Made available in DSpace on 2014-10-09T12:42:54Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:07:52Z (GMT). No. of bitstreams: 1 05403.pdf: 3608647 bytes, checksum: 066e3f6af2ef001c7431582e2ce35791 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP / FAPESP:96/01220-7

Os núcleos, ímpar-ímpar ANTPOT. 132,134 La foram estudados através de técnicas de espectroscopia em linha de reações tipo (HI, xn). Foram usados feixes de ANTPOT. 10,11 B(40-48 MeV) e ANTPOT. 14 N (55 MeV) em alvos de ANTPOT. 128,128 Te e ANTPOT. 122 Sn no acelerador Pelletron. Foi observada uma banda rotacional, presumidamente sobre a configuração h IND. 11/2 e h IND. 11/2 em cada um dos isótopos, mostrando valores de \"signature splitting\" moderados. No ANTPOT. 132 La uma outra banda foi observada essencialmente sem \"signature splitting\". Os resultados são comparados com as previsões do \"Cranking Shell Model\" triaxial. A relação entre triaxialidade e \"signature splitting\" na região de transição A ~ 130 é discutida. / The odd-odd nuclei 132,134La were studied by means of in-beam -ray spectroscopy techniques, using (HI, xn) reactions with 10,11B (40-48 MeV), 14N (55 MeV) beams on 128,128Te and 122 Sn targets. A band, probably based on the h11/2 and h11/2 configuration, was observed in each La isotope showing moderate signature splitting. Another band was observed in 132La with essentially no signature splitting. The results are compared with the triaxial Cranking Shell Model predictions. The relation between triaxiality and signature splitting in the A ~ 130 transitional mass region is discussed.

Ces dernières années, les matériaux à transition de spin (TS) ont suscité un intérêt marqué en raison de leurs applications potentielles, notamment en tant que capteurs ou dispositifs électroniques; typiquement, ces complexes présentent - via un stimulus externe (ex. : température, rayonnement) - une transition de spin réversible "Haut Spin (HS)  Bas Spin (BS)". Dans ce contexte, le travail présenté a porté sur la conception et les études magnétostructuralesde monocristaux de nouveaux systèmes FeII à TS à base de ligands 4-R-1,2,4-triazole comprenant un espaceur alkyl, en combinaison avec soit (i) des entités tétracyanométallates inorganiques ([M(CN)4]2-, M = NiII, PtII, PdII) ou (ii) des cyanocarbanions organiques spécifiques ((tcnsR')-: anions 1,1,3,3-tétracyano-2 thioalkylpropénide) - et ce afin de comprendre in fine l'origine physico-chimique de la forte coopérativité dans ces matériaux remarquables, mais aussi de rationaliser le contrôle et l’optimisation des propriétés de TS. Dans un premier temps, un nouveau sel de polymère 1D [Fe(bntrz)3][Pt(CN)4].H2O (1) - présentant une TS abrupte et une résilience exceptionnelle lors de cycles répétés de commutation - a été synthétisé; les études structurales fines - réalisées sur monocristaux - des états HS et BS ont clairement révélé l'impact des interactions à longue distance sur les propriétés de la TS dans ce système. Ensuite, la substitution de l'anion « rigide » tétracyanométallate ([Pt(CN)4]2-) par l'entité plus « flexible » (tcnset)- nous a conduit au premier exemple de complexe neutre trinucléaire à base de triazole [Fe3(bntrz)6(tcnset)6] (2) présentant une TS complète en une seule étape au-dessus de la température ambiante. La variation systématique du substituant R' de l'anion fonctionnalisé(tcnsR')- a permis l’obtention de deux nouveaux systèmes à TS, à savoir le complexe trinucléaire neutre [Fe3 (bntrz)6(tcnspr)6] (3) et le dérivé 1D [Fe3(bntrz)8(tcnsme)4].