The infared optical properties of Sr2RuO4 and SmTiO3 including an object-oriented resistivity interface /

The perovskite crystal structure is host to many different materials from insulating to superconducting providing a diverse range of intrinsic character and complexity. A better fundamental description of these materials in terms of their electronic, optical and magnetic properties undoubtedly precedes an effective realization of their application potential. SmTiOa, a distorted perovskite has a strongly localized electronic structure and undergoes an antiferromagnetic transition at 50 K in its nominally stoichiometric form. Sr2Ru04 is a layered perovskite superconductor (ie. Tc % 1 K) bearing the same structure as the high-tem|>erature superconductor La2_xSrrCu04. Polarized reflectance measurements were carried out on both of these materials revealing several interesting features in the far-infrared range of the spectrum. In the case of SmTiOa, although insulating, evidence indicates the presence of a finite background optical conductivity. As the temperature is lowered through the ordering temperature a resonance feature appears to narrow and strengthen near 120 cm~^ A nearby phonon mode appears to also couple to this magnetic transition as revealed by a growing asymmetry in the optica] conductivity. Experiments on a doped sample with a greater itinerant character and lower Neel temperature = 40 K also indicate the presence of this strongly temperature dependent mode even at twice the ordering temperature. Although the mode appears to be sensitive to the magnetic transition it is unclear whether a magnon assignment is appropriate. At very least, evidence suggests an interesting interaction between magnetic and electronic excitations. Although Sr2Ru04 is highly anisotropic it is metallic in three-dimensions at low temperatures and reveals its coherent transport in an inter-plane Drude-like component to the highest temperatures measured (ie. 90 K). An extended Drude analysis is used to probe the frequency dependent scattering character revealing a peak in both the mass enhancement and scattering rate near 80 cm~* and 100 cm~* respectively. All of these experimental observations appear relatively consistent with a Fermi-liquid picture of charge transport. To supplement the optical measurements a resistivity station was set up with an event driven object oriented user interface. The program controls a Keithley Current Source, HP Nano-Voltmeter and Switching Unit as well as a LakeShore Temperature Controller in order to obtain a plot of the Resistivity as a function of temperature. The system allows for resistivity measurements ranging from 4 K to 290 K using an external probe or between 0.4 K to 295 K using a Helium - 3 Cryostat. Several materials of known resistivity have confirmed the system to be robust and capable of measuring metallic samples distinguishing features of several fiQ-cm.

Optical properties of organic superconductor K-(BETS)2FeBr4 /

K-(BETS)2FeBr4 is a quasi-2D charge transfer organic metal with interesting electronic and magnetic properties. It undergoes a transition to an antiferromagnetic (AF) state at ambient pressure at the Neel temperature (T^^) = 2.5 K, as well as to a superconducting (SC) state at 1.1 K [1]. The temperature dependence of the electrical resistivity shows a small decrease at T;v indicating the resistivity drops as a result of the onset of the ordering of Fe'*''" spins. A sharp drop in the resistivity at 1.1 K is due to its superconducting transition. The temperature dependence of the susceptibility indicates an antiferromagnetic spin structure with the easy axis parallel to the a-axis. The specific heat at zero-field shows a large peak at about 2.4 K, which corresponds to the antiferromagnetic transition temperature (Tat) and no anomaly is observed around the superconducting transition temperature (1.1 K) demonstrating that the magnetically ordered state is not destroyed by the appearance of another phase transition (the superconducting transition) in the 7r-electron layers [1], [2]. This work presents an investigation of how the low frequency electromagnetic response is affected by the antiferromagnetic and superconducting states, as well as the onset of strong correlation. The location of the easy axis of three samples was determined and polarized thermal reflectance measurements of these «-(BETS)2FeBr4 samples oriented with their vertical axis along the a- and c axes were then carried out using a *He refrigerator cryostat and a Martin-Puplett type polarizing interferometer at various temperatures (T = 0.5 K, 1.4 K. 1.9 K, 2.8 K) above and below the superconducting state and/or antiferromagnetic state. Comparison of the SC state to the normal state along the o- and c-axes indicates a rising thermal reflectance at low frequencies (below 10 cm"' ) which may be a manifestation of the superconducting energy gap. A dip-Hke feature is detected at low frequencies (below 15 cm"') in the thermal reflectance plots which probe the antiferromagnetic state along the two axes, and may be due to the opening of a gap in the excitation spectrum as a result of the antiferromagnetism. In another set of experiments, thermal reflectance measurements carried out along the a- and c-axes at higher temperatures (10 K-80 K) show that the reflectivity decreases with increasing temperature to 60 K (the coherence temperature) above which it increases again. Comparison of the thermal reflectance plots along the a- and c-axes at higher temperatures reveals an anisotropy between these two axes. The Hagen-Rubens thermal reflectance plots corresponding to an average over the ac-plane were calculated using experimental hterature resistivity values. Comparison of the Hagen-Rubens plots with the experimental thermal reflectance along the a- and c-axes indicates that both exhibit the general trend of a decrease in thermal reflectance with increasing frequency, however the calculated Hagen-Rubens thermal reflectance at different temperatures is much lower than the experimental curves.

