Work reported in this thesis mainly comprises of the assignments and analysis of the rotational spectra and structures of three weakly bound complexes: C2H4•••H2S, C6H5CCH•••H2O and C6H5CCH•••H2S. All the data have been collected using a home built Pulsed Nozzle Fourier Transform Microwave Spectrometer. Apart from this, the thesis also deals with a criterion of classifying a weakly bound complex to a ‘hydrogen-bonded’ one. First chapter of the thesis gives a brief intermolecular interactions and molecular clusters of π system. It also briefly touches on the structural determination by rotational spectroscopy and the basic information one can gain from the rotational spectrum. Second chapter of the thesis gives a brief introduction to the experimental and theoretical methodology. It also gives a description of the software used in the FTMW spectrometer which was rebuilt using Labview 7.1. Third chapter of the thesis deals with the rotational spectra and structure of eight isotopologoues of C2H4•••H2S complex. The lines are split into four components for the parent isotopologue due to the presence of large amplitude motion. The smaller splitting is 0.14 MHz and the higher splitting is 1.67 MHz in (B+C)/2 for the parent isotopologue. Spectral splitting pattern of the isotopologues confirmed that smaller splitting is due to the rotation of ethylene about its C-C bond axis along with the contraction of S-H bond whereas the larger motion arises due to the interchange of equivalent hydrogens of H2S in the complex. A detailed spectral analysis and ab initio calculation for this system have been described in chapter III. The fourth chapter of the thesis describes the rotational spectroscopic studies of five isotopologues of C6H5CCH•••H2O complex. Rotational spectra unequivocally confirm the structure of the complex to be a one where H2O is donating one of its hydrogen to the acetylenic π cloud forming a O-H••• π bond whereas the ring ortho C-H bond forms C-H•••O bond with the water oxygen. For theparent isotopomer the lines are split into two components due to the rotation of H2O about its C2 symmetric axis. The fifth chapter of thesis describes the rotational spectroscopic and ab initio studies of five isotopologues of C6H5CCH•••H2S complex. Rotational spectra indicate the structure to be the one where H2S is sitting on the top of the phenyl ring and shifted towards the acetylenic group. The sixth chapter of the thesis describes a criterion for calling a complex to be hydrogen bonded based on the dynamic structure rather than the static structure of the complex. The question asked is if the anisotropy of the interaction is strong enough to hold the ‘hydrogen bond’ when one takes dynamics into account. The proposed criterion is that the zero point energy of the motion which takes the hydrogen away from the acceptor should be much less than the barrier height of the respective motion supporting at least one bound level below the barrier. Ab initio calculations have been done on four model systems Ar2•••H2O, Ar2•••H2S, C2H4••• H2O and C2H4••• H2S to emphasize this criterion.

In solution, the environment around the solute is determined solely by the solvent molecules, which are present closer to the solute. This interaction between solute and solvent shell is very crucial for equilibrium structure and reactivity of the solute. In the thesis, first we have investigated control of solvent polarity on the excited structure of 2,2,2 trifluroacetophenone and later effect of electronic excitation on the solvent shell organization has been described. It has been reported in literature that the lowest energy triplet configuration of 2,2,2 trifluroacetophenone corresponds to n,π* state. There are some other reports in favor of the probable existence of 2,2,2 trifluroacetophenone in n,π* lowest triplet state. Thus, transient absorption and time resolved resonance Raman spectroscopic methods have been used along with theoretical calculations to investigate the discrepancy in the assignment of the lowest triplet state configuration It has been observed that the lowest triplet state of 2,2,2 trifluroacetophenone is indeed nπ* and there is a solvent polarity induced change in triplet state energy ordering and structure changes. The absorption spectrum of hydrated electron is broad and structureless. So, it was though that the broadening feature could be attributed to homogeneous and inhomogeneous broadening. Transient resonance Raman spectrum of the water bending mode in presence of hydrated electron has been recorded at different excitation wavelengths. Interestingly, it has been observed that, peak position of water bending mode in presence of hydrated electron alters with change of excitation wavelength. A model has been proposed based on the experimental data.

