The application of the structural correlation method to determine the reaction coordinate for a putative ring closure reaction

The cr ystal structure of the compound 2-benzoylethylidene-3-(2,4- dibromophenyl)-2,3-dihydro-5-phenyl-l,3,4-thiadiazole* C23H16Br2NZOS (BRMEO) has been determined by using three dimensiona l x-ray diffraction data. The crys tal form is monoclinic, space group P21/c, a = 17.492(4), o -.t' 0 R 0 b =: 16.979(1), c = 14.962(1) A, "X. =o= 90 ',= 106.46(1) , z = 8, graphite-monochromatized Mo~ rad iation, Jl= 0.710J3~, D = 1.62g/cc and o D = 1.65g/cc. The data were col lected on ~ Nonius CAD-4 c diffractometer. The following atoms were made anisotropic: Br, S, N, 0, C7, and C14-C16 for each i ndependent molecu le ; the rest were left isotropic. For 3112 independent refl ec tions with F > 6G\F), R == 0.057. The compound has two independent molecules within the asymmetric unit. Two different conformers were observed which pack well together. /l The S---O interaction distances of 2.493(6) and 2 . 478(7) A were observed for molecules A and B respectively. These values are consistent with earlier findings for 2-benzoylmethylene-3-(2,4-dibromophenyl)- ~~ 2,3-dihydro-5-phenyl-l,3,4-thiadiazole C22H14Br2N20S (BRPHO) and 2-benzoylpropylidene-3-(2,4-dibromophenyl)-2,3-dihydroiii ,'r 5-phenyl-l,3,4-thiadiazole C24H18Br2N20S (BRPETO ) where S---O distances are l ess than the van der Waals (3.251\) but greater than those expected for () a single bond (1.50A). From the results and the literature it appears obvious that the energy/reaction coordinate pathway has a minimum between the end structures (the mono- and bicyclic compounds). * See reference (21) for nomenclature.

The vibrational spectra and the normal coordinate analysis of thiocarbonye halides /|nby C. R. Subramaniam. -- 260 St. Catharines, Ont. : [s. n.],

The infrared and the Raman spectra of eSelF has been obtained for the first time and has been analysed to give the in-plane normal vibrational frequencies of the molecule, in the ground state. A normal co-ordinate analysis has been carried out for the molecules CSF2, CSClF and eSel 2 using a Urey-Bradley type of potential function and the elements of the [L] matrix elements, the distribution of the potential energy in Urey-Bradley space, and the displacement vector diagrams for the normal modes of vibration for these molecules, have been obtained. The bond for~e constants obtained through the normal co-ordinate analysis, have given some interesting results. The stretching force constant, Kes ' varies markedly with halogen substitution and the force constants KeF and Keel also vary with substitution.

Electrophysiological correlates of performance monitoring in middle and late adolescence

The ability to monitor and evaluate the consequences of ongoing behaviors and coordinate behavioral adjustments seems to rely on networks including the anterior cingulate cortex (ACC) and phasic changes in dopamine activity. Activity (and presumably functional maturation) of the ACC may be indirectly measured using the error-related negativity (ERN), an event-related potential (ERP) component that is hypothesized to reflect activity of the automatic response monitoring system. To date, no studies have examined the measurement reliability of the ERN as a trait-like measure of response monitoring, its development in mid- and late- adolescence as well as its relation to risk-taking and empathic ability, two traits linked to dopaminergic and ACC activity. Utilizing a large sample of 15- and 18-year-old males, the present study examined the test-retest reliability of the ERN, age-related changes in the ERN and other components of the ERP associated with error monitoring (the Pe and CRN), and the relations of the error-related ERP components to personality traits of risk propensity and empathy. Results indicated good test-retest reliability of the ERN providing important validation of the ERN as a stable and possibly trait-like electrophysiological correlate of performance monitoring. Ofthe three components, only the ERN was of greater amplitude for the older adolescents suggesting that its ACC network is functionally late to mature, due to either structural or neurochemical changes with age. Finally, the ERN was smaller for those with high risk propensity and low empathy, while other components associated with error monitoring were not, which suggests that poor ACe function may be associated with the desire to engage in risky behaviors and the ERN may be influenced by the extent of individuals' concern with the outcome of events.