(tcnsme)2,4H2O (4), avec des caractéristiques structurales et des comportements de TS distincts. Enfin, dans le but d'évaluer précisément l'impact de différents substituants en 4ème position sur le ligand 1,2,4-triazole, deux nouveaux matériaux 3D basés sur le triazole 2-(3-(4H-l,2,4-triazol-4-yl)propyl)isoindoline-1,3-dione (phtptrz) - i.e. {Fe3(μ2-phtptrz)6[μ2-Pt(CN)4]3}.C2H5OH,5.5H2O (5) et {Fe(phtptrz)[Pt(CN)4].H2O} (6) - ont été synthétisés et caractérisés; une TS en deux étapes est observée pour le composé 5, tandis que le dérivé 6 exprime un comportement paramagnétique caractéristique de l’état de spin S = 2. / In recent years, the spin-crossover (SCO) materials have attracted much interest because of their potential applications such as sensors or electronic displays; these complexes typically exhibit - via an external disturbance (e.g. temperature, radiation) - a reversible “High Spin (HS) Low Spin (LS)” spin transition. In this context, the present work has focused on the design and the magneto-structural investigations of single crystals of novel FeII SCO systems based on 4-R-1,2,4-triazole ligands including an alkyl spacer - with either (i) inorganic tetracyanometallates ([M(CN)4]2-, M = NiII, PtII, PdII) or (ii) specific organic cyanocarbanions ((tcnsR’)-: 1,1,3,3-tetracyano-2-thioalkylpropenide anions) - in order to ultimately understand the physicochemical origin of the strong cooperativity in such striking materials, but also to rationalize the tuning of the SCO properties. At first, a new 1D polymer [Fe(bntrz)3][Pt(CN)4].H2O (1) salt - exhibiting an abrupt spin transition and an exceptional resilience upon repeated switching - has been synthesized; the accurate single crystal investigations of both HS and LS states of the latter clearly revealed the impact of the longrange interactions on SCO properties in this system. Then, the substitution of the ‘rigid’ [Pt(CN)4]2- tetracyanometallate anion by the more ‘flexible’ (tcnset)- entity lead us to the first example of triazole-based SCO FeII trinuclear neutral complex [Fe3(bntrz)6(tcnset)6] (2) exhibiting a complete one-step spin transition above room temperature. The systematic variation of the R’ substituent from the functionalized (tcnsR’)- anion resulted in two new FeII SCO systems, i.e. the neutral trinuclear complex [Fe3(bntrz)6(tcnspr)6] (3) and the 1D [Fe3(bntrz)8(tcnsme)4](tcnsme)2.4H2O (4) derivative, with distinct structural characteristics and SCO behaviours. Finally, with the purpose to further evaluate the impact of different substituents at the 4th position onto 1,2,4-triazole ligand, two new 3D materials based on the functionalised triazole 2-(3-(4H-1,2,4-triazol-4-yl)propyl)isoindoline-1,3-dione (phtptrz) - {Fe3(μ2-phtptrz)6[μ2-Pt(CN)4]3}.C2H5OH,5.5H2O (5) and {Fe(phtptrz)[Pt(CN)4].H2O} (6) - have been synthesized and characterized; a two-step SCO behaviour is observed only in 5, while 6 shows a characteristic paramagnetic behavior.

