Two distinct research projects were carried out in this dissertation. In the first project the results of first principle calculations on endo- and exohedral complexes of polyhedral oligomeric silsesqiuoxanes (POSS) with atomic and ionic species were carried out. Detailed studies were performed on structures, stabilities and electronic properties of these complexes. The stabilities of the endohedral Tn-POSS ( n = 8, 10 and 12) complexes depends on both the cage size and the nature of the endohedral species. Alkali metal ion encapsulation leads to cage contraction. Electron density was transferred from the cage to the alkali metal cations. Halide encapsulation caused the cages to expand. Electron density was transferred from the halides to the cage. Noble gas encapsulation has minimum effect on the cage structure. Electron transfer between cage framework atoms and He and Ne were negligible. However, a small amount of electron transfer between Ar and POSS cages occurred. Ionization potentials calculated for T10-POSS and T12-POSS endohedral complexes with alkali metals indicate that these complexes have "superalkali" behavior. Several transition metal encapsulations into the T8-POSS cage gave thermodynamically stable endohedral complexes. The HOMO-LUMO gaps for the transition metal endohedral complexes were reduced versus that of pure cage. In almost all cases, the exohedral Tn (n = 8, 10, 12) complexes were energetically more stable than their corresponding endohedral counterparts except for the complex with F-. The exohedral Fpenetrates directly into the Tn-POSS cage forming an endohedral complex. In the second project ab initio electronic structure calculations based on density functional theory were performed to study small silicon clusters containing an endohedral atoms or ions. The formation of endohedral clusters M@Si12 (Li0,1,-1, Na0,1,-1, K+, He, F- and Cl-) depended on the Si12 cage structure and the nature of the embedding species. Only Li0,1,-1, Na0,1,-1 and He form endohedral clusters with different Si12 cage isomers. All observed endohedral clusters are stable and have large HUMO-LUMO gaps (>1eV). The endohedral clusters Li-@Si12 and Na-@Si12 are thermodynamically more stable than their neutral and cationic counterparts. The stability order predicted for the alkali metal series was anionic clusters > neutral clusters> cationic clusters. Encapsulations of halides are completely unfavorable and halide insertions cause the Si12 cage rupture. Encapsulation of two Li atoms into the Si18 cage generates the endohedral Li2@Si18 complex. Encapsulating Na atoms into Si18 cage leads to an exohedral Na2Si18 cluster. Endohedral Si20@Li20 was also investigated and characterized.

No description available.

A series of tetravalent zirconium and hafnium complexes were developed in their abundant chemistry and photophysical properties, where those complexes were supported by diarylamido-phosphino [iPr-PNP]- (bis(o-diisopropylphosphinophenyl)amide) ligand. [iPr-PNP]MCl3 (M = Zr, Hf) were prepared by sequentially reacting [iPr-PNP]H with n-butyllithium and following MCl4(THF)2 in toluene solution under ambient temperature. UV-Vis absorption, emission, excitation spectrum, cyclic voltammetry experiments, and density functionalization theory (DFT) calculations are applied to approach their unique photophysical phosphorescence properties. Alkyls which are lack of £]-hydrogen have been used to achieve in synthesis of degenerate ([iPr-PNP]MR3, R = Me, CH2SiMe3) or non-degenerate ([iPr-PNP]M(E)(R)2, R = CH2SiMe3, E = Cl, Me) derivatives since we could control the desired product from steric effect. Strong fluxional exchange was found in those complexes. By variable temperature NMR monitoring and X-ray diffraction, their fluxionality seems interesting not only in mechanism, but it does affect our reaction. By heating [iPr-PNP]Zr(Cl)(CH2SiMe3)2 in solution, we can afford new alkylidene complexes [iPr-PNP]M(Cl)(=CHSiMe3) via self £\-abstraction. Through variable temperature analysis, the activation energy of £\-abstraction have £GH‡ = 18.5 kcal/mol and £GS‡ = -19.8 cal/mol¡PK. Here we also can identified multiple alkylidene derivatives of [iPr-PNP]Zr(Me)(=CHSiMe3)2. The computational studies of [MeNPiPr]Ni(R)(L) ([MeNPiPr]- = o-diisopropylphosphinoII phenyl-2,6-dimethylanilite, R = Me, CH2SiMe3; L = 2,4-Lutidine, Py, PMe3) in C-H activation has been fully established. Start on dissociation mechanism, we considered three major pathways to explain the activation mechanisms including isomerisation, direct intermolecular benzene activation, and intramolecular sp3 C-H acitvaition. Here we also account H-D exchange as experimental observation. Important intermediates and transition states are found to locate the energy maps to assist our experiments.