3D movement and muscle activity patterns in a violin bowing task

Objective: Overuse injuries in violinists are a problem that has been primarily analyzed through the use of questionnaires. Simultaneous 3D motion analysis and EMG to measure muscle activity has been suggested as a quantitative technique to explore this problem by identifying movement patterns and muscular demands which may predispose violinists to overuse injuries. This multi-disciplinary analysis technique has, so far, had limited use in the music world. The purpose of this study was to use it to characterize the demands of a violin bowing task. Subjects: Twelve injury-free violinists volunteered for the study. The subjects were assigned to a novice or expert group based on playing experience, as determined by questionnaire. Design and Settings: Muscle activity and movement patterns were assessed while violinists played five bowing cycles (one bowing cycle = one down-bow + one up-bow) on each string (G, D, A, E), at a pulse of 4 beats per bow and 100 beats per minute. Measurements: An upper extremity model created using coordinate data from markers placed on the right acromion process, lateral epicondyle of the humerus and ulnar styloid was used to determine minimum and maximum joint angles, ranges of motion (ROM) and angular velocities at the shoulder and elbow of the bowing arm. Muscle activity in right anterior deltoid, biceps brachii and triceps brachii was assessed during maximal voluntary contractions (MVC) and during the playing task. Data were analysed for significant differences across the strings and between experience groups. Results: Elbow flexion/extension ROM was similar across strings for both groups. Shoulder flexion/extension ROM increaslarger for the experts. Angular velocity changes mirrored changes in ROM. Deltoid was the most active of the muscles assessed (20% MVC) and displayed a pattern of constant activation to maintain shoulder abduction. Biceps and triceps were less active (4 - 12% MVC) and showed a more periodic 'on and off pattern. Novices' muscle activity was higher in all cases. Experts' muscle activity showed a consistent pattern across strings, whereas the novices were more irregular. The agonist-antagonist roles of biceps and triceps during the bowing motion were clearly defined in the expert group, but not as apparent in the novice group. Conclusions: Bowing movement appears to be controlled by the shoulder rather than the elbow as shoulder ROM changed across strings while elbow ROM remained the same. Shoulder injuries are probably due to repetition as the muscle activity required for the movement is small. Experts require a smaller amount of muscle activity to perform the movement, possibly due to more efficient muscle activation patterns as a result of practice. This quantitative multidisciplinary approach to analysing violinists' movements can contribute to fuller understanding of both playing demands and injury mechanisms .

A speculative systems model of the dynamic interaction among students, faculty and administration in the community college, with particular reference to intrinsic motivation and the teacher-administrator interface

The challenge the community college faces in helping meet the needs of the living open system of society is examined in this study. It is postulated that internalization student outcomes are required by society to reduce entropy and remain self-renewing. Such behavior is characterized as having an intrinsically motivated energy source and displays the seeking and conquering of challenge, the development of reflective knowledge and skill, full use of all capabilities, internal control, growth orientation, high self-esteem, relativistic thinking and competence. The development of a conceptual systems model that suggests how transactions among students, faculty and administration might occur to best meet the needs of internalization outcomes in students, and intrinsic motivation in faculty is a major purpose of this study. It is a speculative model that is based on a synthesis of a wide variety of variables. Empirical evidence, theoretical considerations, and speculative ideas are gathered together from researchers and theoretici.ans who are working on separate answers to questions of intrinsic motivation, internal control and environments that encourage their development. The model considers the effect administrators·have on faculty anq the corresponding effect faculty may have on students. The major concentration is on the administrator--teacher interface.For administrators the model may serve as a guide in planning effective transactions, and establishing system goals. The teacher is offered a means to coordinate actions toward a specific overall objective, and the administrator, teacher and researcher are invited to use the model to experiment, innovate, verify the assumptions on which the model is based, and raise additional hypotheses. Goals and history of the community colleges in Ontario are examined against current problems, previous progress and open system thinking. The nature of the person as a five part system is explored with emphasis on intrinsic motivation. The nature, operation, conceptualization, and value of this internal energy source is reviewed in detail. The current state of society, education and management theory are considered and the value of intrinsically motivating teaching tasks together with "system four" leadership style are featured. Evidence is reviewed that suggests intrinsically motivated faculty are needed, and "system four" leadership style is the kind of interaction-influence system needed to nurture intrinsic motivation in faculty.