Metal acetylacetonates of the general formula [M(acac)3] (MIII=Cr, Mn, Fe, Co) are among the best investigated coordination compounds. Many of these first-row transition metal complexes are known to have unique electronic properties. Independently, photophysical research with different β-diketonate ligands pointed towards the possibility of a special effect of the 2,4,6-trimethylphenyl substituted acetylacetonate (mesacac) on the electron distribution between ligand and metal (MLCT). We therefore synthesized and fully characterized the previously unknown octahedral title complex. Its solid-state structure shows a Jahn-Teller elongation with two Mn−O bonds of 2.12/2.15 Å and four Mn−O bonds of 1.93 Å. Thermogravimetric data show a thermal stability up to 270 °C. High-resolution mass spectroscopy helped to identify the decomposition pathways. The electronic state and spin configuration of manganese were characterized with a focus on its magnetic properties by measurement of the magnetic susceptibility and triple-zeta density functional theory (DFT) calculations. The high-spin state of manganese was confirmed by the determination of an effective magnetic moment of 4.85 μB for the manganese center.

Com o objetivo de ampliar o conhecimento da estrutura dos núcleos duplamente ímpares da região de massa A = 130- 140, foram medidos os estados de spin elevado do ANTIPOT. 138 Pr, que se aproxima da camada fechada N = 82, através de técnicas de espectroscopia y em linha utilizando a reação ANTPOT. 128 Te (ANTIPOT. 14 N,4ny). Pela primeira vez, três bandas rotacionais foram observadas neste núcleo. Uma análise teórica da sistemática desta região foi feita com base nos modelos de \"Cranking Shell Model\" e \"Projected Shell Model\". De um modo geral, uma boa concordância foi obtida entre os resultados experimentais e teóricos. O primeiro modelo indica a coexistência de formas no ANTIPOT. 138 Pr (N=79}, enquanto o segundo sugere forma unicamente oblata. Por outro lado, os dois modelos prevêm uma transição de forma de prolato (N = 73) para oblato (N = 79) passando por uma região de triaxialidade em torno de N = 77. / With the view of extending the systematics of the odd-odd, A = 130 - 140 mass region nuclei towards the N =82 closed shell, high spin states in 138Pr nucleus have been investigated with the 128 Te(l4N,4n7) reaction, using on-line 7-ray spectroscopy techniques. For the first time three rotational bands were observed in this nucleus. A theoretical analysis of the mass region A = 130 - 140 was carried out with the Cranking Shell Model and the Projected Shell Model. Generally speaking, a good agreement was obtained between the experimental and the theoretical results. The first model indicates a shape coexistence in the 138 Pr (N =79) nucleus, while the second one shows an oblate shape. On the other hand, both models suggest a shape transition from prolate (N=73) to oblate (N=79) passing through a triaxial region around N=77.

Com o objetivo de ampliar o conhecimento da estrutura dos núcleos duplamente ímpares da região de massa A = 130- 140, foram medidos os estados de spin elevado do ANTIPOT. 138 Pr, que se aproxima da camada fechada N = 82, através de técnicas de espectroscopia y em linha utilizando a reação ANTPOT. 128 Te (ANTIPOT. 14 N,4ny). Pela primeira vez, três bandas rotacionais foram observadas neste núcleo. Uma análise teórica da sistemática desta região foi feita com base nos modelos de \"Cranking Shell Model\" e \"Projected Shell Model\". De um modo geral, uma boa concordância foi obtida entre os resultados experimentais e teóricos. O primeiro modelo indica a coexistência de formas no ANTIPOT. 138 Pr (N=79}, enquanto o segundo sugere forma unicamente oblata. Por outro lado, os dois modelos prevêm uma transição de forma de prolato (N = 73) para oblato (N = 79) passando por uma região de triaxialidade em torno de N = 77. / With the view of extending the systematics of the odd-odd, A = 130 - 140 mass region nuclei towards the N =82 closed shell, high spin states in 138Pr nucleus have been investigated with the 128 Te(l4N,4n7) reaction, using on-line 7-ray spectroscopy techniques. For the first time three rotational bands were observed in this nucleus. A theoretical analysis of the mass region A = 130 - 140 was carried out with the Cranking Shell Model and the Projected Shell Model. Generally speaking, a good agreement was obtained between the experimental and the theoretical results. The first model indicates a shape coexistence in the 138 Pr (N =79) nucleus, while the second one shows an oblate shape. On the other hand, both models suggest a shape transition from prolate (N=73) to oblate (N=79) passing through a triaxial region around N=77.

The presented thesis includes investigations to fully characterize the electronic structure and magnetic properties ofselected manganese containing high-spin molecules by means of various X-ray spectroscopic, magnetic and theoretical methods. The investigations on the Mn4 star-shaped molecule havelead to a number of interesting results. Magneto-chemical studies exhibit very weak exchange coupling constantsbetween the four Mn(II) ions, leading to complicated low lying states in which the ground state is not well separated, resulting from a dominant weak ferromagnetic coupling and a giant moment of up to 20 µB/f.u. XMCD measurements revealed that almost the completemagnetic moment is located around the Mn(II) ions.This is in agreement with only a few charge transfer states foundwithin the detailed X-ray absorption spectroscopic study. The electronic structure and detailed magnetic properties of the star-shaped heteronuclear CrIIIMnII3 complex have been precisely investigated.With XPS the homovalency of Mn and Cr have been verified. The XA-spectra of the manganese and chromium L edges were measured and compared to earlier investigated Mn4 spectra.The combination high-magnetic field magnetic measurements and element selective XMCD of Mn and Cr L edges and quantum model calculations lead to a complete analysis of the magnetic structure of the CrMn3 magnetic core. The III valence state of the manganese ions in MnIII6O2Salox has been verified. From X-ray diffraction, typical Jahn-Teller distorted oxygen octahedra have been found for Mn(III) ions. Comparisons of XPS and XAS spectra of the complex to corresponding spectraof maganite and tetranuclear manganese(II) cluster it was definitely possible to identify MnIII6O2Salox as a pure Mn(III) compound.