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.]

Creating a Generation of Upstanders: Curriculum Resource to Help Ontario Educators Build Safe Schools

This project focuses on the bullying found in the 21st century elementary classrooms, more specifically in grades 4-8. These grades were found to have high levels of bullying because of major shifts in a student’s life that may place a student of this age at risk for problems with their peer relationships (Totura et al., 2009). Supporting the findings in the literature review, this handbook was created for Ontario grade 4-8 classroom teachers. The resource educates teachers on current knowledge of classroom bullying, and provides them with information and resources to share with their students so that they can create a culture of upstanders. Upstanders are students who stand up for the victims of bullying, and have the self-esteem and strategies to stand up to classroom bullies. These upstanders, with the support of their classroom teachers and their peers, will be a force strong enough to build the government-mandated Safe School environment.

Creating a Generation of Upstanders: Curriculum Resource to Help Ontario Educators Build Safe Schools

This project focuses on the bullying found in the 21st century elementary classrooms, more specifically in grades 4-8. These grades were found to have high levels of bullying because of major shifts in a student’s life that may place a student of this age at risk for problems with their peer relationships (Totura et al., 2009). Supporting the findings in the literature review, this handbook was created for an Ontario grade 4-8 classroom teachers. The resource educates teachers on current knowledge of classroom bullying, and provides them with information and resources to share with their students so that they can create a culture of upstanders. Upstanders are students who stand up for the victims of bullying, and have the self-esteem and strategies to stand up to classroom bullies. These upstanders, with the support of their classroom teachers and their peers, will be a force strong enough to build the government-mandated Safe School environment.

Ligand design for molecule-based magnetic and/or conducting materials

Work in the area of molecule-based magnetic and/or conducting materials is presented in two projects. The first project describes the use of 4,4’-bipyridine as a scaffold for the preparation of a new family of tetracarboxamide ligands. Four new ligands I-III have been prepared and characterized and the coordination chemistry of these ligands is presented. This project was then extended to exploit 4,4’-bipyridine as a covalent linker between two N3O2 macrocyles. In this respect, three dimeric macrocycles have been prepared IV-VI. Substitution of the labile axial ligands of the Co(II) complex IV by [Fe(CN)6]4- afforded the self-assembly of the 1-D polymeric chain {[Co(N3O2)H2O]2Fe(CN)6}n•3H2O that has been structurally and magnetically characterized. Magnetic studies on the Fe(II) complexes V and VI indicate that they undergo incomplete spin crossover transitions in the solid state. Strategies for the preparation of chiral spin crossover N3O2 macrocycles are discussed and the synthesis of the novel chiral Fe(II) macrocyclic complex VII is reported. Magnetic susceptibility and Mössbauer studies reveal that this complex undergoes a gradual spin crossover in the solid state with no thermal hysteresis. Variable temperature X-ray diffraction studies on single crystals of VII reveal interesting structural changes in the coordination geometry of the macrocycle accompanying its SCO transition. The second project reports the synthesis and characterization of a new family of tetrathiafulvalene derivatives VIII – XII, where a heterocyclic chelating ligand is appended to a TTF donor via an imine linker. The coordination chemistries of these ligands with M(hfac)2.H2O (M( = Co, Ni, Mn, Cu) have been explored and the structural and magnetic properties of these complexes are described.

Colin Duquemin fonds, 1935, 1968-2001, n.d.

Colin Duquemin was born in 1932 in Guernsey, British Channel Islands, and came to Canada as a young adult. He attended McMaster University (B.A.), the University of Toronto (B.Ed.), the State University of New York at Buffalo (M.A.) and the University of London, London, England (M.Sc.). He began his career as a tea taster and tea buyer in Colombo, Ceylon (Sri Lanka), but later became a teacher. He spent most of his teaching career as a manager of the St. Johns Outdoor Studies Centre, north of Fonthill, Ontario, developing environmentally related programmes for elementary and secondary school students. He was also active in many local organizations, serving as Associate Director of the St. Catharines Grape and Wine Festival Board, Chairman of the St. Catharines Historical Museum Board, President of the Niagara Military Institute and President of the Canadian Canal Society. In addition to the numerous curriculum materials he authored, Colin wrote the Driver’s Guide Series, highlighting the many points of interest in the Niagara region, including the Welland Canal, battlefields of the War of 1812, and the Niagara Parkway. He also wrote A Guide to the Grand River Canal (1980) with Daniel Glenney, The Fur Trade in Rupert’s Land: Opening up the Canadian Northwest (1992), Stick to the Guns! A short history of the 10th field battery, Royal Regiment of Canadian Artillery (1996), Niagara Rebels: the Niagara Frontier Incidents in the Upper Canada Rebellion, 1837-1838 ( 2001), and edited and contributed to A Lodge of Friendship: the History of Niagara Lodge, No. 2, A.F. & A.M, Niagara-on-the-Lake, Ontario, Canada, 1792-1992 (1991). He died in December 2012.