Electronic and magnetic properties of LaV1-xO3 /

A series of LaVi^xOs compounds (x=0.00, 0.02, 0.04, 0.06, 0.08) were prepeired using the standard solid reaction. The samples were chareicterized by X-ray diffraction (XRD), fourprobe resistivity, smd magnetic susceptibility studies. Powder X-ray diffraction analysis indicated the formation of a single-phase sample with a orthorhombic structure which was first found in GdFeOs (space group Pnma) . The Unit Cell program was used for calculating lattice peirameters from XFID data. The XRD spectnim could be indexed on a cubic lattice with Og = 2ap ~ (7.8578 to 7.9414 A). The lattice parameter was observed to increase as the Vanadium vacancy increased. Four-probe resistivity measurements exhibited semiconductor behavior for all sajnples from room temperature down to 19K. The resistivity of samples increased with increasing Vanadium vacancy. The resistivity of samples demonstrated activated conduction with an activation energy of approximately 0.2 eV. The activation energy increased with increasing lattice parameter. Field cool magnetic susceptibility measurements were performed with field of 500 G from 300 K to 5 K. These measurements indicated the presence of an antiferromagnetic transition at about 140 K. The data was fitted above Neel temperature to Ciurie-Weiss law yielding a negative parameignetic Curie temperature. This implies that antiferromagnetic ordering is present.

Effect of the position of the double-bond in monounsaturated phospholipids on the dynamics of model membranes

Therllloelynalllics of lllodel 11lel1ll)rane systeills containing 1110nollnsaturatecl I)lloSI)holil) ids is strongly infllienced l)y the I)osition of the C==C dOlll)le })ond in tIle acyl chain. The telllI)eratllres of both chain-nlelting (TM) and La -+ HI! (TH) I)hase traIlsitions are lowered by IIp to 20°C when C==C is Inoved froln positions 6 or 11 to I)osition 9 in an 18-carl)on chain. This work is an attellll)t to ellicidate the uIlderlying Illoleclilar Illechanisllls reSI)Onsi])le for tllese draillatic tllerillodynaillic changes. Mixtllres of di-18: 1 l)hoSI)hatidylethanolanline with C==C at l)ositioIlS 6, 9, 11 were llsed, witll a sI1lall aI1lOlint of I)erdellterated tetradecanol, known to })e a gooel rel)Orter of the cllain Illoleclilar order. SI)ectral second 11I0I1lents were llsed to Illonitor tIle La -+ HII I)hase transition, which was fOllnd to ])e ])road (2-6°C), with a slight llysteresis on heatiIlg/cooling. The orientational order I)rofiles were nleasllred 1lSiIlg 2H Illiclear Illagnetic resonance and changes in these order I)rofiles between La aIld HII I)hases silow l)oth a local increase in order in the vicinity of the C==C bonds and an o\Terall decrease ill the average orientational order of the chain as a whole. These Sll])tle changes recluire })oth high-fidelity SI)ectrosCol)y and a careflll data analysis that takes into aCCOllnt the effects due to l)artiall1lagnetically-indllced orientational ordering of the l)ilayers. In tIle COIltext of SOllle recently rel)Orted cross-relaxation 11leaSlirenlents in Silllilar l)llOSI)llolil)iels, 0111' reslilts sllggest that large-anll)litllde conforlllational changes in the interior of tIle I110del 111eI11])ranes I)lay a 1110re significant role than I)reviollsly thOllght.