Neste trabalho foram realizados estudos conformacionais de algumas lactonas sesquiterpenicas e cálculos teóricos de deslocamento químico. O estudo conformacional é dividido em tres etapas distintas. A primeira etapa se dá pela busca conformacional em mecânica molecular, onde foram encontradas as possíveis conformações assumidas pelo sistema em estudo. Na segunda etapa, as conformações encontradas foram otimizadas em mecânica quântica. O último passo neste estudo foi o cálculode deslocamento químico e a posterior correlação com os dados experimentais. / This work is aimed on the theoretical calculation of chemical shifts of sesquiterpene lactones, based on the conformational preferences of the compounds. This conformational study is set up in three stages. The first one is a conformational search using molecular mechanics, to assess the relevant conformations of the system under study. In the second stage, the conformations are optimized by quantum mechanics, for the refinement of both the structural assignment and energy calculation of the most stable conformers found in the previous step. The last step is the theoretical calculation of chemical shifts. Finally the weighted average of calculated values is compared to experimental data.

Neste trabalho foram realizados estudos conformacionais de algumas lactonas sesquiterpenicas e cálculos teóricos de deslocamento químico. O estudo conformacional é dividido em tres etapas distintas. A primeira etapa se dá pela busca conformacional em mecânica molecular, onde foram encontradas as possíveis conformações assumidas pelo sistema em estudo. Na segunda etapa, as conformações encontradas foram otimizadas em mecânica quântica. O último passo neste estudo foi o cálculode deslocamento químico e a posterior correlação com os dados experimentais. / This work is aimed on the theoretical calculation of chemical shifts of sesquiterpene lactones, based on the conformational preferences of the compounds. This conformational study is set up in three stages. The first one is a conformational search using molecular mechanics, to assess the relevant conformations of the system under study. In the second stage, the conformations are optimized by quantum mechanics, for the refinement of both the structural assignment and energy calculation of the most stable conformers found in the previous step. The last step is the theoretical calculation of chemical shifts. Finally the weighted average of calculated values is compared to experimental data.

