Les sources d'approvisionnement en énergie proviennent essentiellement des matières fossiles, qui se raréfient et dont la combustion relargue dans l'atmosphère des polluants et gaz à effet de serre.Un vecteur d'énergie apparaît comme l'avenir pour subvenir aux besoins énergétiques de la planète : l'hydrogène ; cependant, son coût de production reste très élevé.Dans la nature, des enzymes, les hydrogénases, sont capables de produire et d'oxyder l'hydrogène de manière très efficace. Les scientifiques se sont alors inspirés de ces enzymes afin de concevoir des complexes qui seraient des catalyseurs bien plus robustes pour produire de l'hydrogène.Au cours de cette thèse, nous avons pris comme source d'inspiration les hydrogénases [NiFe], dont le site actif est composé d'un coeur bimétallique Ni-Fe coordiné par quatres ligands thiolates.Nous avons synthétisé divers ligands en vue d'obtenir des complexes polymétalliques de Ni, Fe ou Ru, rassemblant ce qui semble être quelques unes des propriétés clés de l'activité des hydrogénases [NiFe] : ligands thiolate sur le nickel, dont deux pontants avec le second métal, géométrie tétraédrique du nickel. Pour cela, de nouvelles familles de ligands polythiolates ont été conçues et préparées.Les complexes ainsi préparés ont été caractérisés et leur activité évaluée par différentes techniques, dont la voltammétrie cyclique et l'électrolyse couplé à une GC, qui nous ont permis d'évaluer l'activité de nos catalyseurs (TON, TOF, surtension). Un des catalyseurs actifs a été utilisé comme support pour des simulations en DFT qui nous ont aidés à mieux comprendre le mécanisme catalytique de production d'hydrogène. / The energy supply sources are mainly based on fossil materials which are growing scarce and release pollutants and greenhouse gases.In this context, an energy vector appears as the future to feed the energetic needs of the planet: the Hydrogen; but its current production costs remain very high.Nature has deviced enzymes, hydrogenases, able to produce and oxidize hydrogen very efficiently. Nevertheless, the manipulation of these organisms is not easy, notably because of their susceptibility (oxygen inhibition, organic solvents, high temperatures), and their production costs are high.So, scientists have taken this inspiration source in order to design biomimetic and bioinspired models, which would much more robust and cheap catalysts to produce hydrogen.During this thesis, we have drawn our inspiration from [NiFe] hydrogenases, where the active site is a Ni-Fe core coordinated by four thiolate ligands. Our goal has been to design new polythiolate ligands, that gather some of the key hydrogenases [NiFe] properties responsible for their activity: thiolate ligands on the nickel, among them two brinding with the second metal, nickel tetraedric geometry.The synthesised complexes have been characterized and their activity tested (TON, TOF, overvoltage) by different techniques, among them cyclic voltammetry and electrolysis coupled to a GC.Finally, the bests have been tested further, thank to bulk electrolysis, which, coupled to a GC system, has enabled us to qualify and quantify the hydrogen production.One of our most active catalysts has been used as a support for DFT calculations, helping us to better undersand the catalytic hydrogen evolving mechanism.

The work presented in this thesis has broadly established a few findings about the structure¬hyperpolarizability relation in molecular compounds: First, by measuring βHRS of an organic keto-enol tautomer, benzoylacetanilide in a binary solvent, I have shown that the first hyperpolarizability can be manipulated favourably by changing the composition of the solvent or by altering the pH of the solution. BA which exists in the pure keto form in water and as a keto-enol tautomer in ethanol, co-exists in equilibrium with the keto and enol forms at pH 11 in aqueous solution. The β value of the anion form is 709 x 10¬30 esu , whereas that of the enol is 232 x 10-30 esu and of the keto is 88 x 10-30 esu. There is an enhancement of β by ~ 8 times for the anion and ~3 times for the enol compared to the keto form. This opens up the possibility of finding large nonlinearities in organic molecules by simply ionizing it. Second, in organometallic complexes of divalent Ru, the first hyperpolarizability could be manipulated by altering the valence state of the metal center by oxidation or reduction or by introducing highly polarisable halogen atoms as substitutions in ligands attached to the metal center. The enhancement of first hyperpolarizability was observed in mononuclear [RuII(acac)2(CH3CN)2] complex by 1.7 times when the metal center was oxidized from RuII to RuIII. As it is already known that the complexes like [(acac)2Ru-bptz-Ru(acac)2] produce stable mixed valent compound, the enhancement of β by ~1.6 times is appearing because of that species only. Exploring Large Nonlinearity in Tautomers In this thesis I have taken a linear ketone for studying the effect of structure on β via the enol and anion formation mediated by solvent and pH of the medium. In the present study the proton transfer in BA took place in the ground state of the ketone and the enol or anion are produced in the ground states. The proton transfer reaction (tautomerism) can also happen in the excited state as well in some molecules where there is a substantial barrier to the proton transfer reaction in the ground state. In such systems, once the ketone is excited using ultraviolet light the barrier to proton transfer in the medium is overcome and a proton transfer in the excited state takes place and the enol is produced. Since such a system will be at higher energy, it will be interesting to do a two-laser experiment where the excited state hyperpolarizability is measured in a time resolved manner and the β value is determined in the excited state. Building Molecular Nonlinearity in Step-by-Step Electron Transfer In this thesis, I have dealt with a binuclear complex of Ru(II) which in one-step electrochemical oxidation produced a mixed valence compound which had substantially higher β value compared to the unoxidized complex. In this way it is possible to build a multicentered complex and see if sequential one-electron transfer and subsequent oxidation/reduction of the metal centers produce a mixed-valent metal compound with large molecular nonlinearity. The indication from the present study is that such a scheme should double the β value in each one-electron transfer step. Also the linker group/moiety between the successive metal centers will play an important role in dictating the efficiency of electron transfer. If the metal d-electrons in a multinuclear complex are linked through a π-conjugation, one would expect manifold enhancement of β. Such metal arrays can also be designed in 2 or 3 dimensions. The dimensionality of the multinuclear metal complexes can easily be changed by supramolecular design and synthesis strategy. Such metal networks may or may not generate large β molecules since electronic polarization in such systems may not be superimposable in a coherent fashion and may not add in a positive sense. All these remain to be tested and explored in the future.