Structural, stratigraphic and geochemical studies of the Horwood Peninsula - Gander Bay Area, Northeast Newfoundland /

The Horwood Peninsula - Gander Bay area is located at NE Newfoundland in the Botwood Zone (Williams et a1., 1974) or in the Dunnage Zone (Williams, 1979) of the Central Mobile Belt of the Newfoundland Appalachians. The area is underlain by Middle Ordovician to possible Lower Silurian rocks of the Davidsville and Indian Islands Groups, respectively. Three conformable formations named informally : the Mafic Volcanic Formation, the Greywacke and Siltstone Formation and the Black Slate Formation, have been recognized in the Davidsville Group. The Greywacke and the Black Slate Formations pass locally into a Melange Formation. From consideration of regional structure and abundant locally-derived mafic volcanic olisto- 1iths in the melange, it is considered to have originated by gravity sliding rather than thrusting. Four formations have been recognized in the Indian Islands Group. They mainly contain silty slate and phyllite, grey cherty siltstone, green to red micaceous siltstone and limestone horizons. Repetition of lithological units by F1 folding are well-demonstrated in one of formations in this Group. The major structure in this Group on the Horwood Peninsula is interpreted to be a synclinal complex. The lithology of this Group is different from the Botwood Group to the west and is probably Late Ordovician and/or Early Silurian in age. The effects of soft-sediment deformation can be seen from the lower part of the Davidsville Group to the middle part of the Indian Islands Group indicating continuous and/or episodic slumping and sliding activities throughout the whole area. However, no siginificant depOSitional and tectonic break that could be assigned to the Taconian Orogeny has been recognized in this study. Three periods of tectonic deformation were produced by the Acadian Orogeny. Double boudinage in thin dikes indicates a southeast-northwest sub-horizontal compression and main northeast-southwest sub-horizontal extension during the D1 deformation. A penetrative, axial planar slaty cleavage (Sl) and tight to isocJ.ina1 F1 folds are products of this deformation. The D2 and D3 deformations formed S2 and S3 fabrics associated with crenulations and kink bands which are well-shown in the slates and phyllites of the Indian Islands Group. The D2 and D3 deformations are the products of vertical and northeast-southwest horizontal shortening respectively. The inferred fault between the Ordovician slates (Davidsville Group) and the siltstones (Indian Islands Group) suggested by Williams (1963, 1964b, 1972, 1978) is absent. Formations can be followed without displacement across this inferred fault. Chemically, the pillow lavas, mafic agglomerates, tuff beds and diabase dikes are subdivided into three rock suites : (a) basaltic komatiite (Beaver Cove Assemblage), (b) tholeiitic basalt (diabase dikes), (c) alkaline basalt (Shoal Bay Assemblage). The high Ti02 , MgO, Ni contents and bimodal characteristic of the basaltic komatiite in the area are comparable to the Svartenhuk Peninsula at Baffin Bay and are interpreted to be the result of an abortive volcano-tectonic rift-zone in a rear-arc basin. Modal and chemical analyses of greywackes and siltstones show the trend of maturity of these rocks increasing from poorly sorted Ordovician greywackes to fairly well-sorted Silurian siltstones. Rock fragments in greywackes indicate source areas consisting of plagiogranite, low grade metamorphic rocks and ultramafic rocks. Rare sedimentary structures in both Groups indicate a southeasterly provenance. Trace element analyses of greywackes also reveal a possible island-arc affinity.

High-Spin and Emissive Molecular Materials: Synthesis and Characterization of New Polynuclear Ni(II) Complexes from the Use of Aromatic Schiff Bases as Bridging Ligands

