The development of a co-axially configured submillimeter spectrometer is reported. The spectrometer has been constructed to observe molecular complexes that exhibit non-covalent interactions with energies much less than that of a traditional covalent bond. The structure of molecular complexes such as those formed between a rare gas and a hydrogen halide, Rg:HX where Rg is a rare gas (Rg=Ne, Ar and Kr) and HX (X=F, Cl, Br and I) can be determined directly and accurately. The center of mass interaction distance, RCM, as well as the angle of the hydrogen halide is determined, along with direct evaluation of the intermolecular vibrations as well as accurate isomerization energies between the hydrogen bound and van der Waals forms. The accuracy of the frequency determination of rovibrational transitions using the submillimeter spectrometer is also evaluated by direct comparison with the state-of-theart pulsed nozzle Fourier transform microwave spectrometer, and this accuracy is estimated to be less than 1 kHz at 300 GHz. The tunneling or geared bending vibration of a dimer of hydrogen bromide or hydrogen iodide has been investigated. The selection rules, nuclear statistics and intensity alternation for transitions observed in these dimmers, which is a consequence of interchanging two identical nuclei in the low frequency geared bending vibration of the molecular complex, are reported. Furthermore, the rotation and quadrupole coupling constants are used to determine a vibrationally averaged structure of the complex. The energy of the low frequency bending vibration can then be compared with ab initio based potential energy surfaces. A study of the multiple isomeric forms of the molecular complex OC:HI is also presented. Multiple isotopic substitutions are used to determine the relevant ground state structures and data reported evidence for an anomalous isotope effect supporting a ground state isotopic isomerization effect. All spectroscopic data that has been reported here has been additionally used to subsequently model and generate vibrationally complete morphed potential energy surfaces that are capable or reproducing the experimentally observed data. The utility of this procedure is evaluated on a predicative basis and comparisons made with newly observed data.

No description available.

no / The formation of crystalline molecular complexes of benzoic acid and isonicotinamide with 1:1 and 2:1 compositions has been investigated through solution cocrystallization. The 1:1 complex was solely obtained from ethanol solutions, while either complex could be grown from aqueous and methanol solution by variation of the initial composition. The crystal structures of the 2:1 complex and a monohydrate of isonicotinamide were determined by single crystal X-ray diffraction. The intermolecular interactions in the crystal structure of the complex were compared with other published carboxylic acid:isonicotinamide molecular complexes, which highlights the robust nature of the acid · · · pyridine and acid · · · amide hydrogen bond, which exist in most cases. Complementary computational studies into the binding of pairs of these molecules by ab initio calculations were found to support the experimental observations and highlight the role of solvent in controlling the final crystalline form for multicomponent systems, through altering the hierarchy of intermolecular interactions.

Neste trabalho foram estudados três complexos de transferência de carga formados por aminas aromáticas e SO2. As aminas escolhidas foram a N,N-dimetilanilina (DMA), N,N-dietilanilina (DEA) e N-metilanilina (NMA). A interação entre a espécie doadora (amina) e a espécie aceptora (SO2) está bem esclarecida na literatura e trata-se de um reação típica de ácido-base de Lewis, porém existem alguns aspectos inexplorados e sem registros na literatura. Um desses aspectos é o fato de que complexos formados entre as aminas aromáticas e o SO2 dão origem a soluções oleosas com coloração vermelha intensa. O máximo de absorção eletrônica (UV-VIS) desses compostos está na faixa de 350 nm, com uma cauda que se estende pela região do visível, responsável pela cor. Um fato curioso é que a cor desses complexos se altera com a variação da temperatura de forma reversível. Em baixas temperaturas o complexo torna-se amarelo pálido e em altas temperaturas, vermelho escuro muito intenso. Um dos principais objetivos deste trabalho foi reinvestigar a interação de transferência de carga entre aminas aromáticas e SO2 na tentativa de responder tal