Orientador: Claudio Francisco Tormena / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T02:29:08Z (GMT). No. of bitstreams: 1 Favaro_DenizeCristina_D.pdf: 6372818 bytes, checksum: c89cc5eb491bd0129e563fc2dd200aac (MD5) Previous issue date: 2014 / Resumo: A tese "Estudo dos mecanismos de transmissão dos acoplamentos escalares via ligações e/ou via nuvem eletrônica próxima no espaço e estudos de difusão (DOSY) de 19F" é composta de 5 capítulos. O primeiro capítulo é uma visão geral sobre Ressonância Magnética Nuclear (RMN), sequências de pulso para determinação experimental das constantes de acoplamento, mecanismos envolvidos na transmissão desse importante parâmetro de RMN e Teoria dos Orbitais Naturais de Ligação (NBO). No segundo capítulo há uma introdução sobre acoplamentos transmitidos "espacialmente" (TS). Posteriormente, os valores de nJFN, cujo n4, são correlacionados com distância (dFN) e densidade eletrônica ao longo do caminho do acoplamento. No terceiro capítulo os mecanismos de transmissão da constante de acoplamento JFH em 2-F-benzaldeído foram investigados. A motivação para este estudo foi a observação do maior valor dessa constante em meio polar. Os resultados teóricos mostraram que a forma sinperiplanar é a mais estável, porém a porcentagem da forma antiperiplanar aumenta em solvente polar. Além disso, os resultados teóricos suportam um JFH maior para a forma anti. Esses resultados corroboram com o dado experimental acima mencionado. Seguindo a apresentação dos resultados, o capítulo 4 versa sobre o uso de constante de acoplamento vicinal (3JCH) para a determinação da estereoquímica de duplas ligações. Primeiro apresentamos a metodologia sel-HSQMBC-TOCSY utilizada para determinação do acoplamento 3JCH. Posteriormente apresentamos uma racionalização para os valores observados para derivados de quinolina e pirrolizidinonas, mostrando a importância da ocupância dos orbitais e da % de caráter s dos carbonos envolvidos para a transmissão desse acoplamento. Por fim, no capítulo 5 são apresentados os resultados para os experimentos de DOSY (Diffusion Ordered SpectroscopY). Neste capítulo apresentamos a sequência Oneshot-19F{1H} uma modificação da sequência original Oneshot-1H para detecção de 19F com desacoplamento de 1H / Abstract: The thesis "Study of the mechanisms of transmission of the scalar couplings through bond and/or through the electronic cloud close in space and studies of diffusion (DOSY) of 19F" is composed by 5 chapters. The first chapter is an overview of Nuclear Magnetic Resonance (NMR), pulse sequences to determine experimentally scalar spin-spin coupling constants (SSCC), mechanisms involved in the transmission of SSCC and Natural Bond Orbital analysis (NBO). The second chapter introduced the through space coupling constant (TS) transmission pathway. In addition, it was proposed a correlation among the values of nJFN, with n?4, the distance (dFN) and the electronic density along the coupling pathway. In the third chapter the mechanisms involved in the transmission of the JFH coupling constant in 2-F-benzaldehyde were investigated. The experimental observation of a higher coupling constant in polar solvent compared to the nonpolar one was our motivation to evaluate in details this coupling constant. It is important to highlight that was not possible to determine experimentally this coupling constant in nonpolar solvent because the value is smaller than spectral resolution. From theoretical calculation it was observed that the syn periplanar is the most stable conformer, however the population of the antiperiplanar conformer increases in polar solvent. Besides, the theoretical results support higher JFH value for the antiperiplanar conformer in comparison to syn periplanar. These results are in agreement with the experimental. Following the discussion, chapter 4 is related to the application of vicinal coupling constant (3JCH) for relatively stereochemical determination. The experimental 3JCH coupling was measured using sel-HSQMBC-TOCSY pulse sequence. In addition, it was done a rationalization of the couplings observed for quinolines and pirrozilidinones derivatives, suggesting that the % s character of the carbons and occupancy of the orbitals involved in the coupling pathway describes the experimental behavior. Finally, chapter 5 introduces the use of DOSY (Diffusion Ordered SpectroscopY). For this purpose, It was designed a pulse sequence dubbed Oneshot-19F{1H} ¿ consisting in a modification of the original Oneshot-1H to allow radiofrequency changes between 1H and 19F channels and a 1H decoupling during 19F acquisition / Doutorado / Quimica Organica / Doutora em Ciências