Correlates of reading readiness in kindegarten children

The gene,nil purpose (If this thesis was to examine certain variables considered to be associated with reading readiness in kindergarten children Twenty-four children from a parent-funded parochial school i.n 5t Catharines. Ontaj-io were exanlined in this study, The children.'s reading readiness level, measured by the Test of Ea1'1y Reading Ability (JERA:) and by teacher"s ratings was correlated with various cognitive variables, These variables consisted (If a rough index of intelligence as measured by the Peabody Picture Vocabulary Test - Revised CPPVT-Rl Form M, mean len.gth of utterance (MUn, the sum of relative,. subordinate and coordinate clauses, the !wmber of core statements children make when telling stories and a memory test. All but the memory test related to at least one measure of reading readiness, Although the memory test did not correlate significantly with reading readiness, the children appeaj~ed to be sensitive to the stimulus set size in terms of their study time, In addition. interi'uption in the interval between studying the stimuli and the ,reca1i test had a negathre effect on pe.rfornlance and set size had a substantial effect 011 recognition performance, The educational implications of these correlates of reading readiness are discussed as weH as the implications for future research.

Ethnic conflicts and international politics : an analysis of the communal regional, and global dimensions of the Cyprus problem

The thesis assesses the impact of international factors on relations between Greek and Turkish Cypriots during and after the Cold War. Through an analysis of the Cyprus problem it explores both why external actors intervene in communal conflicts and how they influence relations between ethnic groups in plural societies. The analytical framework employed throughout the study draws on contributions of International Relations theorists and students of ethnic conflict. The thesis argues that, as in the global political system, relations between ethnic groups in unranked communal systems are anarchic; that is, actors within the system do not recognize a sovereign political authority. In bipolar communal systems dominated by two relatively equal groups, the struggle for security and power often leads to appeals for assistance from external actors. The framework notes that neighboring states and Great Powers may heed calls for assistance, or intervene without a prior request, if it is in their interest to do so. The convergence of regional and global interests in communal affairs exacerbates ethnic conflicts and precludes the development of effective political institutions. The impact of external intervention in ethnic conflicts has the potential to alter the basis of communal relations. The Cyprus problem is examined both during and after the Cold War in order to gauge how global and regional actors and the structure of their respective systems have affected relations between ethnic groups in Cyprus. The thesis argues that Cyprus's descent into civil war in 1963 was due in part to the entrenchment of external interests in the Republic's constitution. The study also notes that power politics involving the United States, Soviet Union, Greece and Turkey continued to affect the development of communal relations throughout the 1960s, 70s, and, 80s. External intervention culminated in July and August 1974, after a Greek sponsored coup was answered by Turkey's invasion and partition of Cyprus. The forced expulsion of Greek Cypriots from the island's northern territories led to the establishment of ethnically homogeneous zones, thus altering the context of communal relations dramatically. The study also examines the role of the United Nations in Cyprus, noting that its failure to settle the dispute was due in large part to a lack of cooperation from Turkey, and the United States' and Soviet Union's acceptance of the status quo following the 1974 invasion and partition of the island. The thesis argues that the deterioration of Greek-Turkish relations in the post-Cold War era has made a solution to the dispute unlikely for the time being. Barring any dramatic changes in relations between communal and regional antagonists, relations between Greek and Turkish Cypriots will continue to develop along the lines established in July/August 1974. The thesis concludes by affirming the validity of its core hypotheses through a brief survey of recent works touching on international politics and ethnic conflict. Questions requiring further research are noted as are elements of the study that require further refinement.