questão. Para tal, foram utilizadas técnicas espectroscópicas (Raman e Infravermelho), sobretudo a espectroscopia Raman ressonante, com o auxílio de cálculos teóricos baseados na teoria do funcional da densidade (DFT). Os espectros Raman ressonante mostraram a intensificação seletiva de uma banda em cerca de 1140 cm-1 tanto com a variação da radiação quanto com a variação de temperatura. O fato dessa banda ter sido intensificada preferencialmente em radiações de excitação na região do visível e em altas temperaturas, permitiu que fosse proposta a presença de um outro cromóforo em solução. Portanto, além do complexo já bem caracterizado com estequiometria 1:1, propôs-se a presença de um complexo com estequiometria 2:1, ou seja, duas aminas conectadas por uma molécula de SO2, formando um complexo de transferência de carga com maior deslocalização eletrônica. A comparação entre as diferentes aminas mostrou que a formação dessas espécies associadas depende de um delicado balanço entre basicidade, impedimento estérico e possibilidade de interações específicas como ligações de hidrogênio. / In this work three charge-transfer complexes formed by aromatic amines and SO2 were studied. The chosen amines were N,N-dimethylaniline (DMA), N,N-diethylaniline (DEA) e N-methylaniline (NMA). The interaction between the donor (amine) and acceptor (SO2) is well established in the literature and is classified like a typical Lewis acid-base reaction, however there are some unexplored aspects that are lacking in the literature. One of such aspects is the fact that the complexes formed between the aromatic amines and SO2 gives origin of an oily intense red color solution. The maximum of electronic absorption (UV-VIS) of these complexes is near to 350 nm, with a tail that extends along the visible region, which is responsible for the color. A curious fact is that the complex color changes with the temperature variation in a reversible manner. At low temperatures, the color complex becomes pale yellow and at high temperatures, it turns a very intense dark red solution. One of the main objectives of this work was to reinvestigate the charge-transfer interaction between aromatic amines and SO2 trying to answer this question. For this, it was utilized spectroscopic techniques (Raman and Infrared), especially resonance Raman spectroscopy, with the support of theoretical calculations based on the Density Functional Theory (DFT). The resonance Raman spectra showed the selective enhancement of a band nearly 1140 cm-1 with both, the changing of the exciting radiation and the temperature variation. The fact of this band was preferentially enhanced with visible exciting radiations and at higher temperatures, allowed the proposition of the presence of another chromophore in solution. Therefore, besides the already well characterized complex with 1:1 stoichiometry, it was proposed the presence of a complex possessing a 2:1 stoichiometry, i.e. with two amines connected by a SO2 molecule, forming a charge transfer complex with higher electronic delocalization. The comparison among the different amines showed that the formation of such associated species depends on a delicate balance between basicity, sterical hindrance and the possibility of specific interactions such as hydrogen bonding

Neste trabalho foram estudados três complexos de transferência de carga formados por aminas aromáticas e SO2. As aminas escolhidas foram a N,N-dimetilanilina (DMA), N,N-dietilanilina (DEA) e N-metilanilina (NMA). A interação entre a espécie doadora (amina) e a espécie aceptora (SO2) está bem esclarecida na literatura e trata-se de um reação típica de ácido-base de Lewis, porém existem alguns aspectos inexplorados e sem registros na literatura. Um desses aspectos é o fato de que complexos formados entre as aminas aromáticas e o SO2 dão origem a soluções oleosas com coloração vermelha intensa. O máximo de absorção eletrônica (UV-VIS) desses compostos está na faixa de 350 nm, com uma cauda que se estende pela região do visível, responsável pela cor. Um fato curioso é que a cor desses complexos se altera com a variação da temperatura de forma reversível. Em baixas temperaturas o complexo torna-se amarelo pálido e em altas temperaturas, vermelho escuro muito intenso. Um dos principais objetivos deste trabalho foi reinvestigar a interação de transferência de carga entre aminas aromáticas e SO2 na tentativa de responder tal questão. Para tal, foram utilizadas técnicas espectroscópicas (Raman e Infravermelho), sobretudo a espectroscopia Raman