Integrating Media Education Into the Curriculum: What Chinese Educators Can Learn from Ontario Education

This study sought to determine if and how the Ontario approach to integrating media education into the curriculum can be applied to Chinese education. The study used thematic analyses to identify the Ontario curriculum‘s attributes and approach to teaching media literacy, and to investigate relevant policies and national curriculum standards in Chinese compulsory education to reveal the status quo of Chinese media education. Finally, the study explored the feasibility of applying the Ontario media education model in China. Findings indicate that the Ontario model can be employed in the Chinese context, but only partly so, because current Chinese media education is limited by protectionism and restrictive policies corresponding to the use of media merely as research tools.

Therapeutic Recreation Education in Canada: A Review of the Current Curriculum

Abstract This descriptive study sought to identify the similarities and differences between the various educational institutions offering therapeutic recreation curriculum across Canada. The study utilized mixed methods, including open and closed-ended questions on a survey and document analysis. The research participants were from 14 educational institutions located across the nation. Results from this study identify similarities and differences in the curriculum used to prepare students pursuing a career in the TR field. Core competencies and standards of practice for the field of therapeutic recreation were defined and discussed. Accreditation and the accrediting bodies in the field of TR are reviewed because of their significant impact on curriculum. Implications regarding certification and regulation pertaining to the education for therapeutic recreation practitioners were discussed along with suggestions for future research.

Estelle Cuffe Hawley fonds, 1852-1999, n.d.

Estelle Cuffe Hawley (1894-1995) was an educator, businesswoman and politician, who became the first woman alderman on the St. Catharines City Council. She began her career as a teacher in Peterborough in 1913, and later taught in St. Catharines at Connaught School and St. Paul’s Ward School, where she served as Principal for six years. In 1928-29, she worked as an exchange teacher in Edmonton, Alberta. This would be Estelle’s last year in the teaching profession. She moved back to St. Catharines in 1930 and began a career in business, as an employee of Sun Life Assurance Co. She remained in this profession until around 1952. It was during this period that she became very active in the community and local politics. In 1934 she was elected to the St. Catharines Board of Education, where she advocated for the improvement of teachers’ salaries, the introduction of nursing services in schools, and the inclusion of music in the curriculum. She served as a member of the school board until 1937. The following year, she became the first woman elected to the St. Catharines City Council. As an alderman, she worked to improve the community's social welfare services, serving consecutively as chairman of all committees. She established comprehensive health services (including medical, dental and nursing), in the public, separate and secondary schools of St. Catharines, the first program of its kind in Canada. She was also instrumental in establishing minimum housing standards and engaging the public in local government by arranging a series of lectures by city officials. She remained a member of City Council until 1943. The following year she campaigned unsuccessfully for the mayoralty. In 1953 she married Hubert Hawley and moved to Orillia. She continued to remain active in the community, serving as President of the Ontario Recreation Association from 1950-1953, and editor of their Bulletin from 1955-1961. During the 1960s, she worked with various groups, including the Voice of Women, the Mental Health Association and the Freedom from Hunger Campaign. In addition to this work, Estelle wrote poetry and short stories, some of which were published in the Peterborough Review, the Globe and Mail and the Canadian Churchman. Some of her short stories (often about her childhood experiences) were broadcast on the CBC, as well as her experiences as a Town Councillor (under the pseudonym Rebecca Johnson in 1961). She also broadcast a segment that was part of a series called “Winning the Peace” in April 1944. Estelle was a sought-after public speaker, speaking on topics such as peace, democracy, citizenship, education, and women’s rights. In 1976, Brock University conferred an honorary Doctor of Law degree to Estelle for her leadership as an educator, businesswoman and a stateswoman. Her husband Hubert died that same year, and Estelle subsequently moved to Mississauga. With the assistance of an Ontario Heritage Foundation grant, she began work on her memoir. She later moved back to Orillia and died there in 1995, at the age of 101.