Investigation of molecular polarizabilities and derivatives in halomethanes

The research undertaken was to obtain absolute Raman intensities for the symmetric stretching vibrations of the methyl halides, CH3X with (X=F, CI, Br), by experiment and theory. The intensities were experimentally measured using the Ar+ ion gas laser as excitation source, a Spex 14018 double monochromator and a RCA C-31034 photomultiplier tube as detector. These intensities arise from changes in the derivative of the polarizability (8 a'), with respect to vibration along a normal coordinate (8qi). It was intended that these derivatives obtained with respect to normal coordinates would be converted to derivatives with respect to internal coordinates, for a quantitative comparison with theory. Theoretical numerical polarizability derivatives for the stretching vibrations are obtained using the following procedure. A vibration was simulated in the molecule by increasi.ng and decreasing the respective bond by the amount ±o.oosA for the C-H bonds and ±o.oIA for the C-X (X=F, CI, Br) bond. The derivative was obtained by taking the difference in the polarizability for the equilibrium geometry and the geometry when a particular bond is changed. This difference, when divided by the amount of change in each bond and the number of bonds present results in the derivative of the polarizability with respect to internal coordinate i.e., !1u/!1r. These derivatives were obtained by two methods: I} ab initio molecular orbital calculation and 2} theory of atoms in molecules (AIM) analysis. Due to errors in the experimental setup only a qualitative analysis of the results was undertaken relative to the theory. Theoretically it is predicted that the symmetric carbonhalogen stretch vibrations are more intense than the respective carbon-hydrogen stretch, but only for the methyl chloride and bromide. The carbon fluorine stretch is less intense than the carbon-hydrogen stretch, a fact which is attributed to the small size and high electronegativity of the fluorine atom. The experimental observations are seen to agree qualitatively with the theory results. It is hoped that when the experiment is repeated, a quantitative comparison can be made. The analysis by the theory of atoms in molecules, along with providing polarizabilities and polarizability derivatives, gives additional information outlined below. The theory provides a pictorial description of the main factors contributing to the molecular polarizability and polarizability derivative. These contributions are from the charge transfer and atomic dipole terms i.e., transfer of charge from one atom to another and the reorganization of atomic electronic charge distribution due to presence of an electric field. The linear relationship between polarizability and molecular volume was also observed.

On the path integral formulation and the evaluation of quantum statistical averages

Four problems of physical interest have been solved in this thesis using the path integral formalism. Using the trigonometric expansion method of Burton and de Borde (1955), we found the kernel for two interacting one dimensional oscillators• The result is the same as one would obtain using a normal coordinate transformation, We next introduced the method of Papadopolous (1969), which is a systematic perturbation type method specifically geared to finding the partition function Z, or equivalently, the Helmholtz free energy F, of a system of interacting oscillators. We applied this method to the next three problems considered• First, by summing the perturbation expansion, we found F for a system of N interacting Einstein oscillators^ The result obtained is the same as the usual result obtained by Shukla and Muller (1972) • Next, we found F to 0(Xi)f where A is the usual Tan Hove ordering parameter* The results obtained are the same as those of Shukla and Oowley (1971), who have used a diagrammatic procedure, and did the necessary sums in Fourier space* We performed the work in temperature space• Finally, slightly modifying the method of Papadopolous, we found the finite temperature expressions for the Debyecaller factor in Bravais lattices, to 0(AZ) and u(/K/ j,where K is the scattering vector* The high temperature limit of the expressions obtained here, are in complete agreement with the classical results of Maradudin and Flinn (1963) .

The electronic spectra and the determination of the excited state geometry of 3A" propynal /|nby Chhiu-Tsu Lin. -- 260 St. Catharines, Ont. : [s. n.],