ressonante, com o auxílio de cálculos teóricos baseados na teoria do funcional da densidade (DFT). Os espectros Raman ressonante mostraram a intensificação seletiva de uma banda em cerca de 1140 cm-1 tanto com a variação da radiação quanto com a variação de temperatura. O fato dessa banda ter sido intensificada preferencialmente em radiações de excitação na região do visível e em altas temperaturas, permitiu que fosse proposta a presença de um outro cromóforo em solução. Portanto, além do complexo já bem caracterizado com estequiometria 1:1, propôs-se a presença de um complexo com estequiometria 2:1, ou seja, duas aminas conectadas por uma molécula de SO2, formando um complexo de transferência de carga com maior deslocalização eletrônica. A comparação entre as diferentes aminas mostrou que a formação dessas espécies associadas depende de um delicado balanço entre basicidade, impedimento estérico e possibilidade de interações específicas como ligações de hidrogênio. / In this work three charge-transfer complexes formed by aromatic amines and SO2 were studied. The chosen amines were N,N-dimethylaniline (DMA), N,N-diethylaniline (DEA) e N-methylaniline (NMA). The interaction between the donor (amine) and acceptor (SO2) is well established in the literature and is classified like a typical Lewis acid-base reaction, however there are some unexplored aspects that are lacking in the literature. One of such aspects is the fact that the complexes formed between the aromatic amines and SO2 gives origin of an oily intense red color solution. The maximum of electronic absorption (UV-VIS) of these complexes is near to 350 nm, with a tail that extends along the visible region, which is responsible for the color. A curious fact is that the complex color changes with the temperature variation in a reversible manner. At low temperatures, the color complex becomes pale yellow and at high temperatures, it turns a very intense dark red solution. One of the main objectives of this work was to reinvestigate the charge-transfer interaction between aromatic amines and SO2 trying to answer this question. For this, it was utilized spectroscopic techniques (Raman and Infrared), especially resonance Raman spectroscopy, with the support of theoretical calculations based on the Density Functional Theory (DFT). The resonance Raman spectra showed the selective enhancement of a band nearly 1140 cm-1 with both, the changing of the exciting radiation and the temperature variation. The fact of this band was preferentially enhanced with visible exciting radiations and at higher temperatures, allowed the proposition of the presence of another chromophore in solution. Therefore, besides the already well characterized complex with 1:1 stoichiometry, it was proposed the presence of a complex possessing a 2:1 stoichiometry, i.e. with two amines connected by a SO2 molecule, forming a charge transfer complex with higher electronic delocalization. The comparison among the different amines showed that the formation of such associated species depends on a delicate balance between basicity, sterical hindrance and the possibility of specific interactions such as hydrogen bonding

L'objectif central de cette thèse est l'évaluation de la possibilité d'utilisation de complexes moléculaires à transitions de spin pour des applications en nano-électronique. Dans un premier temps, les propriétés électriques du complexe [Fe(Htrz)2(trz)](BF4) et de ces analogues [Fe1-xZnx(Htrz)2(trz)](BF4) ont été analysées sous forme de poudres au moyen de la spectroscopie diélectrique. Il a été montré que les conductivités AC et DC aussi bien que la constante diélectrique et que la fréquence de relaxation diélectrique subissent une baisse importante lors de la transition de l'état bas spin (BS) vers l'état haut spin (HS). Les molécules à base de cations de fer gardent leurs propriétés de transition de spin dans les échantillons dilués de Zn, mais les courbes de transition de spin sont considérablement altérées. La substitution par Zn des centres de fer actifs mène à une importante baisse de la conductivité électrique d'environ 6 ordres de grandeur (pour Zn/Fe = 0.75). Nous concluons de ces résultats que les ions Fe(II) participent directement au processus de transport des charges, qui a été analysé dans le cadre d'un modèle de conductivité par saut de porteurs de charge activé thermiquement. Des particules micrométriques de [Fe(Htrz)2(trz)](BF4) ont été alors intégrées par diélectrophorèse entre des électrodes d'or. Ainsi, nous avons obtenu un dispositif