The employment of the bridging/chelating Schiff bases, N-salicylidene-4-methyl-o-aminophenol (samphH2) and N-naphthalidene-2-amino-5-chlorobenzoic acid (nacbH2), in nickel cluster chemistry has afforded eight polynuclear Ni(II) complexes with new structural motifs, interesting magnetic and optical properties, and unexpected organic ligand transformations. In the present thesis, Chapter 1 deals with all the fundamental aspects of polynuclear metal complexes, molecular magnetism and optics, while research results are reported in Chapters 2 and 3. In the first project (Chapter 2), I investigated the coordination chemistry of the organic chelating/bridging ligand, N-salicylidene-4-methyl-o-aminophenol (samphH2). The general NiII/tBuCO2-/samphH2 reaction system afforded two new tetranuclear NiII clusters, namely [Ni4(samph)4(EtOH)4] (1) and [Ni4(samph)4(DMF)2] (2), with different structural motifs. Complex 1 possessed a cubane core while in complex 2 the four NiII ions were located at the four vertices of a defective dicubane. The nature of the organic solvent was found to be of pivotal importance, leading to compounds with the same nuclearity, but different structural topologies and magnetic properties. The second project, the results of which are summarized in Chapter 3, included the systematic study of a new optically-active Schiff base ligand, N-naphthalidene-2-amino-5-chlorobenzoic acid (nacbH2), in NiII cluster chemistry. Various reactions between NiX2 (X- = inorganic anions) and nacbH2 were performed under basic conditions to yield six new polynuclear NiII complexes, namely (NHEt3)[Ni12(nacb)12(H2O)4](ClO4) (3), (NHEt3)2[Ni5(nacb)4(L)(LH)2(MeOH)] (4), [Ni5(OH)2(nacb)4(DMF)4] (5), [Ni5(OMe)Cl(nacb)4(MeOH)3(MeCN)] (6), (NHEt3)2[Ni6(OH)2(nacb)6(H2O)4] (7), and [Ni6(nacb)6(H2O)3(MeOH)6] (8). The nature of the solvent, the inorganic anion, X-, and the organic base were all found to be of critical importance, leading to products with different structural topologies and nuclearities (i.e., {Ni5}, {Ni6} and {Ni12}). Magnetic studies on all synthesized complexes revealed an overall ferromagnetic behavior for complexes 4 and 8, with the remaining complexes being dominated by antiferromagnetic exchange interactions. In order to assess the optical efficiency of the organic ligand when bound to the metal centers, photoluminescence studies were performed on all synthesized compounds. Complexes 4 and 5 show strong emission in the visible region of the electromagnetic spectrum. Finally, the ligand nacbH2 allowed for some unexpected organic transformations to occur; for instance, the pentanuclear compound 5 comprises both nacb2- groups and a new organic chelate, namely the anion of 5-chloro-2-[(3-hydroxy-4-oxo-1,4-dihydronaphthalen-1-yl)amino]benzoic acid. In the last section of this thesis, an attempt to compare the NiII cluster chemistry of the N-naphthalidene-2-amino-5-chlorobenzoic acid ligand with that of the structurally similar but less bulky, N-salicylidene-2-amino-5-chlorobenzoic acid (sacbH2), was made.

Grade nine teachers' perception of how teachers, parents, peers, administrators, and community members affect the development of the grade nine student /

The purpose of this study was to examine grade nine teachers' perception of how teachers, parents, peers, administrators, and community members influence the overall development of grade nine students. Ten grade nine teachers (four male and six female) participated in the study which consisted of the completion of a one hour, tape-recorded interview. The central findings were as follows: 1) the grade nine student has evolved; 2) peers have an important impact on the four developmental areas (physical, emotional, social, and academic) of the grade nine student; and 3) the role of the grade nine teacher appears to have dramatically changed over the last seventeen years. Suggestions and recommendations for future research in this field are based on findings related to the enhancement of the secondary school experience for the grade nine adolescent.

