Self-assembled molecular complexes and coordination polymers of CdII, hexamine, and monocarboxylates: structural analysis and theoretical studies of supramolecular interactions

Four new cadmium(II) complexes [Cd-2(bz)(4)(H2O)(4)(mu 2-hmt)]center dot Hbz center dot H2O (1), [Cd-3(bz)(6)(H2O)(6)(mu 2-hmt)(2)]center dot 6H(2)O (2), [Cd(pa)(2)(H2O)(mu(2)-hmt)](n) (3), and {[Cd-3(ac)(6)(H2O)(3)(mu(3)-hmt)(2)]center dot 6H(2)O}(n) (4) with hexamine (hmt) and monocarboxylate ions, benzoate (bz), phenylacetate (pa), or acetate (ac) have been synthesized and characterized structurally. Structure determinations reveal that 1 is dinuclear, 2 is trinuclear, 3 is a one-dimensional (1D) infinite chain, and 4 is a two-dimensional (2D) polymer with fused hexagonal rings consisting of Cd-II and hmt. All the Cd-II atoms in the four complexes (except one CdII in 2) possess seven-coordinate pentagonal bipyramidal geometry with the various chelating bidentate carboxylate groups in equatorial sites. One of the CdII ions in 2, a complex that contains two monodentate carboxylates is in a distorted octahedral environment. The bridging mode of hmt is mu 2- in complexes 1-3 but is mu 3- in complex 4. In all complexes, there are significant numbers of H-bonds, C-H/pi, and pi-pi interactions which play crucial roles in forming the supramolecular networks. The importance of the noncovalent interactions in terms of energies and geometries has been analyzed using high level ab initio calculations. The effect of the cadmium coordinated to hmt on the energetic features of the C-H/pi interaction is analyzed. Finally, the interplay between C-H/pi and pi-pi interactions observed in the crystal structure of 3 is also studied.

Theoretical perspectives on the development of a meta-methodology for value management

This paper provides a new set of theoretical perspectives on the topic of value management in building procurement. On the evidence of the current literature it is possible to identify two distinct methodologies which are based on different epistemological positions. An argument is developed which sees these two methodologies to be complementary. A tentative meta-methodology is then outlined for matching methodologies to different problem situations. It is contended however that such a meta-methodology could never provide a prescriptive guide. Its usefulness lies in the way in which it provides the basis for reflective practice. Of central importance is the need to understand the problem context within which value management is to be applied. The distinctions between unitary, pluralistic and coercive situations are seen to be especially significant.

The molecular structure of propylene sulphide (methylthiirane) by gas-phase electron diffraction and theoretical calculations: a molecule used in MOCVD

Gas-phase electron-diffraction (GED) data together with results from ab initio molecular orbital calculations have been used to determine the structure of propylene sulphide. Values found for the main structural parameters for the molecule are consistent with those obtained from microwave studies and are compared here with those found for similar sulphur containing rings of general formula S(CH2)n (n = 2–5). A high ring strain enthalpy was calculated for propylene sulphide which is consistent with the small C–S–C angle (48.2(6)degrees) and the relatively long C–S bond lengths (ra = 1.831(2) Å). This is thought to account for the ease of ring opening in propylene sulphide observed in MOCVD reactions and the ready polymerisation of the molecule.

Reflective practice among MATESOL graduates in the UAE: theoretical construct or ongoing benefit?

Many teacher training programs, including the MATESOL program at the American University of Sharjah (AUS) in United Arab Emirates, encourage their trainees to reflect on their practice. However, whether or not reflection becomes a part of the trainees’ practice once they leave these programs is a thought-provoking question, which formed the core of the current study. The study was qualitative in nature, using interviewing as its method of data collection. The researcher conducted semi-structured interviews with four AUS MATESOL program graduates, and investigated their perceptions of and engagement with reflective practice. The findings of the study indicate that the participants have generally developed an understanding of and appreciation for reflection and reflective practice, are aware of its values, and use different forms of reflection in order to reflect on their practice. However, some of them hold some uncertainties and misconceptions about reflective practice and its different aspects.

Development of a semantic graph-based scene description

Software representations of scenes, i.e. the modelling of objects in space, are used in many application domains. Current modelling and scene description standards focus on visualisation dimensions, and are intrinsically limited by their dependence upon their semantic interpretation and contextual application by humans. In this paper we propose the need for an open, extensible and semantically rich modelling language, which facilitates a machine-readable semantic structure. We critically review existing standards and techniques, and highlight a need for a semantically focussed scene description language. Based on this defined need we propose a preliminary solution, based on hypergraph theory, and reflect on application domains.