montrant un phénomène de bistabilité lors de la caractérisation I-V, T. La stabilité du matériau initial et le dispositif électronique ont été contrôlés avec précision et les effets concomitants de changements de températures, d'irradiation lumineuse et du champ électrique sur l'intensité du courant ont été analysés en détail. D'une part, nous avons montré que le dispositif peut être adressé de manière préférentielle par une irradiation lumineuse en fonction de son état de spin, et d'autre part, nous avons démontré la commutation de l'état métastable HS vers l'état stable BS par application d'un champ électrique à l'intérieur du cycle d'hystérésis. Les effets de champ ont été discutés dans le cadre de modèles de type Ising statiques et dynamiques, tandis que les phénomènes photo-induits étaient attribués à des effets de surface. Le complexe [Fe(H2B(pz)2)2(phen)] a également été caractérisé par spectroscopie diélectrique sous forme de poudre et ensuite intégré par évaporation thermique sous vide au sein d'un dispositif vertical entre les électrodes en Al et ITO. Cette approche nous a permis de sonder la commutation de l'état de spin dans la couche de [Fe(bpz)2(phen)] par des moyens optiques tout en détectant les changements de résistance associés, à la fois dans les régimes à effet tunnel (jonction de 10 nm) et dans les régimes à injection (jonctions de 30 et 100 nm). Le courant tunnel dans les jonctions à transition de spin diminue durant la commutation de l'état BS vers l'état HS, tandis que le comportement de rectification des jonctions " épaisses " ne révélait aucune dépendance significative à l'état de spin. L'ensemble de ces résultats ouvre la voie à de nouvelles perspectives pour la construction de dispositifs électroniques et spintroniques incorporant des matériaux à transition de spin. / The central theme of this thesis is the evaluation of potential interest and applicability of molecular spin crossover (SCO) complexes for nanoelectronic applications. The electrical properties of the [Fe(Htrz)2(trz)](BF4) complex and its Zn substituted analogues were analyzed first in the bulk powder form using broadband dielectric spectroscopy. It has been shown that the ac and dc conductivities as well as the dielectric constant and the dielectric relaxation frequency exhibit an important drop when going from the low spin (LS) to the high spin (HS) state. The iron ions kept their spin transition properties in the Zn diluted samples, but the SCO curves were significantly altered. The Zn substitution of active iron centers led to an important decrease of the electrical conductivity of ca. 6 orders of magnitude (for Zn/Fe = 0.75). We concluded from these results that the ferrous ions directly participate to the charge transport process, which was analyzed in the frame of an activated hopping conductivity model. Micrometric particles of [Fe(Htrz)2(trz)](BF4) were then integrated by dielectrophoresis between interdigitated gold electrodes leading to a device exhibiting bistability in the I-V,T characteristics. The stability of the starting material and the electronic device were carefully controlled and the concomitant effect of temperature changes, light irradiation and voltage bias on the current intensity were analyzed in detail. We showed that the device can be preferentially addressed by light stimulation according to its spin state and the switching from the metastable HS to the stable LS state was also demonstrated by applying an electric field step inside the hysteresis loop. The field effects were discussed in the frame of static and dynamic Ising-like models, while the photo-induced phenomena were tentatively attributed to surface phenomena. The [Fe(bpz)2(phen)] complex was also investigated by dielectric spectroscopy in the bulk powder form and then integrated by high vacuum thermal evaporation into a large-area vertical device with Al (top) and ITO (bottom) electrodes. This approach allowed us to probe the spin-state switching in the SCO layer by optical means while detecting the associated resistance changes both in the tunneling (10 nm junction) and injection-limited (30 and 100 nm junctions) regimes. The tunneling current in the thin SCO junctions showed a drop when going from the LS to the HS state, while the rectifying behavior of the 'thick' junctions did not reveal any significant spin-state dependence. The ensemble of these results provides guidance with new perspectives for the construction of electronic and spintronic devices incorporating SCO molecular materials.

