Studies on the Stereochemistry of 2-(Nitromethylidene)-Heterocycles

The ¹H-NMR spectra of 2-(nitromethylidene)pyrrolidine ( 7 ), 1-methyl-2-(nitromethylidene)imidazolidind ( 10 ) and 3-(nitromethylidene)tetrahydrothiazine ( 11 ) in CDCl₃ and (CD₃)₂SO indicate that these compounds have the intramolecularly H-bonded structures (Z)- 7 , (E)- 10 and (Z)- 11 while the N-methyl derivative 8 of 7 is (E)-configurated in both solvents. 1-Benzylamino-1-(methyltio)-2-nitroehtylene ( 13 ), an acylic model, has the H-bonded configuration (E)- 13 in CDCl₃ and in (CD₃)₂SO. 2-(Nitromethylidene)thiazolidine ( 3 ) has the (E)-configuration in CDCl₃ but exists in (CD₃)₂SO as a mixture of (Z)- and (E)-isomers with the former predominating. Both species are detected to varying proportions in a mixture of the two solvents. ¹⁵N-NMR spectroscopy of 3 ruled out unambiguously the nitronic acid structure 6 and the nitromethyleimine structure 5 . The N-methyl derivative 4 of 3 is (Z)-configurated in (CD₃)₂SO. Comparison of the olefinic proton shifts of (Z)- 3 and (Z)- 4 with those of analogues and also of 1,1-bis(methylti)-2-nitroethylene ( 12 ) shows decreased conjugation of the lone pair of electrons of the ring N-atom in (Z)- 3 and (Z)- 4 . This is also supported by ¹³C-NMR studies. Plausible explanations for the phenomenon are offered by postulating that the ring N-atoms are pyramidal in (Z)- 3 and (Z)- 4 and planar in other cases or, alternatively, that the conjugated nitroenamine system gets twisted due to steric interaction between the NO₂-group and the ring S-atom. Single-crystal X-ray studies of 3 and 8 show that the former exists in the (Z)-configuration and the latter in (E)-configuration; the ring N-atom in the former has slightly more pyramidal character than in the latter.     

Aromatic amines and their derivatives,Part 2. Synthesis,spectroscopic properties,and molecular and crystal structure ofN-acetyl-4,N-dimethyl-6-(N-acetyl-p-toluidinomethyl)aniline

The synthesis and selected aspects of the UV, IR, and¹H NMR spectra of the title compound are described. The crystals of the title compound are triclinic witha=12.999(9),b=8.911(4),c=9.199(5) Å;=105.56(3),=113.50(4), =92.53(3)°;Z=2; space groupP¯1. Its X-ray crystal structure analysis provides information regarding the conformational features of the amide linkage when no intermolecular hydrogen bonding involving this group is present. The X-ray study shows that the C-N bond is longer [1.363(4) Å] than that found normally in peptide molecules. The compound shows a peculiar disorder involving one of the two amide groups present in the molecule. The conformation of theN-methyl acetanilide moiety and its relation to the¹H NMR spectrum of the compound are discussed.     

Physico-chemical characterization of MCM-41 silica spheres made by the pseudomorphic route and grafted with octadecyl chains

This work reports on the first comprehensive characterization of octadecyl (C(18)) modified MCM-41 silica spheres, prepared via the pseudomorphic route, followed by grafting with mono- or trifunctional octadecyl (C(18)) alkyl chains and endcapping with hexamethyldisilazane. Small angle X-ray scattering (SAXS), nitrogen adsorption-desorption and scanning electron microscopy (SEM) measurements were performed to obtain information about the MCM-41 pore structure, surface properties and morphological features. The degree of grafting and cross-linking of the silanes were determined by (29)Si magic angle spinning NMR spectroscopy, while FTIR and (13)C NMR were employed to study the conformational behavior of the surface-immobilized alkyl chains. The SAXS pattern proved the existence of a hexagonal mesopore arrangement for both the ungrafted and the grafted MCM-41 silica spheres. In addition, there is evidence of some long-range distortion in the pore structure. SEM measurements revealed the same morphological features for the parent silica and the MCM-41 silica spheres before and after C(18) grafting. The achieved surface loading for the MCM-41 material is rather low. It was also shown that a substantial amount of the accessible surface silanol groups is endcapped by trimethylsilane which in turn results in a very low surface coverage due to the octadecyl chains. The nitrogen sorption studies provided values for the surface area, total pore volume and pore diameter which are very typical for mesoporous materials. The reduction in surface area and total pore volume upon surface grafting is related to the binding of trimethylsilane in the interior of the pores, while due to the spatial restrictions octadecyl chains are primarily attached near the pore entrance. The experimental FTIR and (13)C NMR data point to a very low conformational order of the C(18) chains which is in accordance with the observed low surface coverage and the resulting spatial freedom for these surface-immobilized alkyl chains.     