Impurity free eluission spectra of HCCCHO and DCCCHO have been rephotographed using the electronic-energy-exchange method with benzene as a carrier gas. The near ultraviolet spectra of ReeCHO and DCCCHO were photographed in a sorption under conditions of high resolution with absorption path lengths up to 100 meters. The emission and absorption spectra of Propynal resulting from 3 n 1 t 1\ - A excitation has been reanalyzed in som.e detail. Botrl of the eH out-of-plane wagging modes were found to have negative anharmonicity. A barrier height of 56.8/0.0 cm- 1 and a nonplanar oft , , equilibrium angle of 17 3 /30 are calculated for the V 10/ lJ 11 modes. The in-plane and out-of-plane v1. brational modes in the 3A." and 1a~. ' elec ronic states of Propynal were subjected to a normal coordinate treatment in the approximat :on of tIle Urey-Bradley force field. From the relative oscillator strengths of the trans1·t1·0ns connect i ng t he v ibrat1•0n1ess lA' , state and t,he V1· bron1·C 3· if levels of the A state, the differences in equilibrium configuration were evaluated from an approximate Franck-Condon analysis based on the ground state normal coordinates. As this treatment gave 512 possible geometrical structures for the upper state, it 4 was necessary to resort to a comparison of the observed and calculated moments of inertia along with chemical intuition to isolate the structure. A test of the correctness of the calculated structure change and the vibrational assignment was raade by evaluating the intensities of the inplane and out-oi-plane fundarnental, sequence, and cross sequellce transitions y the exact Franck-Condon method.

ESI-MS[n] of anticancer pt[iv] organoamido complexes and their interactions with DNA-model compounds /

The general solution behaviour and" the major fragmentation pathways of the anticanceractive PtIV coordination complexes, trans, trans, cis, cis-[PtCIOH{N(pFC6F4) CH2h(pY)2] (1), trans, cis, cis-[Pt(OH)2{N(p-FC6F4)CH2h(Py)2] (2), trans, cis, cis-[Pt(OH)2{N(p-HC6F4)CH2h(Py)2] (3), trans, trans, cis, cis-[PtCIOH{N(pHC6F4) CH2h(Py)2] (4), and trans, trans, cis, cis-[PtOH(OCH3){N(p-HC6F4)CH2h(PY)2] (5) (Py = pyridine) have been deduced by positive-ion tandem-in-time ESI-MS. Overall, the acquired full-scan, positive-ion ESI-MS spectra of 2, 3, and 5 were characterized by the presence of relatively low-intensity [M+Nar and [M+Kt mass spectral peaks, whereas those of 1 and 4 were dominated by extremely intense [M+Hr peaks. Complexes 2 and 3 were also noted to form [2M+Ht and [2M+Nat dilneric cations. The source of Na + and K+ ions is believed to be the sample, the solvent systems used or the transport line carrying the sample solutions into the ES ion source. Further, the fragmentation pathway of all complexes studied was found to be almost identical with concurrent loss of py and H20 molecules, loss of a {N(p-YC6F4)CH2} (Y = F, H) group and/or concomitant release of the latter group and a py ligand being the most conunon. The photochemical degradation behaviour of 1 and 2 was also investigated using either fluorescent or ultraviolet light and some products of that degradation were positively identified. Altogether, light irradiation of solutions of both complexes resulted in cation cationisation, reductive-elimination, ligand-release, ligand-exchange and ligand-addition reactions. Finally, positive- and negative-ion ESI-MSn spectra of 5' -GMP, guanosine, inosine and products of their reactions with 1, 2,3, and 4 were also recorded. On the whole, full-scan ESI-MS spectra of the pure nucleobases revealed the presence of cationic and anionic species that are highly reflective of both their solution ionic composition and their propensity t9 form polymeric clusters. Analyses of mass spectra acquired from their reaction solutions with the aforementioned platinum complexes indicated very slow kinetics. However, all complexes investigated formed, to various degrees, Pt-nucleobase adducts with guanosine and inosine, but not with 5'-GMP. The products included species having coordination numbers of III, IV, V, and VI, among which the first-time· observed, coordinatively saturated, jive-coordinate PtlI-nucleobase complexes were of most interest. The latter complexes are presumably stabilized by 7tback- donation involving the filled d orbitals of the PtII centre and the empty pz· orbital of MeCN. All products, whose peaks appeared inlull-scan ESI-MS spectra, are believed to represent solution species rather than artifacts of gas-phase processes. Finally, negativeion ESI-MSn spectra recorded in reaction solutions of 1 and 4 with guanosine and of the latter complex with inosine revealed the negative-ion-ESI-MS first-time observed, noncovalent, nucleoside-chloride adducts, with the source of chloride anion being complexes 1 and 4 theillselves. In contrast, no such adducts were observed to form with Na25'-GMP or its protonated fonn. Few suggestions are offered for the possible cause(s) behind the absence of such adduct ions.