Made available in DSpace on 2017-07-20T12:40:20Z (GMT). No. of bitstreams: 1 Mariana_N_Levandowski.pdf: 3613595 bytes, checksum: 6d13f04a1872ade8572c9eae481770c6 (MD5) Previous issue date: 2017-02-13 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This study presents a theoretical and experimental analysis of the conformational equilibrium of phenylacetic acid and its derivatives, namely: o-fluorophenylacetic, ochlorophenylacetic, o-bromophenylacetic, o-nitrophenylacetic, hydroxyphenylacetic, m-fluorophenylacetic, p-fluorophenylacetic, p-nitrophenylacetic, p-hydroxyphenylacetic, p-mercaptophenylacetic and p-aminophenylacetic. Thetechniques used were computational calculations and nuclear magnetic resonance and infrared spectroscopy.The study made it possible to verify the conformational preference of each compound, determined by their energies and geometries, which were evaluated both for the isolated molecule, at distinct theory levels, and in different solvents, with the IEF-PCM solvation model. By using natural bond orbital calculations, it was possible to identify the main orbital interactions for each conformation. With the total deletion calculations, it was verified that there was a balance between the steric and hyperconjugative effects in the stabilization of the most stable structures. The majority conformers of halogenated compounds in ortho revealed the same spatial orientation between the carbonyl and the benzene ring, similar to that of the phenylacetic acid. In the derivatives, nitro and hydroxylated in ortho, there was the presence of an intramolecular hydrogen bond, but in none of these cases the interaction referred to one of the main conformers. The infrared experiments in solvents of different polarities, allowed the identification of more than one band, enabling the attribution of conformers present in the equilibrium as well as the observation of the same tendency as the one obtained theoretically. The coupling constant 1JCH was evaluated through nuclear magnetic resonance. No significant variation of this constant was observed, showing that the major contribution to the equilibrium is related to the majoritarian conformer, which prevails even with the change in the polarity of the medium, for each compound under evaluation. / Neste trabalho foi apresentado uma análise teórica e experimental do equilíbrio conformacional do ácido fenilacético e seus derivados, sendo eles: ofluorofenilacético, o-clorofenilacético, o-bromofenilacético, o-nitrofenilacético, ohidróxifenilacético, m-fluorofenilacético, p-fluorofenilacético, p-nitrofenilacético, phidróxifenilacético,p-mercaptofenilacético e p-aminofenilacético. As técnicas utilizadas foram os cálculos computacionais e as espectroscopias de ressonância magnética nuclear e infravermelho. Com este estudo foi possível verificar a preferência conformacional de cada composto, determinadas pelas suas energias e geometrias, as quais foram avaliadas tanto para a molécula isolada, em distintos níveis de teoria, quanto em diferentes solventes, com o modelo de solvatação IEFPCM. Através dos cálculos dos orbitais naturais de ligação foi possível identificar as principais interações orbitais para cada conformação. Com os cálculos de deleção total, verificou-se que houve um balanço entre os efeitos estérico e hiperconjugativo na estabilização das estruturas mais estáveis. Os confôrmeros majoritários dos compostos halogenados em orto mostraram a mesma orientação espacial entre a carbonila e o anel benzênico, semelhante ao ácido fenilacético. Nos derivados,nitrado e hidroxilado em orto, houve a presença de uma ligação de hidrogênio intramolecular, em nenhum dos casos esta interação era referente a um dos confôrmeros principais. Utilizando a técnica de infravermelho na região do fundamental da carbonila, em solventes de diferentes polaridades, permitiram identificar a presença de mais de uma banda, sendo possível a atribuição dos confôrmeros presentes no equilíbrio, bem como observar a mesma tendência obtida teoricamente. Com a espectroscopia de ressonância magnética nuclear foi avaliada a constante de acoplamento 1JCH. Não houve uma variação significativa desta constante, mostrando que a maior contribuição no equilíbrio está relacionada com o confôrmero majoritário, que prevalece mesmo com a mudança da polaridade do meio, de cada composto avaliado.

No description available.

Nanotubular structures from a new family of misfit compounds LnS–TaS₂ with (Ln = La, Ce, Nd, Ho, Er) and LaSe–TaSe₂ (some of them not known hitherto) are reported. Stress relaxation originating from the lattice mismatch between the alternating LnS(Se) and TaS₂(Se) layers, combined with seaming of the dangling bonds in the rim, leads to the formation of a variety of nanotubular structures. Their structures are studied via scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy (STEM) and selected area electron diffraction (SAED). Tubules exhibiting a single folding vector for the LnS(Se) as well as TaS₂(Se) layers were often found. The small values of the c-axis periodicities are indicative of a strong interaction between the two constituent layers which was also supported by Raman spectroscopy and theoretical calculations.