No description available.

The thesis entitled “Structure-function control in organic co-crystals/salts via studies on polymorphism, phase transitions and stoichiometric variants” consists of five chapters. The main emphasis of the thesis is on two aspects, one to characterize co-crystal polymorphism in terms of propensity of intermolecular interactions to form co-crystals/salts or eutectics. The other aspect is to explore the feasibility of using such co-crystals/salts to exhibit properties like proton conduction, dielectric and ferroelectric behaviour. Gallic acid and its analogues possess functionalities to provide extensive hydrogen bonding capabilities and are chosen as the main component while the coformers are carefully selected such that they either accept or reject the hydrogen bonding offered. Such co-crystallization experiments therefore provide an opportunity to unravel the intricate details of the formation of crystalline polymorphs and/or eutectics at the molecular level. Further these co-crystal systems have been exploited to evaluate proton conductivity, dielectric and ferroelectric features since the focus is also on the design aspect of functional materials. In the context of identifying and utilizing Crystal Engineering tools, the discussions in the following chapters address not only the structural details but identify the required patterns and motifs to enable the design of multi-component co-crystals/salts and eutectics. In particular, the presence/absence of lattice water in gallic acid has been evaluated in terms of importing the required physical property to the system. Chapter 1 discusses the structural features of tetramorphic anhydrous co-crystals (1:1; which are synthon polymorphs) generated from a methanolic solution of gallic acid monohydrate and acetamide, all of which convert to a stable form on complete drying. The pathway to the stable form (1:3 co-crystal) is explained based on the variability in the hydrogen bonding patterns followed by lattice energy calculations. Chapter 2A studies the presence/absence and geometric disposition of hydroxyl functionality on hydroxybenzoic acids to drive the formation of co-crystal/eutectic in imide-carboxylic acid combinations. In Chapter 2B the crystal form diversity of gallic acid-succinimide co-crystals are evaluated with major implications towards the design and control of targeted multi-component crystal forms. The co-crystal obtained in this study shows a rare phenomenon of concomitant solvation besides concomitant polymorphism and thus making it difficult to obtain a phase-pure crystal form in bulk quantity. This issue has been resolved and formation of desired target solid form is demonstrated. Thus, this study addresses the nemesis issues of co-crystallization with implications in comprehending the kinetics and thermodynamics of the phenomenon in the goal of making desired materials. Chapter 3 focuses on the systematic co-crystallization of hydroxybenzoic acids with hexamine using liquid assisted grinding (LAG) which show facile solid state interconversion among different stoichiometric variants. The reversible interconversion brought about by varying both the acid and base components in tandem is shown to be a consequence of hydrogen bonded synthon modularity present in the crystal structures analyzed in this context. In Chapter 4A, the rationale for the proton conduction in hydrated/anhydrous salt/co-crystal of gallic acid - isoniazid is provided in terms of the structural characteristics and the conduction pathway is identified to follow Grotthuss like mechanism which is supplemented by theoretical calculations. Chapter 4B describes an extensive examination of the hydrated salt of gallic acid-isoniazid which unravels the irreversible nature of the dielectric property upon dehydration and suggests that the “ferroelectric like” behaviour is indeed not authenticated. This chapter brings out the significance role of lattice water in controlling the resulting physical property (dielectric/ferroelectric in this case). Chapter 5 describes the structural features of two hydrated quaternary salts of hydroxybenzoic acids-isoniazid-sulfuric acid and the phase transitions at both low and high temperatures are shown to be reversible. Single Crystal to Single Crystal (SCSC) in situ measurement corroborated by thermal and in situ Powder X-ray Diffraction studies proves the claim. Further, the properties exhibited by these materials are also governed by lattice water content.