Devido à escassez de dados espectroscópicos sobre as interações de aminas aromáticas com SO2 e devido também à importância que complexos de transferência de carga assumem numa série de processos, inclusive biológicos, realizou-se um estudo objetivando a caracterização dessa interação através de várias técnicas espectroscópicas, como a espectroscopia Raman, no Infravermelho, no visível-ultravioleta e de Ressonância Magnética Nuclear. A partir dos dados obtidos nesses estudos concluímos que ocorre transferência de carga da amina para o SO2 ; essa transferência ocorre a partir do orbital ocupado de maior energia da amina , localizado principalmente no átomo de nitrogênio, para o orbital vago de mais baixa -energia do SO2 (π * ) localizado no a-tomo de enxofre. Os espectros vibracionais mostram que não é possível correlacionar as frequências de estiramento do SO2 complexado com o pKb (ou potencial de ionização) da base e sugerem que fatores estéricos podem ser importantes, influenciando o recobrimento dos orbitais do doador e do aceptor. No caso particular da ANI.SO2 , alterações na região de estiramento N-H do espectro no infravermelho , indicam que muito provavelmente ocorre a formação de ligações de hidrogênio entre a amina e o SO2 além da interação através do átomo de nitrogênio. ° comportamento termocrômico dos complexos foi investigado através de espectroscopia Raman à baixa temperatura. As informações preliminares obtidas sugerem que o desaparecimento da côr é devido a uma depopulação dos estados vibracionais excitados, a partir dos quais se efetuam as transições eletrônicas com fatores de Franck-Condon muito favoráveis / The shortage of spectroscopic data on the interactions between amines and SO2, together with the relevance that molecular complexes have in several process, including biological ones, stimulated us to study these systems by Raman, Infrared, Visible-Ultra violet and NMR spectroscopic techniques. From the data obtained, it\'s possible to conclude that there is charge transfer from the HOMO of the amines, which is localized mainly at the nitrogen atom, to the LUMO of SO2, localized at the sulfur atom. The vibrational spectra show that it is impossible to correlate any of the SO2 vibrational bands to the pKb of the donor and suggest that steric hindrance may play an important role in such interations, affecting the overlap of donor and aceptor orbitals; in the case of ANI.SO2 , the band shape in the N-H stretching region led us to conclude that hidrogen bonding between the amine and SO2 occurs, together with the specific interation through the nitrogen atom. The complexes show Pré-Resonance Raman Effect and from its study one concludes that SO2 belongs to the chromophoric group. The thermochromism that the complexes present was investigated by Raman Spectroscopy at low temperature. The informations obtained strongly suggest that the vanishing of its colour may be atributed to a depopulation of an vibrational excited state from which the charge transfer eletronic transition can occur with apreciable Franck-Condon factors.

L’objectif principal de ce travail de thèse était d’évaluer les propriétés électro catalytiques de différents composés moléculaires vis-à-vis de la réduction électrochimique basse température du dioxyde de carbone, en vue d’applications dans des cellules d’électrolyse à électrolyte polymère solide. Après avoir mesuré les performances de métaux modèles (cuivre et nickel) servant de référence, nous avons testé les performances de quelques composés moléculaires à base de nickel. Le rôle catalytique de ces différents composés a été mis en évidence en mesurant les courbes intensité-potentiel dans différents milieux. Nous avons évalué l’importance de la source en hydrogène dans le mécanisme réactionnel. Les produits de réduction du dioxyde de carbone formés dans le mélange réactionnel ont été analysés par chromatographie en phase gazeuse. Nous avons ensuite abordé la possibilité de développer des cellules d’électrolyse à électrolyte polymère solide. Nous avons testé des cellules utilisant soit des anodes à eau liquide pour le dégagement d’oxygène, soit des anodes à hydrogène gazeux. L’utilisation de complexes moléculaires à base de nickel à la cathode a permis d’abaisser le potentiel de la cathode et de réduire le CO₂ mais la réaction de dégagement d’hydrogène reste prédominante. / The main objective of this research work was to put into evidence the electrocatalytic activity of various molecular compounds with regard to the electrochemical reduction of carbon dioxide, at low temperature, in view of potential application in PEM cells. First, reference values have been measured on copper and nickel metals. Then the performances of some molecular compounds have been measured. The electrochemical activity of these different compounds has been put into evidence by recording the current-potential relationships in various media. The role of a hydrogen source for the reduction processes has been evaluated. The formation of reduction products has been put into evidence and analyzed by gas phase chromatography. Then, a PEM cell has been developed and preliminary tests have been performed. PEM cells with either an oxygen-evolving anode or a hydrogen-consuming anode have been tested. Using nickel molecular complexes, it has been possible to lower the potential of the cathode and to reduce CO₂ but the parasite hydrogen evolution reaction was found to remain predominant.