6a,6b,12a,12b‐Tetra­hydro­cyclo­octa­[3,4]­cyclo­buta­[1,2][8]­annulene

The cis,syn,cis‐tricyclic [2+2]‐dimer of cyclo­octatetraene, C₁₆H₁₆, crystallizes in space group Pca2₁ with two mol­ecules in the asymmetric unit. An extensive network of weak C—H⋯π(Czdbnd;C) interactions between the two independent mol­ecules, A and B, as well as A⋯A and B⋯B interactions, are observed in the supramolecular assembly. The C—H groups point more towards one C atom than to the centre of the Czdbnd;C bond. Notable among the interactions are bifurcated (cyclo­butane)C—H⋯Czdbnd;C contacts that span transannularly the eight‐membered ring.     

A preliminary assessment of microstructural and compositional characteristics of two variants of precarbonated and postcarbonated concrete mixes

The hydration, precarbonation, and postcarbonation microstructural and compositional attributes of 2 variants of concrete were studied using scanning electron microscope, energy dispersive spectroscopy, and X‐ray diffraction techniques. Results obtained showed presence of large number of diffraction peaks indicative of SiO₂ as major phase. Higher pH, alkalinity, and absence of effects of carbonation were suggested from the presence of portlandite peaks. Evidence of effect of carbonation was studied through the analysis of the experimental diffraction peaks obtained postexposure to accelerated carbonation in a controlled environment. Presence of all the 3 polymorphs of calcium carbonate (CaCO₃) such as aragonite, vaterite, and calcite depending upon the moisture content and the material constituting the concrete sample were envisaged signifying carbonation. Precipitation of these CaCO₃ crystals was responsible for depletion of CH as well as calcium–silicate–hydrate, ettringite with the progress of carbonation as suggested by their absence in the X‐ray diffraction diffractograms of the carbonated samples. The crystal structure of the newly formed minerals in both the variants of concrete sample was highly controlled by the stages of carbonation, with development of amorphous CaCO₃ (amalgamated with that of calcium hydrates) in early stages of carbonation as well as fully developed rhombohedral CaCO₃ crystals in later stages.     

On the cyanogen halides

Proceedings - Mathematical Sciences -     

Exploring the Potential of Fulvalene Dimetals as Platforms for Molecular Solar Thermal Energy Storage: Computations,Syntheses, Structures,Kinetics, and Catalysis

A study of the scope and limitations of varying the ligand framework around the dinuclear core of FvRu₂ in its function as a molecular solar thermal energy storage framework is presented. It includes DFT calculations probing the effect of substituents, other metals, and CO exchange for other ligands on ΔH_storage. Experimentally, the system is shown to be robust in as much as it tolerates a number of variations, except for the identity of the metal and certain substitution patterns. Failures include 1,1′,3,3′‐tetra‐tert‐butyl ( 4 ), 1,2,2′,3′‐tetraphenyl ( 9 ), diiron ( 28 ), diosmium ( 24 ), mixed iron‐ruthenium ( 27 ), dimolybdenum ( 29 ), and ditungsten ( 30 ) derivatives. An extensive screen of potential catalysts for the thermal reversal identified AgNO₃–SiO₂ as a good candidate, although catalyst decomposition remains a challenge.     

Adsorption-induced surface stresses in alkanethiolate-au self-assembled monolayers

First-principles calculations were employed to elucidate the origin of adsorption-induced surface stresses in alkanethiolate self-assembled monolayers on an Au(111) surface. Our results suggest a mechanism that accounts for the huge relief of the tensile stress compared to the bare surface in terms of a local rearrangement of surface Au atoms accompanying charge removal from the surface towards the Au-S bond. A purely interadsorbate interaction model is shown to be inconsistent with the anisotropy and the magnitude of the calculated stress.