A time-resolved electron paramagnetic resonance spectroscopy study of paramagnetic porphyrins /

There is considerable interest in intramolecular energy transfer, especially in complexes which absorb visible light, because it is crucial to the better understanding of photoharvesting systems in photosynthetic organisms and for utilizing solar energy as well. Porphyrin dimers represent one of the best systems for the exploration of light-induced intramolecular energy transfer. Many kinds of porphyrins and porphyrin dimers have been studied over the past decade, however little attention has been paid to the influence of paramagnetic metals on the behavior of their excited states. In this thesis, Electron Paramagnetic Resonance Spectroscopy (EPR) is used to study such compounds. After light irradiation, porphyrins easily produce a variety of excited states, which are spin polarized and can be detected by the time-resolved (TR) EPR technique. The spin polarized results for vanadyl porphyrins, their electrostatically-coupled dimers, a covalently-linked copper porphyrin-free base porphyrin dimer, and free base porphyrins are presented in this thesis. From these results we can conclude that the spin polarization patterns of vanadyl porphyrins come primarily from the trip-quartet state generated by intersystem crossing (lSC) from the excited sing-doublet state through the trip-doublet state. The spin polarization pattern of electrostatically-coupled vanadyl porphyrin-free base porphyrin dimer is produced by the triplet state of the free base porphyrin half which is coupled to the unpaired electron on the vanadyl ion.

Molecular Magnetism: The Design, Synthesis, and Characterization of New Building Blocks for Molecule-based Magnetic Materials

Two classes of building blocks have been prepared and characterized and their coordination chemistry explored working towards the preparation of new molecule-based magnetic materials. In the first project, the amine functionality of 3,3'-diamino-2,2'- bipyridine was exploited for the preparation of a new family of ligands (H2L 1)-(H2L 4). The molecular structures of three ligands have been fully characterized by X-ray crystallography. [molecular structure diagram will not copy here, but is available in full pdf.] The coordination chemistry of these ligands with divalent first row transition metal ions was investigated. For ligand (H2L1), the molecular structures of four coordination complexes with stoichiometries [Zn2(Ll)(OAc)(MeO)]2 (I), [Cu2(L1)(OAc)2 (II), [Li(L1)]3 (III), and [Ni(L1)]3 (IV) were determined by X-ray crystallography. For ligand (H2L2), a Cu(II) complex of stoichiometry [Cu3(L2)(OAc)3MeO] (V) was determined by X-ray crystallography. The magnetic properties of complexes (II), (III), and (V) have been fully elucidated. In project two, synthetic strategies for the preparation of porphyrin molecules bearing triol substituents is presented. Following this approach, three new porphyrin derivatives have been prepared and characterized [Zn(HPTPP-CH2C(CH20H)3)] (VI), [P(TPP)(OCH2C(CH2)H)3)2]+CL- (VII), and [P(OEP)(C6H5)(OCH2C(CH2OH)3)]+Cl- (VIII). Attempts to exchange the labile methoxide bridges of a tetraironIIl single molecule magnet of stoichiometry [Fe4(OMe)6(dpm)6] (Hdpm = dipivaloylmethane) with the triol appended porphyrins will be discussed. [molecular structure diagram will not copy here, but is available in full pdf.]

Andrew Bloomfield collection, 2006-2012

Andrew Bloomfield, and his twin sister Victoria, were born on May 6, 1968 in Auckland, New Zealand. The following year, the family moved to Guelph, Ontario. It became apparent from the time Andrew was 14 months old that he differed considerably from his twin sister, and he was subsequently diagnosed with autism when he was four years old. As a result, he lived away from his family for much of his early life in order to participate in programs for autistic people. Andrew found this very difficult, but also made some significant progress. He became able to relate to and care for his dog, and was able to express his thoughts with Augmentative and Alternative Communication, especially using Supported Typing. His twin sister Victoria was an important person in his life, and her untimely death in a car accident in 1996 devastated him. However, his network of friends and family have provided immense support and helped him build a fulfilling and meaningful life. In 2004 Andrew founded a group of other adult communicators who "type to talk" which he named "Bridges-Over-Barriers". They meet monthly in Guelph and contributed to the 2010 volume with accompanying documentary film on DVD. He lives in his own home in Guelph, guaranteed by a housing trust, and has written several books, including an autobiography, Bridges over Barriers in My Life with Autism.

Community and the Recognition of the Other: A Levinasian Examination of The City, Inc. 1987-1992

This case study examines how The City, Inc.’s work within North and South Minneapolis, Minnesota neighborhoods from 1987 and 1992 was framed within a compilation of articles drawn from prominent Twin Cities’ daily newspapers. Positioned within a conceptual framework based on the ethical philosophy of Emmanuel Levinas, this study explores how the idea of community, as constructed and reinforced through organizational initiatives and local print media, impacts the everyday relationships of those within and between communities. Framed within a discourse analysis, Levinasian ethics considers what aspects of community discourse restrict and oppress the relation with the other. The study concludes by suggesting how the identified aspects of conditional belonging, finding the trace, and building community can be valuable in offering an alternative to assessment-style research by considering the relationship and responsibility of the one for the other.