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) .

Out of the darkness and into the light : a study of inauthentic and authentic speech

Introduction Man can be described as the being who shows himself in speech, and from birth to death is continually speaking. Communication is so close to us, so woven into our very being, that we have little understanding of the way it is constituted; for it is as hard to obtain distance from communication as it is to obtain distance from ourselves. All communication is not alike. There are two basic modesl of communication, the inauthentic and the authentic, between which there occurs a constant tension. It is in the inauthentic mode, points out Heidegger, that we find ourselves "proximately and for the most part"; 1. Being and Time, pg. 68 Dasein decides as to the way it will comport itself in taking up its task of having being as an issue for it. " •.• it~, in its very being 'choose' itself and win itself; it can also lose itself and never win itself or only "seem" to do so. But only in so far as it is essentially something which can be authentic--that is, something of its own--can it have lost itself and not yet won itself." 2. therefore Heidegger also terms it "everydayness".2 Caught up in the world of everydayness, our speaking covers over and conceals3 our rootedness in being, leaving us in the darkness of untruth. The image of darkness may be inferred from Heidegger's use of the image of "clearing,,4 to depict being as 2. ibid. pg. 69 "Dasein's average everydayness, however, is not to be taken as a mere 'aspect'. Here too, and even in the mode of inauthenticity, the structure of existentiality lies ~ priori and here too Dasein's being is an issue for it in a definite way; and Dasein comports itself towards it the mode of average everydayness, even if this is only the mode of fleeing in the face of it and forgetfulness thereof." 3. ibid. pg. 59 "covering over" and "concealing" are 1;yays Dasein tries to flee its task of having being as an issue for itself. " ••• This being can be covered up so extensively that it becomes forgotten and no question arises about it or its meaning ••• n How everyday speaking accomplishes this will be taken up in detail in the second chapter which explores Dasein's everyday speech. 4. ibid, pg. 171 lI ••• we have in mind nothing other than the Existential - ontological structure of this entity (Dasein), that it is in such a way as to be its 'there'. To say that it is -' illuminated' [tlerleuchtet"] means that as Being-in-theworld it is cleared [gelichtetJ in itself7 not through any other entity, but in such a way that it is itself the clearing. Only for an entity which is eXistentially cleared in this way does what is present-at-hand become accessible in the light or hidden in the dark •••• " 3 dis-coveredness and truth. Our first task will be to explore the nature of communication in general and then to explore each of the modes manifested in turn. The structure of the inauthentic mode of communication can be explored by asking the following questions: What is this speaking about? Who is it that is speaking and who is spoken to? Does this speaking show man in his speech? The authentic mode is distinguished by the rarity with which we encounter it; as the inauthentic conceals, so the authentic reveals our rootedness in being. Yet this rarity makes it difficult to delineate its elusive structure clearly. Its constituent elements can be brought into focus by asking the same questions of this mode that we previously asked of the inauthentic mode. Our initial response to the disclosure of the authentic mode is to attempt to abandon the inauthentic mode and leave the darkness behind dwelling only in the "lighted place". All through the ages, some men pushing this to extreme, have, upon uncovering their relatedness to being, experienced a deep longing to dwell in such a "place" of pure truth and oft times denigrated or attempted to exclude the everyday world. Such 4. flight is twice mistaken: first it atbempts to fix truth as unchanging and static and secondly, it opposes this to untruth which it seeks to abolish. This is both the wrong view of truth and the wrong view of untruth as Heidegger points out in The Origin of The-Work of Art: The Way-to-be of truth, i.e., of discoveredness, is under the sway of refusal. But this refusal is no lack or privation, as if truth could be simply discoveredness rid of all covers. If it could be that, it would no longer be itself . ••• Truth in its way-to-be is untruth.5 Pure light is not the nature of Being nor is pure unconcealedness possible for man. Failure to remember this is the failure to realize that communication destroys itself in such flight because it no longer maintains the contingency of its task, i.e., the dis-closedness of being. We are reminded of the strong attraction this flight from darkness held for Plato. Light, truth and Being are all beyond the darkness and have nothing to do with it. In Book VII of the R~public, Socrates' explanation of the Allegory of the Cave to Glaucon points to a decided preference men have for the "lighted place". 5. The Origin Of The Work Of Art, pg. 42 5. Come then, I said, and join me in this further thought, and do not be surprised that those who attained to this height are not willing to occupy themselves with the affairs of men, but their souls ever feel the upward urge and yearning for that sojourn above. For this, I take it, is likely if in this point too the likeliness of our image holds. 6 Despite the attraction to pure truth, human communication is more complex than putting down one mode of communication and picking up another. Due to the fact that we are always on the way, the title of my thesis will have to be amended: OUT OF THE DARKNESS AND INTO THE LIGHT--AGAIN AND AGAIN. It must be this way because this is what it means to be human. This is the point made by Mephisto to Faust in pointing out that man, standing between God and the devil, needs both darkness and light: Er findet sich in einem ewigen Gl~t Uns hat er in die Finsternis gebracht, Und euch taugt einzig Tag und Nacht. 7 6. Republic z (517 c & d) It should be noted however, that while the philosopherking must be compelled to return to the cave for purely political reasons, once he has taken adequate view of the "brightest region of being" he has the full truth and his return to darkness adds nothing to the truth. 7. Faust, pg. 188 6. This thesis proposes to examine the grounds that give rise to communication, uncovering the structure of its inauthentic and authentic modes and paying close attention to tpeir interrelationship and to their relationship to language as "the house of Being": language that both covers and opens up man's rootedness in Being, transforming him as he moves along his way, taking up his "ownmost task" of becoming who he is. roots. He is the being who shows himself inn that reflects his forgetfulness or remembrance of his rootedness in being. Man comes into an already existent world and is addressedl through things in the world which are c

