The design, synthesis and characterization of new building blocks for the preparation of molecule-based magnetic materials /

Two new families of building blocks have been prepared and fully characterized and their coordination chemistry exploited for the preparation of molecule-based magnetic materials. The first class of compounds were prepared by exploiting the chemistry of 3,3'-diamino-2,2'-bipyridine together with 2-pyridine carbonyl chloride or 2-pyridine aldehyde. Two new ligands, 2,2'-bipyridine-3,3'-[2-pyridinecarboxamide] (Li, 2.3) and N'-6/s(2-pyridylmethyl) [2,2'bipyridine]-3,3'-diimine (L2, 2.7), were prepared and characterized. For ligand L4, two copper(II) coordination compounds were isolated with stoichiometrics [Cu2(Li)(hfac)2] (2.4) and [Cu(Li)Cl2] (2.5). The molecular structures of both complexes were determined by X-ray crystallography. In both complexes the ligand is in the dianionic form and coordinates the divalent Cu(II) ions via one amido and two pyridine nitrogen donor atoms. In (2.4), the coordination geometry around both Cu11 ions is best described as distorted trigonal bipyramidal where the remaining two coordination sites are satisfied by hfac counterions. In (2.5), both Cu(II) ions adopt a (4+1) distorted square pyramidal geometry. One copper forms a longer apical bond to an adjacent carbonyl oxygen atom, whereas the second copper is chelated to a neighboring Cu-Cl chloride ion to afford chloride bridged linear [Cu2(Li)Cl2]2 tetramers that run along the c-axis of the unit cell. The magnetic susceptibility data for (2.4) reveal the occurrence of weak antiferromagnetic interactions between the copper(II) ions. In contrast, variable temperature magnetic susceptibility measurements for (2.5) reveal more complex magnetic properties with the presence of ferromagnetic exchange between the central dimeric pair of copper atoms and weak antiferromagnetic exchange between the outer pairs of copper atoms. The Schiff-base bis-imine ligand (L2, 2.7) was found to be highly reactive; single crystals grown from dry methanol afforded compound (2.14) for which two methanol molecules had added across the imine double bond. The susceptibility of this ligand to nucleophilic attack at its imine functionality assisted via chelation to Lewis acidic metal ions adds an interesting dimension to its coordination chemistry. In this respect, a Co(II) quaterpyridine-type complex was prepared via a one-pot transformation of ligand L2 in the presence of a Lewis acidic metal salt. The rearranged complex was characterized by X-ray crystallography and a reaction mechanism for its formation has been proposed. Three additional rearranged complexes (2.13), (2.17) and (2.19) were also isolated when ligand (L2, 2.7) was reacted with transition metal ions. The molecular structures of all three complexes have been determined by X-ray crystallography. The second class of compounds that are reported in this thesis, are the two diacetyl pyridine derivatives, 4-pyridyl-2,6-diacetylpyridine (5.5) and 2,2'-6,6'-tetraacetyl-4,4'-bipyridine (5.15). Both of these compounds have been designed as intermediates for the metal templated assembly of a Schiff-base N3O2 macrocycle. From compound (5.15), a covalently tethered dimeric Mn(II) macrocyclic compound of general formula {[Mn^C^XJCl-FkO^Cl-lO.SFbO (5.16) was prepared and characterized. The X-ray analysis of (5.16) reveals that the two manganese ions assume a pentagonal-bipyramidal geometry with the macrocycle occupying the pentagonal plane and the axial positions being filled by a halide ion and a H2O molecule. Magnetic susceptibility data reveal the occurrence of antiferromagnetic interactions between covalently tethered Mn(II)-Mn(II) dimeric units. Following this methodology a Co(II) analogue (5.17) has also been prepared which is isostructural with (5.16).

Sedimentology and micromorphology of drumlin sediments at Chimney Bluffs State Park, New York, United States of America

The drumlin sediments at Chimney Bluffs, New York appear to represent a block-inmatrix style glacial melange. This melange comprises sand stringers, lenses and intraclasts juxtaposed in an apparently massive diamicton. Thin section examination of these glacigenic deposits has revealed microstructures indicative of autokinetic subglacial defonnation which are consistent with a deformable bed origin for the diamicton. These features include banding and. necking of matrix grains, oriented plasma fabrics and the formation of pressure shadows at the long axis ends of elongate clasts. Preservation of primary stratification within the sand intraclasts appears to suggest that these features were pre-existing up-ice deposits that were frozen, entrained, then deposited as part of a defonning till layer beneath an advancing ice sheet. Multi-directional micro-shearing within the sand blocks is thought to reflect the frozen nature of the sand units in such a high strain environment. It is also contended that dewatering of the sediment pile leading to the eventual immobilisation of the defonning till layer was responsible for opening sub-horizontal fissures within the diamicton. These features were subsequently infilled with mass flow poorly sorted sands and silts which were subjected to ductile defonnation during the waning stages of an actively deforming till layer. Microstructures indicative of the dewatering processes in the sand units include patches of fine-grained particles within a coarser-grained matrix and the presence of concentrated zones of translocated clays. However, these units were probably confined within an impermeable diamicton casing that prevented massive pore water influxes from the deforming till layer~ Hence, these microstructures probably reflect localised dewatering of the sand intraclasts. A layered subglacial shear zone model is proposed for the various features exhibited by the drumlin sediments. The complexity of these structures is explained in terms of ii superposing deformation styles in response to changing pore water pressures. Constructional glaciotectonics, as implied by the occurrence of sub-horizontal fissuring, is suggested as the mechanism for the stacking of the sand intraclast units within the diamicton. The usefulness of micromorphology in complimenting the traditional sedimentology of glacigenic deposits is emphasised by the current study. An otherwise massive diamicton was shown to contain microstructures indicative of the very high strain rates expected in a complexly deforming till layer. . It is quite obvious from this investigation that the classification of diamictons needs to be re-examined for evidence of microstructures that could lead to the re-interpretation of diamicton forming processes. RESUME Le pacquet de sediments drumlinaire de Chimney Bluffs, New York, represent un "bloc-en-matrice" genre de melange glaciale. Des structures microscopique comprennent l'evidence pour la defonnation intrinseque attribuee a l'origine lit non resistant du drumlin. PreselVation des structures primaires au coeur des blocs arenaces suggere que ceux sont des depots preexistant qui furent geles, entraines et par la suite sedimentes au milieu d'une couche de debris sous-glaciaires en voie de deformation. Des failles microscopiques a l'interieur des blocs arenaces appuient aussi l'idee d'un bloc cohesif (c'est-a-dire gele) au centre d'un till non resistant. Des implications significatives s'emergent de cette etude pour les conditions sous-glaciaire et les processus de la formation des drumlin.