Petrography and geochemistry of the McArthur Township area, Ontario /

The McArthur Township area in the Archean Abitibi Belt of northeast Ontario contains northwesterly trending volcanic rocks which are located on a limb of a large syncline. The axial trace of the syncline passes through the adjacent Douglas Township. The Archean volcanic rocks and associated sedimentary rocks are intruded and deformed by two large plutons and a few smaller hypabyssal intrusions. A petrographic and geochemical study of the Precambrian rocks exposed 1n the study area was undertaken in order to investigate the metamorphic grade and geochemical characteristics of the rocks. All the samples were studied with the microscope and analysis of 20 major and trace elements were determined on a selection of the less altered specimens by x-ray fluorescence. Three different periods of igneous activity have occurred in the study area. The first two periods were dominated by volcanic extrusive rocks accompanied by gabbroic sills. The third cycle is the diapiric intrusion of the granitic plutons and subsequent metamorphism of the older rocks to the low to medium grade. Two periods of sedimentation are also recognized in the study area which occurred after the first and second cycle of volcanism. Chemically, the lavas are subdivided into three main associations: (1) The komatiitic association is characterized by high MgO, high Ni, low Ti02 and a low FeO*/(FeO* + MgO) ratio. They occupy the base of each volcanic cycle and some of the flows exhibit spinifex textures. (2) The tholeiitic association displays distinct iron and titanium enrichment trends in the intermediate membersor -i r (3) The calc-alkaline association contains low FeO* and TI02 and high Ni contents relative to modern calc-alkaline types. They are formed at the end of each cycle of volcanism and overlie the tholeiitic flows. All three associations of the first volcanic cycle are exposed in the study area, while the second cycle is represented by a komatiltic sequence. The volcanic rocks were possibly formed by multiple partial melting of the Archean mantle to produce parental magmas under various P - T conditions.

Grade 9 students' perceptions of the impact of a Drop Everything and Read (D.E.A.R.) program /

Educators continually look for strategies to enhance and improve the reading practices of their students. This is an especially challenging task for secondary level teachers as high school students often lack intrinsic motivation to read for pleasure (Bucher & Manning, 2004; Horton, 2005; Wooicott, Research Pty. Ltd. 2001). The purpose of this study was to detennine the effects of the Drop Everything and Read (D.E.A.R.) program on writing, on reading, and on grades, from the perspective of eight Grade 9 students. Of particular interest were the students' perceptions of the effect that participation in the program had on their grades, their writing, their motivation to reading, and their concept of themselves as readers. The eight participants were tracked over the course of a semester. Using qualitative research techniques, data were collected from four sources: two student surveys, researcher's daily field observations, students' weekly reading logs, and three open-ended one-on-one interviews. In order to gain an understanding of the impact of the D.E.A.R program, the data were corroborated, and analyzed with NVivo: N7 (2006). From the data analysis, five themes emerged as a function of the Grade 9 students' experiences in the D.E.A.R. program: Reading Preferences, Time Spent Reading, Making Associations with Reading for Pleasure, Perceptions of Self-as-Reader, and Evaluations of the D.E.A.R Program. In the interest of supporting students' positive reading habits and for the future implementation, these five themes are presented as a series of findings together with recommendations for practice.

Exploring the impact of a hands-on intervention on grade 7 girls and their feelings about self, mathematics, science, technology and related careers

Forty-five 12- and 13-year-old females attending Grade 7 in North York, Ontario were randomly selected from a group of 100 females who had volunteered to participate in a oneday hands-on workshop called It's Your Choice at Seneca College. The goals of this intervention were to broaden the career horizons of these students and to help them realize the need to continue mathematics and science through high school in order to keep occupational options unlimited. The young women were given a pre- and post-attitude survey to provide background information. In the month following participation in the workshop the students were interviewed in small groups (S students per group) to discover their perceptions of the impact of the workshop. The interviews revealed that participants felt that after the workshop their feelings of self-confidence increased, specifically with respect to working with their hands. Participants felt more aware of the usefulness and importance of the study of mathematics, science and technology, They also felt that It's Your Choice increased their interest in careers in these domains and helped them to see that these careers are viable choices for females. The interviews also revealed that many of the participants felt that in this society their roles and their choices were influenced and probably limited by the fact that they are female.