The research work reported in this thesis is focused on the chiral analysis, quantification of enantiomeric composition, assignment of absolute configuration of molecules with chosen functional groups. The weak intra-molecular hydrogen bonding interactions are detected by exploiting several multinuclear and multi-dimensional techniques. Pulse sequences have been designed to manipulate the spin dynamics to derive specific information from the complex NMR spectra encountered in diverse situations. Broadly, the thesis can be classified in to three sections. The section I containing two chapters reports the introduction of new chiral auxiliaries and protocols developed for enantiomeric discrimination, measurement of enantiomeric contents, assignment of absolute configuration for molecules possessing specific functional groups using chiral solvating and derivatizing agents. The section II, reports NMR experimental evidence for the observation of the rare type of intramolecular hydrogen bonds involving organic fluorine in biologically important organic molecules, that are corroborated by extensive DFT based theoretical calculations. The section II also discusses the H/D exchange mechanism as a tool for quantification of HB strengths in organic building blocks. The section III reports the two different novel NMR methodologies designed for deriving information on the scalar interaction strengths in an orchestrated manner. The designed sequences are able to completely eradicate the axial peaks, prevents the evolution of unwanted couplings and also yields ultrahigh resolution in the direct dimension, permitting the accurate measurement of scalar couplings for a particular spin. The brief summary about each chapter is given below. Chapter 1 provides a general introduction to one and two dimensional NMR spectroscopy. The pedagogical approach has been followed to discuss the conceptual understanding of spin physics and the NMR spectral parameters. The basic introduction to chirality, existing approaches in the literature for discrimination of enantiomers and the assignment of absolute configuration of molecules with chosen functional groups and their limitations are briefly discussed. The brief introduction to hydrogen bond, experimental methods to obtain the qualitative information about the strengths of hydrogen bonds, and the theoretical approaches employed in the thesis to corroborate the NMR experimental findings have been provided. The mechanism of H/D exchange, the utilization of exchange rates to derive strengths of intra-molecular hydrogen bond in small molecules have also been discussed. This chapter builds the bridge for the rest of the chapters. Each of these topics are discussed at length in the corresponding chapters. Part I: NMR Chiral Analysis: Novel Protocols Chapter 2 discusses a simple mix and shake method for testing the enantiopurity of primary, secondary and tertiary chiral amines and their derivatives, amino alcohols. The protocol involves the in-situ formation of chiral ammonium borate salt from a mixture of C2 symmetric chiral BINOL, trialkoxyborane and chiral amines. The proposed concept has been convincingly demonstrated for the visualization of enantiomers of a large number of chiral and pro-chiral amines and amino alcohols. The protocol also permits the precise measurement of enantiomeric composition. The significant advantage of the protocol is that it can be performed directly in the NMR tube, without any physical purification. The structure of the borate complex responsible for the enantiodifferentiation of amines has also been established by employing multinuclear NMR techniques and DFT calculations. From DOSY and 11B NMR experiments it has been ascertained that there are only two possible complexes or entities which are responsible for differentiating enantiomers. From the combined utility of DFT calculations and the 11B NMR chemical shifts, the structure of the borate complex has been determined to be an amine-coordinated complex with the N atom of the amine. Chapter 3 discusses a simple chiral derivatizing protocol involving the coupling of 2-formylphenylboronic acid and an optically pure [1,1-binaphthalene]-2,2-diamine for the rapid and accurate determination of the enantiopurity of hydroxy acids and their derivatives, possessing one or two optically active centres. It is established that this protocol is not only rapid method for discrimination of enantiomers but also highly effective for assigning the absolute configuration of various chiral hydroxy acids and their derivatives. The developed protocol