The impact of wine closure and packaging type, and light and temperature exposure on the concentration of 3-alkyl-2 -methoxypyrazines and other key constituents of wine

3-alkyl-2-methoxypyrazines (MPs) are grape- and insect-derived odor-active compounds responsible for vegetative percepts that are detrimental to wine quality when elevated. This study tested both the effect of closure/packaging types and light/temperature storage conditions on MPs (isopropyl-, secbutyl-, and isobutyl-MP) in wine. An MP-emiched wine rapidly (after 140 hours) and significantly decreased in MP concentration after natural and synthetic cork contact (immersion of closures in wine). This decrease was greatest with synthetic closures (70% - 89% reduction) and secbutyl-MP. Subsequently storage trials tested the effects of commercial closure/packaging options (natural cork, agglomerate cork, synthetic corks, screwcaps and TetraPak® cartons) on MPs in MP-emiched Riesling and Cabernet Franc over 18 months. Regardless of packaging, isobutyl-MP was the most altered from bottling. Notably, all MP levels tended to decrease to the greatest extent in TetraPak® cartons (~34% for all MPs) and there was evidence of contribution ofisoproyl- and secbutyl-MP from cork-based closures (i.e. ~30% increase in secbutyl-MP after 6 months) or from an unidentified wine constituent. To test the effects of various light/temperature conditions (light exposed at ambient temperature in three different bottle hues, light excluded at ambient temperature and light excluded at a "cellar" temperature (14°C)), MP-emiched Riesling and Cabernet Franc were also analyzed for MP concentrations over 12 months. MPs did not vary consistently with light or temperature. Other odorants and physico-chemical properties were tested in all wines during storage trials and closely agree with previous literature. These results provide novel insights into MPs during ageing, interactions with packaging and storage conditions, and assist in the selection of storage conditions/packaging for optimal wine quality.

Daniel D. Tompkins letter to General Dearborn, June 28, 1812.