The impact of integrated programming on student attitude and achievement in grade 9 academic mathematics and science

This research studioo the effect of integrated instruction in mathematics and~ science on student achievement in and attitude towards both mathematics and science. A group of grade 9 academic students received instruction in both science and mathematics in an integrated program specifically developed for the purposes of the research. This group was compared to a control group that had received science and mathematics instruction in a traditional, nonintegrated program. The findings showed that in all measures of attitude, there was no significant difference between the students who participated in the integrated science and mathematics program and those who participated in a traditional science and mathematics program. The findings also revealed that integration did improve achievement on some of the measures used. The performance on mathematics open-ended problem-solving tasks improved after participation in the integrated program, suggesting that the integrated students were better able to apply their understanding of mathematics in a real-life context. The performance on the final science exam was also improved for the integrated group. Improvement was not noted on the other measures, which included EQAO scores and laboratory practical tasks. These results raise the issue of the suitability of the instruments used to gauge both achievement and attitude. The accuracy and suitability of traditional measures of achievement are considered. It is argued that they should not necessarily be used as the measure of the value of integrated instruction in a science and mathematics classroom.

Participation factors in optional high school health and physical education

Student enrolment rates in optional health and physical education (HPE) classes have been steadily declining, to the point where most Ontario students stop taking HPE after completion of their one required credit, typically taken in grade nine. This study looked at factors that could contribute to HPE enrolment, sampling 227 grade ten students from five schools. These factors included selfefficacy (SE), perceived autonomy support (PAS), task value (TV), motivational regulation (autonomous, AR; controlled, CR), HPE grade average and body size discrepancy (BSD). Qualitative information was also gathered from students regarding likes and dislikes ofHPE, as well as reasons for their HPE enrolment choice. Cronbach Alpha values of each scale fell within acceptable values. ANOVA analysis revealed differences between enrolment groups in SE, TV, AR, HPE grade average, and BSD (p < .05). Reasons students reported for not taking HPE included a dislike of health classes, scheduling challenges, not needing HPE for future endeavors, concerns about social self-presentation, and a dislike of sports and/or competition. This research shows important differences between students and their HPE class choices and calls for a re-evaluation of how HPE classes are structured, advertised and scheduled by high school practitioners. Future works should look toward what other factors could be at play in students' decisions for or against optional HPE and how those factors interact with the constructs that were found to be of significance in this study. Keywords: Health and physical education, high school students, participation.

Asymmetric hydrogenation of alkenes with cationic iridium(I) complexes of 2-phosphino-1-aminoferrocene ligands

Iridium complexes with bidentate P,N ligands represent a class of catalysts that significantly expand the application range of asymmetric hydrogenation. New substrate classes, for which there have previously been no suitable catalysts, can now be efficiently hydrogenated in high conversion and enantioselectivity. These substrates are often of synthetic importance, thus iridium catalysis represents a significant advance in the field of asymmetric catalysis. Planar chiral ferrocenyl aminophosphine ligands in which both heteroatoms were directly bound to the cyclopentadienyl ring were prepared by BF3-activated lithiationsubstitution in the presence of a chiral diamine in 49-59% yield and 75-85% enantiomeric excess. Some of these ligands were recrystallized to enantiomeric purity via ammonium fluoroborate salt formation of the phosphine sulfide. A crystal structure of one of these compounds was obtained and features an intramolecular hydrogen bond between the nitrogen, hydrogen, and sulfur atoms. Neutralization, followed by desulfurization, provided the free ligands in enantiomeric purity. Iridium complexes with these ligands were formed via reaction with [Ir(COD)Clh followed by anion exchange with NaBArF. These complexes were successfully applied in homogeneous hydrogenation of several prochiral substrates, providing products in up to 92% enantiomeric excess. Variation of the dimethyl amino group to a pyrrolidine group had a negative effect on the selectivity of hydrogenation. Variation of the substituents on phosphorus to bulkier ortho-tolyl groups had a positive effect, while variation to the more electron rich dicyclohexyl phosphine had a negative effect on selectivity.