involves the coupling of 2-formylphenylboronic acid with (R)-[1,1-binaphthalene]-2,2-diamine, and 2-formylphenylboronic acid with (S)-[1,1-binaphthalene]-2,2-diamine as chiral derivatizing agents. The absence of aliphatic peaks from the derivatizing agent, large chemical shift separation between the discriminated peaks of diastereomers, and the systematic change in the direction of displacement of peaks for an enantiomer in a particular diastereomeric complex, permitted the unambiguous assignment of absolute configuration. Part II : Rare Type of Intramolecular Hydrogen Bonding In chapter 4 The rare occurrence of intramolecular hydrogen bonds of the type N–H˖˖˖F–C, in the derivatives of imides and hydrazides in a low polarity solvent, is convincingly established by employing multi-dimensional and multinuclear solution state NMR experiments. The observation of 1hJFH, 2hJFN, and 2hJFF of significant strengths, where the spin polarization is transmitted through space among the interacting NMR active nuclei, provided strong and conclusive evidence for the existence of intra-molecular hydrogen bonds. Solvent induced perturbations and the variable temperature NMR experiments unambiguously supported the presence of intramolecular hydrogen bond. The two dimensional HOESY and 15N–1H HSQC experiments reveals the existence of multiple conformers in some of the investigated molecules. The 1H DOSY experimental results discarded any possibility of self or cross-dimerization of the molecules. The results of DFT based calculations, viz., Quantum Theory of Atoms In Molecules (QTAIM) and Non Covalent Interaction (NCI), are in close agreement with the NMR experimental findings. In chapter 5 the rates of hydrogen/deuterium (H/D) exchange determined by 1H NMR spectra have been utilized to derive the strength of hydrogen bonds and to monitor the electronic effects in the site-specific halogen substituted Benz amides and anilines. The theoretical fitting of the time dependent variation in the integral areas of 1H NMR resonances to the first order decay function permitted the determination of H/D exchange rate constants (k) and their precise half-lives (t1/2) with high degree of reproducibility. The comparative study also permitted the determination of relative strengths of hydrogen bonds and the contribution from electronic effects on the H/D exchange rates. Part III: Novel NMR Methodologies for the Precise Measurement of 1H-1H Couplings Chapter 6 describes two novel NMR methodologies developed for the precise measurement of 1H-1H couplings. Poor chemical shift dispersion and the pairwise interaction among the entire coupled network of protons results in the severely complex and overcrowded one dimensional 1H NMR spectra, hampering both the resonance assignments and the accurate determination of nJHH. The available two-dimensional selective refocusing (SERF) based experiments suffer from the evolution of magnetization from uncoupled protons as intense uninformative axial peaks. This creates ambiguity in the identification of peaks belonging to the coupled partners of a selectively excited proton, hindering the extraction of their interaction strengths. This challenge has been circumvented by designing two novel experimental technique, cited as “Clean-G-SERF” and “PS-Clean-G-SERF”. The Clean-G-SERF technique completely eradicates the axial peaks and suppresses the evolution of unwanted couplings while retaining only the couplings to the selectively excited proton. The method permits the accurate determination of spin-spin couplings even from a complex proton NMR spectrum in an orchestrated manner. The PS-Clean-G-SERF technique has been designed for the complete elimination of axial peaks and undesired couplings, with a blend of ultra-high resolution achieved by real time broad band mononuclear decoupling has been discussed in this chapter. The spin dynamics involved in both these pulse sequences have been discussed. The diverse applications of both these novel experiments have been demonstrated.