Transcript [original spelling and grammar retained]: Albany June 28 1812 Sir Your letter of the 23d has been received. I had anticipated your request by ordering the detachment from Washington, Essex, Clinton and Franklin Counties into service and have fixed the days and places of their Rendezvous. Upon application to the quarter master General I find there are but 139 tents & 60 camp kettles at this place & even those I take by a kind of stealth. The Deputy Quarter Master General declines giving an order for their delivery until he shall have a written order from the Quarter Master General, and the latter is willing I Shall take them but will not give the Deputy a written order for that purpose. Under Such circumstances I shall avail myself of the rule of Possession and by virtue of the Eleven Points of Law Send them tomorrow morning without a written order from anyone. You may remember that when you were Secretary of the war department I invited you to forward and deposit in our Frontier Arsenals, arms ammunition and camp equipage free of expense to be ready in case of war and the same invitation to the war department has been repeated some time, Since The United States have now from 5 to 600 regular troops at Plattsburgh, Rome, Canandaigua & c, where those arsenals are, and yet those recruits are now and must be for weeks to come unarmed and unequipped in every respect although within musket Shot of arsenals. The recruits at Plattsburgh are within 50 miles of two tribes of Canadian Indians. In case of an attack upon the Frontiers that portion of the United States army would be as inefficient and unable to defend the inhabitants or themselves even. The Militia Detachments on the Western Frontiers received the news of war with [cherafulness] and determined courage, and I am happy to find they are united late brothers, highly improved in Discipline & ready to devote themselves to any Service or danger which the good of the Country may require. But they are in barracks from which they cannot move a days march for the want of tents and other equipage, and they are in Separate and Independent Detachments without a General Officer to command them or combine their exertions for the accomplishment of any desirable and important object. The only officer of the United States here who can do anything is the Quarter Master General and he has not a tent Camp Kettle or Knapsack in this arsenal except what I have concluded to send off tomorrow morning as above mentioned to furnish men As to Cannon Muskets and Ammunition. I can find now one here who will exercise any authority over them or deliver a Single article upon my requisition. Neither can I find any Officer of the army who feel himself authorized to exercise any authority or do any act which will aid me in the all important object of protecting the Inhabitants of an extended Frontier exposed to the Cruelties of Savages and the depredations of the enemy. If I must rely upon the Militia Solely for Such protection I entreat you to give orders to your Officers to furnish upon my orders, for the use of the Militia Detachments , all needful weapons and articles with which the United States are Supplied and of which we are destitute . You may rely upon all the assistance which my talents, influence or authority can furnish in the active prosecution of the first & necessary way which has been declared by the Constituted Authorities of our beloved Country. I am, Sir, respectfully Your ob. Servt. Daniel D. Tompkins

Electrophysiological constituents of the P100 and N170 ERP complex: De-constructing of face processing using independent component analysis and robust estimation.

The initial timing of face-specific effects in event-related potentials (ERPs) is a point of contention in face processing research. Although effects during the time of the N170 are robust in the literature, inconsistent effects during the time of the P100 challenge the interpretation of the N170 as being the initial face-specific ERP effect. The interpretation of the early P100 effects are often attributed to low-level differences between face stimuli and a host of other image categories. Research using sophisticated controls for low-level stimulus characteristics (Rousselet, Husk, Bennett, & Sekuler, 2008) report robust face effects starting at around 130 ms following stimulus onset. The present study examines the independent components (ICs) of the P100 and N170 complex in the context of a minimally controlled low-level stimulus set and a clear P100 effect for faces versus houses at the scalp. Results indicate that four ICs account for the ERPs to faces and houses in the first 200ms following stimulus onset. The IC that accounts for the majority of the scalp N170 (icNla) begins dissociating stimulus conditions at approximately 130 ms, closely replicating the scalp results of Rousselet et al. (2008). The scalp effects at the time of the P100 are accounted for by two constituent ICs (icP1a and icP1b). The IC that projects the greatest voltage at the scalp during the P100 (icP1a) shows a face-minus-house effect over the period of the P100 that is less robust than the N 170 effect of icN 1 a when measured as the average of single subject differential activation robustness. The second constituent process of the P100 (icP1b), although projecting a smaller voltage to the scalp than icP1a, shows a more robust effect for the face-minus-house contrast starting prior to 100 ms following stimulus onset. Further, the effect expressed by icP1 b takes the form of a larger negative projection to medial occipital sites for houses over faces partially canceling the larger projection of icP1a, thereby enhancing the face positivity at this time. These findings have three main implications for ERP research on face processing: First, the ICs that constitute the face-minus-house P100 effect are independent from the ICs that constitute the N170 effect. This suggests that the P100 effect and the N170 effect are anatomically independent. Second, the timing of the N170 effect can be recovered from scalp ERPs that have spatio-temporally overlapping effects possibly associated with low-level stimulus characteristics. This unmixing of the EEG signals may reduce the need for highly constrained stimulus sets, a characteristic that is not always desirable for a topic that is highly coupled to ecological validity. Third, by unmixing the constituent processes of the EEG signals new analysis strategies are made available. In particular the exploration of the relationship between cortical processes over the period of the P100 and N170 ERP complex (and beyond) may provide previously unaccessible answers to questions such as: Is the face effect a special relationship between low-level and high-level processes along the visual stream?