Devido à escassez de dados espectroscópicos sobre as interações de aminas aromáticas com SO2 e devido também à importância que complexos de transferência de carga assumem numa série de processos, inclusive biológicos, realizou-se um estudo objetivando a caracterização dessa interação através de várias técnicas espectroscópicas, como a espectroscopia Raman, no Infravermelho, no visível-ultravioleta e de Ressonância Magnética Nuclear. A partir dos dados obtidos nesses estudos concluímos que ocorre transferência de carga da amina para o SO2 ; essa transferência ocorre a partir do orbital ocupado de maior energia da amina , localizado principalmente no átomo de nitrogênio, para o orbital vago de mais baixa -energia do SO2 (π * ) localizado no a-tomo de enxofre. Os espectros vibracionais mostram que não é possível correlacionar as frequências de estiramento do SO2 complexado com o pKb (ou potencial de ionização) da base e sugerem que fatores estéricos podem ser importantes, influenciando o recobrimento dos orbitais do doador e do aceptor. No caso particular da ANI.SO2 , alterações na região de estiramento N-H do espectro no infravermelho , indicam que muito provavelmente ocorre a formação de ligações de hidrogênio entre a amina e o SO2 além da interação através do átomo de nitrogênio. ° comportamento termocrômico dos complexos foi investigado através de espectroscopia Raman à baixa temperatura. As informações preliminares obtidas sugerem que o desaparecimento da côr é devido a uma depopulação dos estados vibracionais excitados, a partir dos quais se efetuam as transições eletrônicas com fatores de Franck-Condon muito favoráveis / The shortage of spectroscopic data on the interactions between amines and SO2, together with the relevance that molecular complexes have in several process, including biological ones, stimulated us to study these systems by Raman, Infrared, Visible-Ultra violet and NMR spectroscopic techniques. From the data obtained, it\'s possible to conclude that there is charge transfer from the HOMO of the amines, which is localized mainly at the nitrogen atom, to the LUMO of SO2, localized at the sulfur atom. The vibrational spectra show that it is impossible to correlate any of the SO2 vibrational bands to the pKb of the donor and suggest that steric hindrance may play an important role in such interations, affecting the overlap of donor and aceptor orbitals; in the case of ANI.SO2 , the band shape in the N-H stretching region led us to conclude that hidrogen bonding between the amine and SO2 occurs, together with the specific interation through the nitrogen atom. The complexes show Pré-Resonance Raman Effect and from its study one concludes that SO2 belongs to the chromophoric group. The thermochromism that the complexes present was investigated by Raman Spectroscopy at low temperature. The informations obtained strongly suggest that the vanishing of its colour may be atributed to a depopulation of an vibrational excited state from which the charge transfer eletronic transition can occur with apreciable Franck-Condon factors.

As aminas heterocíclicas alifáticas, piperidina, piperazina e pirrolidina, interagem com o dióxido de enxofre, gasoso ou líquido, dando origem a uma série de compostos em diferentes estequiometrias, os quais foram investigados fundamentalmente por técnicas espectroscópicas vibracionais, infravermelho e Raman, utilizando-se como técnicas auxiliares a espectroscopia eletrônica, espectros de massas e de ressonância magnética nuclear. Os resultados obtidos caracterizam as espécies estudadas como complexos moleculares formados entre as aminas e o SO2, especialmente devido aos deslocamentos de frequências observados nos espectros Raman, para os modos vibracionais de estiramento simétrico e deformação angular do dióxido de enxofre. Os dados indicam no sentido do estabelecimento de intensas ligações de hidrogênio, as quais devem desempenhar importante papel na estabilização dos complexos. Os deslocamentos observados nos espectros Raman encontram-se de acordo com o comportamento previsto para a interação de transferência de carga, em que o LUMO do SO2 apresenta caráter antiligante em relação à ligação S-O e ligante em relação à interação O-O. / The interaction of alifatic heterocyclic amines piperidine, piperazine and pyrrolidine, with sulfur dioxide yields a variety of products of different stoichiometry. The investigation of the formed species were carried out mainly by vibrational spectroscopic techniques, infrared and Raman, and electronic spectroscopy, mass spectrometry and nuclear magnetic resonance spectra were used as auxiliary techniques. The obtained results indicate that the studied species are charge transfer molecular complexes due to the frequency shifts of the symmetric stretching and angular deformation modes of sulfur dioxide in the Raman spectra. The data are in agreement with an S-O antibonding and a O-O bonding character of the LUMO of SO2. Hydrogen bonds play an important role in the complex stabilization.