanol and 1-acetyl-1,4-hydroquinone, 8, apparently by an SN1 mechanism. This is also a minor decomposition pathway for 2b, but the mechanism in that case is not likely to be SN1. Decomposition of 2c in the presence of N3- leads to formation of the explosive 2,3,5,6-tetraazido-1,4-benzoquinone, 14, produced by N3--induced hydrolysis of 8, followed by a series of oxidations and nucleophilic additions by N3-. No products suggestive of N3--trapping of an oxenium ion were detected. The 4-isopropyl dichloroacetic acid ester 3b reacts with N3- to generate the two adducts 2-azido-4-isopropylphenol, 5b, and 3-azido-4-isopropylphenol, 11b. Although 5b is the expected product of N3- trapping of the oxenium ion, kinetic analysis shows that it is produced by a kinetically bimolecular reaction of N3- with 3b. No oxenium ion is involved. The sulfonamide 4c predominantly undergoes a rearrangement reaction under acidic and neutral conditions, but a minor component of the reaction yields 4-tert-butylcresol, 17, and 2-azido-4-tert-butylphenol, 5c, in the presence of N3-. These products may indicate that 4c generates the oxenium ion 1c, but they are generated in very low yields (ca. 10%) so it is not possible to definitively conclude that 1c has been produced. If 1c has been generated, the N3--trapping data indicate that it is a very short-lived and reactive species in H2O. Comparisons with similarly reactive nitrenium ions indicate that the lifetime of 1c is ca. 20-200 ps if it is generated, so it must react by a preassociation process. Density functional theory calculations at the B3LYP/6-31G*//HF/6-31G* level coupled with kinetic correlations also indicate that the aqueous solution lifetimes of 1a-c are in the picosecond range.     

Pincer oxazolines: emerging tools in coordination chemistry and catalysis--where to next?

A brief overview of the coordination chemistry aspects of pincer ligands and their complexes containing at least one oxazoline (i.e., 4,5-dihydro-2-oxazole) unit is presented. This historical perspective is placed into a context of the possible future direction(s) in this particular arena of pincer chemistry. These ideas are compared and contrasted to the overall direction of pincer chemistry since the first such complexes were reported in the 1970s.