Bringing Zombies Back to Life: An Autoethnographical Exploration of Alienation and Political Dis/Engagement in Emerging Adulthood Within Late-Stage Capitalism

In this thesis, by employing an autoethnographic methodology, I am exploring why certain understandings, or assemblages, of political engagement come to have greater meaning in my life and why other assemblages may be more hidden and thus fail to contribute substantially to the meaning of political in my life. Using immanent, Marxist and post-Marxist theories, as well as a zombie narrative, the study will contextualize the movement of assemblages in my life within late-stage capitalism which is juxtaposed with the zombie apocalypse. The placement and displacement of certain understandings of the political within my life will be theorized within the crisis of constituent power that is revealed in an immanent framework. Furthermore, the crisis of the constituent in late-stage capitalism creates new forms of radical alienation which will also be examined. By exploring my own struggles in becoming political I will theorize why political disengagement in emerging adulthood appears to be increasing, as well as possibilities for new forms of political engagement in a late-stage capitalist context.

Photograph - Col. Frank C. McCordick

A photograph of Col. Frank C. McCordick in military uniform standing in a field. The reverse of the photograph reads "Copies of this photograph can be obtained from The Rembrandt Studio, 207 Cuthbertson Block Fort William, Ont, When ordering please quote 402."

Order to create a General Board of Health in the Town of Niagara, June 25, 1832

In the early nineteenth century, a widespread outbreak of cholera occurred in continental Europe, eventually spreading to the British Isles. The disease subsequently spread to Canada as impoverished British immigrants seeking a better life arrived in the country. To help curb the spread of the disease, local Boards of Health were created.

Order to create a General Board of Health in the Town of Niagara, June 25, 1832.

In the early nineteenth century, a widespread outbreak of cholera occurred in continental Europe, eventually spreading to the British Isles. The disease subsequently spread to Canada as impoverished British immigrants seeking a better life arrived in the country. To help curb the spread of the disease, local Boards of Health were created.

Structural, Magnetic and Thermal Studies of Ce1-xEuxCrO3 Nano-Powders

A new series of nano-sized Ce1-xEuxCrO3 (x = 0.0 to 1.0) with an average particle size of 50 - 80 nm were synthesized using a solution combustion method. Nano-powders Ce1-xEuxCrO3 with the canted antiferromagnetic property exhibited interesting magnetic behaviours including the reversal magnetization and the exchange bias effect. The effect of europium doping as the ion with the smaller radius size and different electron con figuration on structural, magnetic and thermal properties of Ce1-xEuxCrO3 were investigated using various experimental techniques, i.e. DC/AC magnetic susceptibility, heat capacity, thermal expansion, Raman scattering, X-ray photoemission spectroscopy, transmission/scanning electron microscopy, X-ray powder diffraction and neutron scattering. An exchange bias effect, magnetization irreversibility and AC susceptibility dispersion in these samples confirmed the existence of the spin disorder magnetic phase in Ce1-xEuxCrO3 compounds. The exchange bias phenomenon, which is assigned to the exchange coupling between glassy-like shell and canted antiferromagnetic core, showed the opposite sign in CeCrO3 and EuCrO3 at low temperatures, suggesting different exchange interactions at the interfaces in these compounds. The energy level excitation of samples were examined by an inelastic neutron scattering which was in good agreement with the heat capacity data. Neutron scattering analysis of EuCrO3 was challenging due to the large neutron absorption cross-section of europium. All diffraction patterns of Ce1-xEuxCrO3 showed the magnetic peak attributed to the antiferromagnetic Cr3+ spins while none of the diffraction patterns could detect the magnetic ordering of the rare-earth ions in these samples.

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.