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Document Description
TitleLigand directed self-assembly of polymetallic [nxn] (n = 2, 3, 4) grid platforms : synthesis, structure and magnetism
AuthorDawe, Louise Nicole, 1980-
DescriptionThesis (Ph.D.)--Memorial University of Newfoundland, 2008. Chemistry
Paginationxxxii, 393 leaves : ill. (chiefly col.) + 1 CD-ROM (4 3/4 in.)
SubjectLigand field theory; Ligands--Magnetic properties; Ligands--Structure; Ligands--Synthesis; Self-assembly (Chemistry); Supramolecular chemistry
Degree GrantorMemorial University of Newfoundland. Dept. of Chemistry
NotesIncludes bibliographical references (leaves 290-304)
AbstractMetallo-supramolecular [n × n ] Mn 2 transition metal grid arrays (with n = 2, 3 and 4) were synthesized by self-assembly reactions with new ditopic imidazole hydrazone, tritopic picolinic dihydrazone and tetratopic pyridazine bis(hydrazone) ligands. Mono-, di-, trinuclear, [2×2] M4 grid and trigonal-bipyramidal clusters formed by self-assembly reactions between the ditopic ligands and metal salts. Their structural characterizations suggest a possible route to the self-assembly of [2×2] M4 grid and trigonal-bipyramidal architectures. Homometallic [3×3] M9 (M = Mn(II), Co(II), Cu(II) and Zn(II)) and heterobimetallic [3×3] Mn(II)5 Cu(II) 4 , Mn(II)5 Zn(II)4 and Mn(II)Cu(II)8 grids, based on a [M9 -(μ-O)12 ] core framework were synthesized. Their structural characterizations, in particular the identification of the Jahn-Teller axes, leading to strict orbital orthogonality and ferromagnetism in the Cu(II) containing complexes, formed the basis for magnetic interpretation and modeling. [3×3] Mn(II) 9 , Cu(II)9 and Co(II) 5 Co(III)4 grids synthesized by self-assembly reactions between metal salts and tritopic ligands with quinoline-type endpieces, leading to extended structural motifs through intermolecular face-to-face and edge-to-face π-π interactions are also reported. 4×[2×2] M 16 (M = Mn(II), Co(II), Cu(II) and Cu(II)12 Cu(I)4 ) grids were synthesized, and their magnetic properties modeled as compartmental [2×2] M 4 -(μ-Ohydrazone )4 squares for the Mn(II) 16 and Co(II)16 in complexes. The structural characterization of the Jahn-Teller axes leading to a combination of orthogonal and non-orthogonal orbital connections for both of the Cu16 grids allowed for fairly simple magnetic models to be devised.
FormatImage/jpeg; Application/pdf
SourcePaper copy kept in the Centre for Newfoundland Studies, Memorial University Libraries
Accompanying Files
Local Identifiera2700622
RightsThe author retains copyright ownership and moral rights in this thesis. Neither the thesis nor substantial extracts from it may be printed or otherwise reproduced without the author's permission.
CollectionElectronic Theses and Dissertations
Scanning StatusCompleted
PDF File(74.15 MB) --
CONTENTdm file name137367.cpd