The [ReCl6]2-, [ReBr6]2- and [ReCl4(ox)]2- anions are crystallised with the organic 4,4’- bipyridinium dication (4,4-H2bipy). Magnetometry reveals exotic behaviour of the [4,4’- H2bipy][ReCl6] and [4,4’-H2bipy][ReBr6] salts which demonstrate spin-canting, antiferromagnetic exchange interactions and metamagnetism. Single crystal X-ray structures at T = 3, 14 and 20 K of the [4,4’-H2bipy][ReBr6] salt reveal the behaviour to be purely of magnetic origin as no structural changes are observed. For the [4,4’-H2bipy][ReCl4(ox)] compound an antiferromagnetic exchange interaction of 10.2 cm-1 between the anions is observed (Chapter 2). The complexes (NBu4)2[(ReCl5)2(μ-pyrazine)], (NBu4)2[(ReBr5)2(μ-pyrazine)], (NBu4)2[(ReBr5)2(μ-pyrimidine)] and (NBu4)2[(ReBr5)2(μ-triazine)] are structurally and magnetically characterised in Chapter 3. Magnetic measurements reveal the ReIV ions bridged by a 1,4-heterocyclic amine to exhibit strong antiferromagnetic coupling induced by the linearity of the bridging ligand. The two dimers bridged by a 1,3-heterocyclic amine exhibit intramolecular ferromagnetic exchange and at low temperature an intermolecular antiferromagnetic coupling is observed for the (NBu4)2[(ReBr5)2(μ-triazine)] complex due to the presence of short intermolecular Br···Br distances. Six molecular ReIVCuII chains of formula {[Cu(L)4][ReCl6]}n (L = imidazole, 1- methylimidazole, 1-vinylimidazole, 1-butylimidazole, 1-vinyl-1,2,4-triazole or dimethylformamide) are characterised structurally and magnetically in Chapter 4. SQUID magnetometry and theoretical calculations reveal the chains to exhibit ferromagnetic exchange interactions, which increase as the Re–Cl–Cu bond angle decreases. The {[Cu(vinylimidazole)4][ReCl6]}n chain exhibit magnetic order at TC = 2.4 K, and the {[Cu(imidazole)4][ReCl6]}n network exhibits ferrimagnetic behaviour. Eight complexes of the [ReCl6]2- and [ReBr6]2- anions crystallised with the [MII(L•)2]2+ (M = Fe, Co or Cu) or [Ni(L•)(CH3CN)3]2+ cations (L• = 4-dimethyl-2,2-di(2-pyridyl)oxazolidine N-oxide) are characterised structurally and magnetically in Chapter 5. The [Co(L•)2]2+ cation shows evidence of a gradual, thermally induced spin-crossover transition in variable-temperature magnetic and structural experiments. The [Ni(L•)(CH3CN)3]2+ cation show exchange of the coordinated acetonitrile molecules for atmospheric water upon drying. The nickel-radical magnetic coupling is ferromagnetic in all cases, demonstrating spin-canting behaviour with an ordering temperature of T = 2.7 K for the [ReCl6]2- based compound, and intermolecular antiferromagnetic exchange interactions for the [ReBr6]2- based complex.

Les jonctions tunnel magnétiques épitaxiées Fe/MgO/Fe(001) présentent des comportements remarquables dans la limite des faibles ou des fortes épaisseurs de MgO. Ainsi, dans le premier cas, une interaction antiferromagnétique entre les deux couches de fer est observée ; dans le second, des effets de filtrage en symétrie conduisent à l?obtention de fortes valeurs de magnétorésistance. Les expériences réalisées au cours de cette thèse visent à étudier et mettre en relation ces deux régimes de propriétés extrêmes. Des analyses en tension et en température nous permettent d?étudier les conséquences d?une modulation de la structure cristalline des électrodes et/ou de l?interface sur le transport polarisé en spin. Dans ce cadre, nous nous intéressons à trois systèmes : des jonctions hybrides Fe/MgO(001)/CoFeB, où l?électrode de CoFeB est déposée par pulvérisation cathodique puis cristallisée in situ, des jonctions Fe/MgO/Fe à texture (001), ainsi que des jonctions Fe/MgO/Fe monocristallines présentant une rugosité artificielle à l?interface barrière/électrode. Le couplage antiferromagnétique dans des systèmes Fe/MgO/Fe(001) à barrière fine est étudié grâce à des mesures de magnétométrie sur la gamme de température [5 K ; 500 K]. Nous considérons aussi l?effet de modifications structurales et/ou chimiques de l?interface par le biais de l?introduction d?une rugosité contrôlée ou d?un contaminant. Les résultats les plus originaux de cette thèse sont obtenus grâce à l?introduction d?une rugosité artificielle à l?interface Fe/MgO ; contre toute attente, ce désordre contrôlé peut en effet augmenter l?effet de magnétorésistance ou l?intensité du couplage antiferromagnétique / Epitaxial magnetic tunnel junctions Fe/MgO/Fe(001) exhibit noteworthy behaviors for both small and large MgO thicknesses. In the first case, a strong antiferromagnetic interaction between Fe layers is observed, whereas symmetry filtering effects occur for large barriers, leading to high TMR values. The aim of the experiments performed during this thesis is to study and link these two behaviors. We consider the effect of a modulation of electrodes and/or interfaces crystalline structure on spin-polarized transport, by means of temperature and voltage analyses. In this framework, we focus on three systems: Fe/MgO(001)/CoFeB hybrid junctions, where the CoFeB electrode is grown by sputtering and in situ recrystallized, textured Fe/MgO/Fe(001) junctions, and finally single crystalline (001)Fe/MgO/Fe junctions with an artificial roughness at the electrode/barrier interface. The antiferromagnetic coupling in epitaxial Fe/MgO/Fe(001) systems with a thin MgO barrier is studied by magnetometry measurements in the [5 K; 500 K] range. We also consider the effect of structural and/or chemical changes resulting from a controlled roughness or a contamination on the coupling. The most interesting results of this thesis are obtained with the introduction of an artificial roughness at the Fe/MgO interface. Unexpectedly, this controlled disorder can improve the magnetoresistance effect or the coupling intensity. In both cases, this result is attributed to a Fe-O hybridization, which emphasizes the role of oxygen in MgO based magnetic tunnel junctions for both behaviors associated with extremely thin or thick barriers