The mechanism of formation of the mixed boron trihalide adducts of trimenthylamine

Boron trihalide and mixed boron trihalide adducts of trimethylamine have been prepared, and characterized by proton and fluorine N.M.R. spectroscopy. The acceptor power of the boron trihalides was seen to increase in the order BF3 < BC13 < BBr3 < BI3, corroborating previous evidence. The mixed boron trihalides had intermediate Lewis acidities. Solution reactions between adducts and free boron trihalides rapidly led to the formation of mixed adducts when the free boron trihalide is a stronger Lewis acid than that in the adduct. A slower reaction is observed when the free BX3 is a weaker Lewis aoid than that complexed. The mechanism of halogen exchange leading to the mixed (CH3)3NBX3 adducts was investigated. 10B labelling experiments precluded B-N bond rupture as a possible mechanism in solution; results are discussed in terms of halogen-bridged intermediates. Pre-ionization may be important for some systems. At higher temperatures, during gas phase reactions,B-N coordinate bond rupture may be the initial step of reaction. Two mixed adduots, namely (CH3)3NBClBr2 and (CH3)3NBHOIBr were prepared and characterized by Mass Spectrometry

New Building Blocks for Dual-Property Molecule-Based Magnets

Two classes of compounds have been prepared and characterized as building blocks for chiral magnets and ferromagnetic conductors. In the fIrst project, the organic framework of a pentadentate, (N302) macro cycle has been synthetically modifIed to introduce phenyl substituents into its organic framework and the synthesis of four new [Fe(In(N302)(CN)2] complexes (I) - (IV) is presented. [Molecular diagram availble in pdf] This work represents the fIrst structural and magnetic studies of a family of spin crossover macrocycles that comprise of both structural and stereo-isomers. Magnetic susceptibility and Mossbauer data for the R,R-complex (I) is consistent with both a thermal and a light induced spin crossover transition. The X-ray data supports a change in geometry accompanying the thermal spin transition, from a high spin (HS) 7 -coordinate complex at room temperature to a low spin (LS) 5-coordinate complex at 100 K. The crystal structure ofthe racemic complex (III) reveals a HS, 7-coordinate complex at 200 K that undergoes no signifIcant structural changes on cooling. In contrast, the magnetic - susceptibility and Mossbauer data collected on a powder sample of the racemic complex are consistent with a LS complex. Finally, the meso complex (IV) was prepared and its structure and magnetic properties are consistent with a 5-coordinate LS complex that remains low spin, but undergoes conformational changes on cooling in solution. The chiral [Fe(H)(N302)(CN)2] macro cycle (I), together with its Mn(H) and Fe(H) derivatives have also been exploited as building blocks for the self-assembly of chiral magnets. In the second project, a synthetic route for the preparation of tetrathiafulvalene (TTF) donors covalently attached to a diisopropyl verdazyl radical via a cross conjugated pyridyl linker IS presented. Following this strategy, four new TTF-py- (diisopropyl)verdazyl radicals have been prepared and characterized (V) - (VIII) . [Molecular diagram available in pdf] The first (2:1) charge transfer complex ofa TTF-py-(diisopropyl)verdazyl radical donor and a TCNQ acceptor has been prepared and structurally characterized. The crystal packing shows that the donor and acceptor molecules are organized in a mixed stacking arrangement consistent with its insulating behaviour. EPR and magnetic susceptibility data support intramolecular ferromagnetic interactions between the TTF and the verdazyl radicals and antiferromagnetic interactions between TTF donors within a stack. In an attempt to increase the intramolecular exchange interaction between the two radicals, a TTF-x-(diisopropyl)verdazyl radical (IX) was prepared, where the two radicals are connected ia a conjugated divinylene linker. The neutral radical donors stack in a more favourable head-to-head arrangement but the bulky isopropyl groups prevent the donor radicals from stacking close enough together to facilitate good orbital overlap. [Molecular diagram available in pdf].