CAPES; Fundação Araucária / A análise conformacional abrange os aspectos da determinação de estruturas geométricas moleculares, energias relativas de confôrmeros e das interações que controlam as estabilidades estruturais. Neste sentido, as preferências conformacionais dos compostos 3-aminopropanol (1), 3-N-metilaminopropanol (2), 3-N,N-dimetilaminopropanol (3), 3-aminobutanol (4), 3-Nmetilaminobutanol (5) e 3-N,N-dimetilaminobutanol (6) foram avaliadas experimentalmente através de espectroscopias de Infravermelho (IV) e Ressonância Magnética Nuclear (RMN), e teoricamente por cálculos usando a Teoria do Funcional de Densidade (DFT). O estudo destes compostos foi importante porque irá melhorar a compreensão das interações que ocorrem nestas moléculas em diferentes ambientes químicos, uma vez que existe uma ampla gama de amino álcoois com aplicações biológicas e sintéticas. Diante disso, os cálculos teóricos mostraram que a ligação de hidrogênio intramolecular (LHI) O-H ...N governa a estabilidade e a preferência conformacional dos compostos 1-6. A LHI favorece uma conformação do tipo pseudo-cadeira de seis membros com substituintes em posições pseudo-equatoriais e pseudo-axiais, os quais apresentam interações repulsivas que também contribuem expressivamente para a estabilidade conformacional, principalmente dos compostos 4-6. Os resultados experimentais obtidos através do IV mostraram que os deslocamentos para o vermelho da banda da ligação OH foram de 193, 225 e 256 cm-1 para os compostos 1, 2 e 3, respectivamente. Estes resultados foram surpreendentes e indicaram que a força da LHI aumenta nesta ordem apesar do efeito estérico também aumentar. Uma primeira metodologia, para calcular a fração molar experimental de confôrmeros com LHI (XLHI) para compostos acíclicos 1,3-dissubstituídos por RMN de 1H, foi proposta neste trabalho. Os resultados de XLHI foram muito interessantes e mostraram que em solventes apolares tais como CCl4 os confôrmeros com LHI são predominantes no equilíbrio conformacional (XLHI = 0,70, 0,69 e 0,78 para os compostos 1-3). Já em solventes polares como DMSO-d6, os valores de XLHI foram bem menores (0,10, 0,08 e 0,08 para os compostos 1-3), indicando uma mudança no equilíbrio conformacional de confôrmeros que faziam LHI para confôrmeros que não tinham este tipo de interação. As análises por Teoria Quântica de Átomos em Moléculas e Interações Não Covalentes evidenciaram, caracterizaram e quantificaram a intensidade da LHI nos compostos 1-6. Estes resultados foram concordantes com os dados experimentais e indicaram que tanto as LHI quanto as interações estéricas influenciam de forma significativa na estabilidade conformacional de todos os compostos estudados. / The conformational analysis covers aspects of the determination of molecular geometric structures, relative energies of conformers and interactions that control structural stabilities. In this sense, the conformational preferences of the compounds (1), 3-N-methylaminopropanol (2), 3-N,N-dimethylaminopropanol (3), 3-aminobutanol (4), 3-N-methylaminobutanol (5) and 3-N,N-dimethylaminobutanol (6) are evaluated experimentally through Infrared (IR) and Nuclear Magnetic Resonance (NMR) spectroscopies and theoretically by calculations using the Density Functional Theory (DFT). The study of these compounds was important because it will improve the understanding of the interactions that occur in these molecules in different chemical environments, since there is a wide range of amino alcohols with biological and synthetic applications. In view of this, theoretical calculations showed that the O-H···N intramolecular hydrogen bonding (IHB) governs the stability and the conformational preference of compounds 1-6. The IHB favors the formation of a chair like six member ring with substituents at pseudo-equatorial-axial positions, which exhibit repulsive interactions that also contribute significantly to the conformational stability, especially of compounds 4-6. The IR experimental results showed a OH band red shift of 193, 225, and 256 cm-1 for compounds 1, 2 and 3, respectively. These results were surprising and indicated that the strength of IHB increases in this order although the steric effect also increases. A first methodology for calculating the experimental molar fraction of hydrogen-bonded conformers (XIHB), in any solvent by 1H NMR, was proposed to attend 1,3-disubstituted acyclic compounds. The XIHB results showed that in non-polar solvents, such as CCl4 solvent, the hydrogen-bonded conformers predominate in the conformational equilibria (XIHB = 0.70, 0.69 and 0.78 for compounds 1-3). In polar solvents, such as DMSO-d6, the XIHB values decrease (0.10, 0.08 and 0.08 in compounds 1-3) indicating a change in conformational equilibria from hydrogenbonded conformers to non-hydrogen-bonded conformers. Quantum Theory of Atoms in Molecules and Non-Covalent Interactions analysis evidences, characterizes and quantifies the strength of IHB in compounds 1-6. These results agreed with the experimental data and indicated that both IHB and steric interactions significantly influence the conformational stability of all compounds studied.