The Implementation of Jenkins’s 21st-Century Skills in the Curriculum: A Cross-National Policy Analysis

This meta-analytic study sought to determine if cross-national curricula are aligned with burgeoning digital learning environments in order to help policy makers develop curriculum that incorporates 21st-century skills instruction. The study juxtaposed cross- national curricula in Ontario (Canada), Australia, and Finland against Jenkins’s (2009) framework of 11 crucial 21st-century skills that include: play, performance, simulation, appropriation, multitasking, distributed cognition, collective intelligence, judgment, transmedia navigation, networking, and negotiation. Results from qualitative data collection and analysis revealed that Finland implements all of Jenkins’s 21st-century skills. Recommendations are made to implement sound 21st-century skills in other jurisdictions.

Novel Magnetic Materials Based on Macrocyclic Ligands: Towards High Relaxivity Contrast Agents and Mononuclear Single-Molecule Magnets

The preparation and characterization of coordination complexes of Schiff-base and crown ether macrocycles is presented, for application as contrast agents for magnetic resonance imaging, Project 1; and single-molecule magnets (SMMs), Projects 2 and 3. In Project 1, a family of eight Mn(II) and Gd(III) complexes of N3X2 (X = NH, O) and N3O3 Schiff-base macrocycles were synthesized, characterized, and evaluated as potential contrast agents for MRI. In vitro and in vivo (rodent) studies indicate that the studied complexes display efficient contrast behaviour, negligible toxicity, and rapid excretion. In Project 2, DyIII complexes of Schiff-base macrocycles were prepared with a view to developing a new family of mononuclear Ln-SMMs with pseudo-D5h geometries. Each complex displayed slow relaxation of magnetization, with magnetically-derived energy barriers in the range Ueff = 4 – 24 K. In Project 3, coordination complexes of selected later lanthanides with various crown ether ligands were synthesized. Two families of complexes were structurally and magnetically analyzed: ‘axial’ or sandwich-type complexes based on 12-crown-4 and 15-crown-5; and ‘equatorial’ complexes based on 18-crown-6. Magnetic data are supported by ab initio calculations and luminescence measurements. Significantly, the first mononuclear Ln-SMM prepared from a crown ether ligand is described.

Investigation of Frustrated Quasi-One-Dimensional Quantum Spin-Chain Materials

Copper arsenite CuAs2O4 and Copper antimonite CuSb2O4 are S=1/2 (Cu2+ 3d9 electronic configuration) quasi-one-dimensional quantum spin-chain compounds. Both compounds crystallize with tetragonal structures containing edge sharing CuO6 octahedra chains which experience Jahn-Teller distortions. The basal planes of the octahedra link together to form CuO2 ribbon-chains which harbor Cu2+ spin-chains. These compounds are magnetically frustrated with competing nearest-neighbour and next-nearest-neighbour intrachain spin-exchange interactions. Despite the similarities between CuAs2O4 and CuSb2O4, they exhibit very different magnetic properties. In this thesis work, the physical properties of CuAs2O4 and CuSb2O4 are investigated using a variety of experimental techniques which include x-ray diffraction, magnetic susceptibility measurements, heat capacity measurements, Raman spectroscopy, electron paramagnetic resonance, neutron diffraction, and dielectric capacitance measurements. CuAs2O4 exhibits dominant ferromagnetic nearest-neighbour and weaker antiferromagnetic next-nearest-neighbour intrachain spin-exchange interactions. The ratio of the intrachain interactions amounts to Jnn/Jnnn = -4.1. CuAs2O4 was found to order with a ferromagnetic groundstate below TC = 7.4 K. An extensive physical characterization of the magnetic and structural properties of CuAs2O4 was carried out. Under the effect of hydrostatic pressure, CuAs2O4 was found to undergo a structural phase transition at 9 GPa to a new spin-chain structure. The structural phase transition is accompanied by a severe alteration of the magnetic properties. The high-pressure phase exhibits dominant ferromagnetic next-nearest-neighbour spin-exchange interactions and weaker ferromagnetic nearest-neighbour interactions. The ratio of the intrachain interactions in the high-pressure phase was found to be Jnn/Jnnn = 0.3. Structural and magnetic characterizations under hydrostatic pressure are reported and a relationship between the structural and magnetic properties was established. CuSb2O4 orders antiferromagnetically below TN = 1.8 K with an incommensurate helicoidal magnetic structure. CuSb2O4 is characterized by ferromagnetic nearest-neighbour and antiferromagnetic next-nearest-neighbour spin-exchange interactions with Jnn/Jnnn = -1.8. A (H, T) magnetic phase diagram was constructed using low-temperature magnetization and heat capacity measurements. The resulting phase diagram contains multiple phases as a consequence of the strong intrachain magnetic frustration. Indications of ferroelectricity were observed in the incommensurate antiferromagnetic phase.