The Synthesis and Coordination Chemistry of Two Families of Polydentate Ligands - Exploring Their Potential for the Preparation of Molecule-Based Magnets

The synthesis and studies of two classes of poly dentate ligands are presented as two projects. In project 1, four new carboxamide ligands have been synthesised via the condensation of 2,2',6,6'-tetrachloroformyl-4,4'-bipyridine or 2,6-dichloroformyl pyridine together with heterocyclic amines containing pyridine or pyrazole substituents. The coordination chemistry of these ligands has been investigated and studies have shown that with a Cu(II) salt, two carboxamide ligands LJ and L2 afford large clusters with stoichiometries [Cu8(L1)4Cl16].CHCl3.5H2O.7CH3OH (I) and [Cu9(L2)6Cl6].CH3OH.5H2O.(C2H5)3N (II) respectively. [molecular diagram availabel in pdf]. X-ray diffraction studies of cluster (I) reveal that it has approximate S4 symmetry and is comprised of four ligands and eight copper (II) centers. Here, coordination takes place via amide 0 atoms, and pyrazole nitrogens. This complex is the first reported example of an octanuclear copper cluster with a saddle-shaped structure. The second cluster comprises nine copper ions that are arranged in a cyclic array. Each ligand coordinates three copper centers and each copper ion shares two ligands to connect six ligands with nine copper ions. The amide nitrogens are completely deprotonated and both amide Nand 0 atoms coordinate the metal centres. The cluster has three-fold symmetry. There are six chloride ions, three of which are bridging two neighbouring Cu(II) centres. Magnetic studies of (I) and (II) reveal that both clusters display weak antiferromagnetic interactions between neighbouring Cu(II) centers at low temperature. In the second project, three complexes with stoichiometries [Fe[N302](SCN)2]2 (III), R,R-[Fe[N3O2](SCN)2 (IV) and R,R-]Fe[N3O2](CN)2] (V) were prepared and characterized, where [N302] is a pentadentate macrocycle. Complex (III) was prepared via the metal templated Schiff-base condensation of 2,2',6,6'-tetraacetyl-4,4'-bipyridine together with 3,6-dioxaoctane-I,8-diamine and comprises of a dimeric macro cycle where the two Fe(II) centres are in a pentagonal-bipyramidal environment with the [N302] ligands occupying the equatorial plane and two axial NCS ligands. Complexes (IV) and (V) were prepared via the condensation of 2,6-diacetylpyridine together with a chiral diamine in the presence of FeCh. The synthetic strategy for the preparation of the chiral diamine (4R,5R)-4,5-diphenyl-3,6-dioxa-I,8-octane-diamine was elucidated. The chirality of both macrocycles (IV) and (V) was probed by circular dichroism spectroscopy. The crystal structure of (IV) at 200 K contains two independent molecules in the unit cell, both of which contain a hepta-coordinated Fe(II) and axial NCS ligands. Variable temperature magnetic susceptibility and structural studies are consistent with a high spin Fe(II) complex and show no evidence of any spin crossover behaviour. In contrast, the bis cyanide derivative (V) crystallizes with two independent molecules in the unit cell, both of which have different coordination geometries consistent with different spin states for the two Fe(II) centres. At 250 K, the molecular structure of (V) shows the presence of both 7- and a 6-coordinate Fe(II) complexes in the crystal lattice. As the temperature is lowered, the molecules undergo a structural change and at 100 K the structural data is consistent with a 6- and 5-coordinate Fe(II) complex in the unit cell. Magnetic studies confirm that this complex undergoes a gradual, thermal, spin crossover transition in the solid state. Photomagnetic measurements indicate this is the first chiral Fe (II) sea complex to exhibit a LIESST.

Certificate of Membership United Empire Loyalists Association of Canada

A certificate that Francis Bond Head Wilson "being of United Empire Loyalist Descent has been regularly proposed, balloted for, and elected a member of this association." It is dated September 14th, 1934.