Hydrosilylation and hydroboration catalyzed by imido-hydride complexes of molybdenum (IV)

This thesis describes the synthesis, structural studies, stoichiometric and catalytic reactivity of novel Mo(IV) imido hydride complexes (Cp)(ArN)Mo(H)(PMe3) (1) and (Tp )(ArN)Mo(H)(PMe3) (2). Both 1 and 2 catalyze hydrosilylation of a variety of carbonyls. Detailed kinetic and DFT studies found that 1 reacts by an unexpected associative mechanism, which does not involve Si-H addition either to the imido group or the metal. Despite 1 being a d2 complex, its reaction with PhSiH3 proceeds via a a-bond metathesis mechanism giving the silyl derivative (Cp )(ArN)Mo(SiH2Ph)(PMe3). In the presence of BPh3 reaction of 1 with PhSiH3 results in formation of (Cp)(ArN)Mo(SiH2Ph)(H)2 and (Cp)(ArN)Mo(SiH2Ph)2(H), the first examples ofMo(VI) silyl hydrides. AI: 1 : 1 reaction between 2, PhSiD3 and carbonyl substrate established that hydrosilylation is not accompanied by deuterium incorporation into the hydride position of the catalyst, thus ruling out the conventional mechanism based on carbonyl insertion carbonyl. As 2 is nomeactive to both the silane and ketone, the only mechanistic alternative we are left with is that the metal center activates the carbonyl as a Lewis acid. The analogous nonhydride mechanism was observed for the catalysis by (ArN)Mo(H)(CI)(PMe3), (Ph3P)2(I)(O)Re(H)(OSiMe2Ph) and (PPh3CuH)6. Complex 2 also catalyzes hydroboration of carbonyls and nitriles. We report the first case of metal-catalyzed hydroboration of nitriles as well as hydroboration of carbonyls at very mild conditions. Conversion of carbonyl functions can be performed with high selectivities in the presence of nitrile groups. This thesis also reports the first case of the HlH exchange between H2 and Si-H of silanes mediated by Lewis acids such as Mo(IV) , Re(V) , Cu(I) , Zn(II) complexes, B(C6Fs)3 and BPh3.

Triarylamminium radical-cation complexes: design and magnetic properties and Base-catalyzed hydrosilylation: mechanism and substrate scope

1. Triarylamminium radical-cation complexes. The detailed study of manganese, copper and nickel metal-radical complexes with triarylamminium ligands was conducted. Stable, neutral and pseudo-octahedral coordination monometallic complexes with simple monodentate 2,2`-bipyridine ligand containing a redox-active N,N`-(4,4`-dimethoxydiphenyl-amino) substituent were synthesized and fully characterized. The one-electron oxidation process and formation of persistent radical-cation complexes was observed by cyclic voltammetry and spectroelectrochemical measurements. Evans method measurements were performed with radical-cation complexes generated by chemical one-electron oxidation with NOPF6 in acetonitrile. The experimental results indicate ferromagnetic coupling between metal and triarylamminium cation in manganese (II) complex and antiferromagnetic coupling in nickel (II) complex. This data is supported by DFT calculations which also lend weight to the  spin polarization mechanism as an operative model for magnetic exchange coupling. Neutral bimetallic complexes with a new ditopic ligand were synthesized and fully characterized, including magnetic and electrochemical studies. Chemical oxidation of these precursor complexes did not generate radical-cations, but dicationic complexes, which was confirmed by UV-vis and EPR-experiments, as well as varied temperature magnetic measurements. DFT calculations for radical-cation complexes are included. A synthetic pathway for polytopic ligand with multiple redox-active triarylamine sites was developed. The structure of the ligand is presumably suitable for -spin polarization exchange model and allows for production of polymetallic complexes having high spin ground states. 2. Base-catalyzed hydrosilylation. A simple reductive base-catalyzed hydrosilation of aldehydes and ketones was adapted to the use of the cheap, safe, and non-toxic polymethylhydrosiloxane (PMHS) instead of the common PhSiH3 and (EtO)3SiH, which present significant cost and safety concerns, respectively. The conversion of silane into pentacoordinate silicate species upon addition of a base was studied in details for the cases of phenyl silane and PMHS and is believed to be essential for the hydrosilylation process. We discovered that nucleophiles (a base or fluoride-anion) induced the rearrangement of PMHS and TMDS into light silanes: MeSiH3 and Me2SiH2, respectively. The reductive properties of PMHS under basic conditions can be attributed to the formation of methyl silane and its conversion into a silicate species. A procedure for the generation of methyl silane and its use in further efficient reductions of aldehydes and ketones has been developed. The protocol was extended to the selective reduction of esters and tertiary amides into alcohols and aldimines into amines with good isolated yields and reduction of heterocyclic compounds was attempted.