Exploring Capacity Building of Ontario Dental Hygiene Educators During National Curriculum Reform

In times of educational change, educators are given the task of implementing new initiatives that meet the needs of a changing environment; yet, they are often dismissed from developmental phases of the reform. This top-down structure deters educators’ personal capacity building as their knowledge, values, assumptions, and beliefs are not acknowledged or explicitly developed as part of the initiative. This study explored Ontario dental hygiene educators’ perspectives of how they may build personal capacity during an externally mandated national curriculum reform, the Entry-to-Practice Competencies and Standards for Canadian Dental Hygienists (National Competencies). Narratives were collected from 5 dental hygiene educators of diverse educational training and teaching organizations. Three themes emerged that included perceptions of structural influence, perceptions of learning access, and perceptions of identity. Each theme was linked to tasks that were required to build personal capacity for sustainable school change. The theoretical framework and the required tasks demonstrated the interconnectedness between educators, leaders, and the organization for building educators’ personal capacity.

Memorandum of expenses for work done and materials provided by Messrs. Brown and McDonell

Memorandum of expenses for work done and materials provided by Messrs. Brown and McDonell, contractors for the Port Dalhousie and Thorold Railway to Sept. 1, 1854, signed by S.D. Woodruff, Sept. 2, 1854.

Single-Molecule Magnets and Multifunctional Molecular Magnetic Materials Based on Polynuclear Metal Complexes

Our work on single molecule magnets and multifunctional magnetic materials is presented in four projects. In the first project we show for first time that heteroatomic-type pseudohalides, such as OCN-, can be employed as structure-directing ligands and ferromagnetic couplers in higher oxidation state metal cluster chemistry. The initial use of cyanato groups in Mn cluster chemistry has afforded structurally interesting MnII/III14 (1) and MnII/III/IV16 (2) clusters in which the end-on bridging cyanates show a preference in binding through their O-atom. The Mn14 compound shows entirely visible out-of-phase alternating currect signals below 5 K and large hysteresis loops below 2 K. Furthermore, the amalgamation of azido groups with the triethanolamine tripodal ligand in manganese carboxylate cluster chemistry has led to the isolation of a new ferromagnetic, high-nuclearity and mixed-valence MnII/III15Na2 (3) cluster with a large ground-state spin value of S = 14. In the second project we demonstrate a new synthetic route to purely inorganic-bridged, transition metal-azido clusters [CoII7 (4) and NiII7 (5)] and coordination polymers [{FeII/III2}n (6)] which exhibit strong ferromagnetic, SMM and long-range magnetic ordering behaviors. We also show that access to such a unique ferromagnetic class of inorganic, N-rich and O-free materials is feasible through the use of Me3SiN3 as the azido-ligand precursor without requiring the addition of any organic chelating/bridging ligand. In the last projects we have tried to bring together molecular magnetism and optics via the synthesis of multifunctional magnetic materials based on 3d- or 4f-metal ions. We decided to approach such challenge from two different directions: firstly, in our third project, by the deliberate replacement of non-emissive carboxylato ligands in known 3d-SMMs with their fluorescent analogues, without perturbing the metal-core structure and SMM properties (complexes 7, 8, and 9). The second route (last project) involves the use of naphthalene or pyridine-based polyalcohol bridging ligands for the synthesis of new polynuclear LnIII metal clusters (Ln = lanthanide) with novel topologies, SMM behaviors and luminescent properties arising from the increased efficiency of the “antenna” organic group. This approach has led us to the isolation of two new families of LnIII8 (complexes 10-13) and LnIII4 (complexes 14-20) clusters.

Letter to Mr. H.L.Vanderlip regarding a truck of cornices and other materials

Letter to Mr. H.L.Vanderlip regarding a truck of cornices and other materials. This is signed S.D. Woodruff, Aug. 17, 1876.