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Guest Species (guest + species)

Distribution by Scientific Domains
Chemistry100%

Selected Abstracts

High-Zirconium-Content Nano-Sized Bimodal Mesoporous Silicas

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2006
David Ortiz de Zárate
Abstract Silica-based nanoparticulated bimodal mesoporous materials with high Zr content (43 , Si/Zr , 4) have been synthesized by a one-pot surfactant-assisted procedure from a hydroalcoholic medium using a cationic surfactant (CTMABr = cetyltrimethylammonium bromide) as structure-directing agent, and starting from molecular atrane complexes of Zr and Si as hydrolytic inorganic precursors. This preparative technique allows optimization of the dispersion of the Zr guest species in the silica walls. The bimodal mesoporous nature of the final high surface area nano-sized materials is confirmed by XRD, TEM, and N2 adsorption,desorption isotherms. The small intraparticle mesopore system (with pore sizes around 2,3 nm) is due to the supramolecular templating effect of the surfactant, while the large mesopores (around 12,24 nm) have their origin in the packing voids generated by aggregation of the primary nanometric mesoporous particles. The basicity of the reaction medium seems to be a key parameter in the definition of this last pore system. The effects induced by the progressive incorporation of Zr atoms on the mesostructure have been examined, and the local environment of the Zr sites in the framework has been investigated by UV/Vis spectroscopy. Observations based on the consequences of post-treatments of the as-synthesized materials with HCl/ethanol mixtures corroborate that the atrane method leads to Zr-rich materials showing enhanced site accessibility and high chemical homogeneity throughout the pore walls. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]

Encapsulation and Stabilization of Reactive Aromatic Diazonium Ions and the Tropylium Ion Within a Supramolecular Host

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 24 2004
Julia L. Brumaghim
Abstract Supramolecular assemblies with internal cavities are being developed as nanoscale reaction vessels to protect or modify the reactivity of guest species through encapsulation. Diazonium cations and the tropylium cation were examined for their ability to encapsulate in the tetrahedral [Ga4L6]12, supramolecular assembly. The 4-(diethylamino)benzenediazonium cation 1 readily formed a 1:1 host,guest complex with this assembly, and this encapsulation prevented 1 from reacting with 2,4-pentanedione in D2O. The tropylium cation also formed a 1:1 host,guest complex with the [Ga4L6]12, assembly, greatly slowing its decomposition in D2O. Encapsulation in the protected environment of this host cavity alters the reactivity of these guest molecules, giving them greater stability. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source]

Guest,Guest,Host Multicomponent Molecular Crystals: Entrapment of Guest,Guest in Honeycomb Networks Formed by Self-Assembly of 1,3,5-Tri(4-hydroxyaryl)benzenes

CHEMISTRY - A EUROPEAN JOURNAL, Issue 26 2010
Jarugu, Narasimha Moorthy Prof.
Abstract Sterically-engineered rigid trigonal molecular modules based on 1,3,5-tri(4-hydroxyphenyl)benzenes H1 and H2 undergo O-H,,,O hydrogen-bonded self-assembly into eight-fold catenated hexagonal (6,3) and two-fold interpenetrated undulated square (4,4) networks, respectively. In the presence of [18]crown-6 as a guest, the triphenol H1 is found to self-assemble into a honeycomb network with hexagonal voids created between three triphenol building blocks. The guest [18]crown-6 molecules are found to be nicely nested in hexagonal enclosures. The empty spaces within the crowns can be further filled with neutral (MeOH/water, MeOH/MeNO2) or ionic guest species such as KI/KAcAc to furnish novel multicomponent assemblies, that is, guest,guest,host, that typify Russian dolls. In contrast, triphenol H2 is found to yield analogous multicomponent molecular crystals in which the guest crown,K+ acts as a spacers in the hydrogen-bonded self-assembly that leads to distorted chicken wire networks. [source]

"Breathing" in Adsorbate-Responsive Metal Tetraphosphonate Hybrid Materials

CHEMISTRY - A EUROPEAN JOURNAL, Issue 27 2009
Rosario M.
Abstract Breathe easy: Reversible H2O and NH3 gas uptake by 2D calcium tetraphosphonates (see figure) is accompanied by framework structural changes similar to those previously reported for some carboxylate-based hybrids. This breathing mechanism is accompanied by a volume increase of 55,%, while maintaining the topology and crystallinity of the material. The structures of various layered calcium tetraphosphonates (CaH6DTMP; H8DTMP=hexamethylenediamine tetrakis(methylenephosphonic acid)), have been determined. Starting from CaH6DTMP,2H2O, thermal treatment and subsequent exposure to NH3 and/or H2O vapors led to four new compounds that showed high storage capacity of guest species between the layers (up to ten H2O/NH3 molecules) and a maximum volume increase of 55,%. The basic building block for these phosphonates consists of an eight-membered ring chelating Ca2+ through two phoshonate groups, and the organic ligand is located within the layers, which are held together by hydrogen bonds. The structural analysis revealed that the uptake/removal of guest species (H2O and NH3) induces significant changes in the framework not only by changing the interlayer distances but also through important conformational changes of the organic ligand. An anisotropic breathing motion could be quantified by the changes of the unit-cell dimensions and ligand arrangements in four crystalline derivatives. Complete characterization revealed the existence of interconversion reactions between the different phases upon gas uptake and release. The observed behavior represents, to the best of our knowledge, the first example of a breathing-like mechanism in metal phosphonates that possess a 2D topology. [source]

Methylazacalixpyridines: Remarkable Bridging Nitrogen-Tuned Conformations and Cavities with Unique Recognition Properties

CHEMISTRY - A EUROPEAN JOURNAL, Issue 36 2006
Han-Yuan Gong
Abstract Methylazacalix[n]pyridines (n = 4, 8) and methylazacalix[m]arene[n]pyridines (m = n = 2, 4) have been synthesized by a convenient fragment coupling approach starting from 2,6-dibromopyridine, 2,6-diaminopyridine, and benzene-1,3-diamine. Thanks to the intrinsic electronic nature of nitrogen, which can adopt mainly sp2 hybridization, allowing it variously to conjugate, partially conjugate, or not conjugate with the adjacent one or two pyridine rings, the resulting nitrogen-bridged calixpyridine derivatives act as a unique class of macrocyclic host molecules with intriguing conformational structures offering fine-tunable cavities and versatile recognition properties. Whilst in solution it is fluxional, in the solid state methylazacalix[4]pyridine adopts a 1,3-alternate conformation with a C2v symmetry in which every two bridging nitrogen atoms conjugate with one pyridine ring. After protonation, the methylazacalix[4]pyridinium species has a different conjugation system of its four bridging nitrogen atoms, yielding the similar twisted 1,3-alternate conformations with an approximate S4 symmetry. The cavity of each protonated methylazacalix[4]pyridine, however, varies finely to accommodate guest species of different size and geometry, such as planar DMF or HO2CCO2, ion, a twisted HO2CCO2, ion, and a tetrahedral ClO4, ion. As giant macrocyclic hosts, both methylazacalix[8]pyridine and methylazacalix[4]arene[4]pyridine interact efficiently with fullerenes C60 and C70 through van der Waals forces. Their ease of preparation, versatile conformational structures, and recognition properties make these multinitrogen-containing calixarenes or cyclophanes unique and powerful macrocyclic hosts in supramolecular chemistry. [source]