Correlation Among Math Anxiety, Attitudes Toward Math, and Math Achievement in Grade 9 Students: Relationships Across Gender

This research evaluated (a) the correlation between math anxiety, math attitudes, and achievement in math and (b) comparison among these variables in terms of gender among grade 9 students in a high school located in southern Ontario. Data were compiled from participant responses to the Attitudes Toward Math Inventory (ATMI) and the Math Anxiety Rating Scale for Adolescents (MARS-A), and achievement data were gathered from participants’ grade 9 academic math course marks and the EQAO Grade 9 Assessment of Mathematics. Nonparametric tests were conducted to determine whether there were relationships between the variables and to explore whether gender differences in anxiety, attitudes, and achievement existed for this sample. Results indicated that math anxiety was not related to math achievement but was a strong correlate of attitudes toward math. A strong positive relationship was found between math attitudes and achievement in math. Specifically, self-confidence in math, enjoyment of math, value of math, and motivation were all positive correlates of achievement in math. Also, results for gender comparisons were nonsignificant, indicating that gender differences in math anxiety, math attitudes, and math achievement scores were not prevalent in this group of grade 9 students. Therefore, attitudes toward math were considered to be a stronger predictor of performance than math anxiety or gender for this group.

Half-sandwich Complexes of Ruthenium; Synthesis and Application to Catalysis

This thesis describes syntheses and catalytic reactivity of several half-sandwich complexes of ruthenium. The neutral ruthenium trihydride complex, Cp(PPri3)RuH3(1), can efficiently catalyse the H/D exchange reaction between various organic substrates and deuterium sources, such as benzene-d6. Moreover, the H/D exchange reactions of polar substrates were also observed in D2O, which is the most attractive deuterium source due to its low cost and low toxicity. Importantly, the H/D exchange under catalytic conditions was achieved not only in aromatic compounds but also in substituted liphatic compounds. Interestingly, in the case of alkanes and alkyl chains, highly selective deuterium incorporation in the terminal methyl positions was observed. It was discovered that the methylene units are engaged in exchange only if the molecule contains a donating functional group, such as O-and N-donors, C=C double bonds, arenes and CH3. The cationic half-sandwich ruthenium complex [Cp(PPri3)Ru(CH3CN)2]+(2) catalyses the chemoselective mono-addition of HSiMe2Ph to pyridine derivatives to selectively give the 1,4-regiospecific, N-silylated products. An ionic hydrosilylation mechanismis suggested based on the experiments. To support this mechanistic proposal, kinetic studies under catalytic conditions were performed. Also, the 1,4-regioselective mono-hydrosilylation of nitrogen containing compounds such as phenanthroline, quinoline and acridine can be achieved with the related Cp*complex [Cp*(phen)Ru(CH3CN)]+(3) (phen = 1,10-phenanthroline) and HSiMe2Ph under mild conditions. The cationic ruthenium complex 2 can also be used as an efficient catalyst for transfer hydrogenation of various organic substrates including carbonyls, imines, nitriles and esters. Secondary alcohols, amines, N-isopropylidene amines and ether compounds can be obtained in moderate to high yields. In addition, other ruthenium complexes, 1,3 and [Cp*(PPri3)Ru(CH3CN)2]+(4), can catalyse transfer hydrogenation of carbonyls although the reactions were sluggish compared to the ones of 2. The possible intermediate, Cp(PPri3)Ru(CH3CN)(H), was characterized by NMR at low temperature and the kinetic studies for the transfer hydrogenation of acetophenone were performed. Recently, chemoselective reduction of acid chlorides to aldehydes catalysed by the complex 2 was reported. To extend the catalytic reactivity of 2, reduction of iminoyl chlorides, which can be readily obtained from secondary amides, to the corresponding imines and aldehydes was investigated. Various substituted iminoyl chlorides were converted into the imines and aldehydes under mild conditions and several products were isolated with moderate yields.

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.

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.