A organização e a estabilidade de compostos de coordenação, no estado sólido, pode ser correlacionada com os ligantes diretamente coordenados a íons metálicos e com as interações não covalentes estabelecidas entre os ligantes e solventes de cristalização. O presente trabalho avaliou a influência dos pré ligantes ácido 2,6-dihidróxibenzoico (Hdhb), ácido benzoico (Hbzt), ácido oxálico (H2ox) e 2,2’-bipiridina (bipi), capazes de realizar interações não covalentes, em sua reatividade frente a sais de cobre(II), cobalto(II) e manganês(II). Foram avaliadas diferentes combinações de ligantes para cada íon metálico e condições de reação, gerando um total de dez produtos caracterizados por DRX de monocristal. Dentre eles, os complexos [Cu2( ox)(bzt)2(bipi)2(H2O)2] (A), [Co(H2O)6](dhb)2·2H2O (B) e [Mn(H2O)6](dhb)2·2H2O (C) são inéditos. Estes produtos foram avaliados em sua composição elementar, analisados por técnicas difratométricas (DRX de pó e de monocristal) e espectroscópicas (IV, Raman, RPE e Uv/Vis). Os dados estruturais foram correlacionados com as propriedades espectroscópicas, termogravimétricas e magnéticas. O produto A foi obtido em 90 % de rendimento a partir da reação de Cu(CH3COO)2·H2O com os pré-ligantes Hbzt, H2ox e bipi, em metanol a 70 °C. A análise por DRX de monocristal revelou que em A todos os ligantes contribuem para a manifestação de interações não covalentes do tipo ligações de hidrogênio e interação . A análise por RPE e medidas de susceptibilidade magnética à temperatura ambiente indicaram a existência de interação magnética entre os centros de cobre(II). Medidas de susceptibilidade magnética com variação de temperatura revelaram uma interação ferromagnética (J = 3,26 cm-1) mais forte que a apresentada por complexos análogos. Medidas termogravimétricas mostraram que a decomposição de A se inicia em 55 °C com a perda de 2 H2O, seguida da perda dos ligantes orgânicos entre 136 e 900 °C. Os produtos B e C, de estruturas análogas, foram obtidos em 97 e 99 % de rendimento, respectivamente, a partir da reação de CoCl2·6H2O ou MnCl2·4H2O com o pré-ligante Hdhb, em água a 70 °C. A análise por DRX de monocristal revelou que não ocorreu a coordenação do íon dhb, provavelmente devido a estabilização do carboxilato livre por duas ligações de hidrogênio intramoleculares assistidas por carga. A rede cristalina de B e C também é estabilizada por interações  e por ligações de hidrogênio intermoleculares formadas a partir das águas coordenadas e de cristalização. A decomposição térmica de B e C se inicia com a perda de moléculas de água a temperaturas inferiores a 55 °C e a perda total da parte orgânica ocorre acima de 600 °C. Os compostos obtidos neste trabalho evidenciaram que a estrutura e o grau de agregação dos compostos são dependentes da habilidade de coordenação do ligante ao íon metálico e das interações não covalentes nos ligantes livres e nos complexos formados. / The organization and stability of coordination compounds could be correlated to structural features, as the number and nature of ligands coordinated to the metallic ions and with noncovalent interactions established between the ligands and with crystallization solvents. The present work evaluated the influence of the pre-ligands 2,6-dihydroxybenzoic acid (Hdhb), benzoic acid (Hbzt), oxalic acid (H2ox), and 2,2' bipyridine (bipi), capable to perform noncovalent interactions, in its reactivity to copper(II), cobalt(II) and manganese(II) salts. For each metallic ion, and reaction condition were evaluated with different combinations of ligands, producing 10 different structures characterized by single crystal XRD. Among them, the complexes [Cu2( ox)(bzt)2(bipi)2(H2O)2] (A), [Co(H2O)6](dhb)2·2H2O (B), and [Mn(H2O)6](dhb)2·2H2O (C) were synthesized for the first time in this work. Those products were characterized by elemental analysis and diffractometric (powder and single crystal XRD) and spectroscopic (IR, Raman, EPR and Uv/Vis) techniques. Moreover, spectroscopic, thermogravimetric and magnetic properties of A, B and C, were attempt correlated with their structural features. Product A was obtained with 90% of yield from the reaction of Cu(CH3COO)2·H2O with the pre-ligands Hbzt, H2ox, and bipy, in methanol at 70 °C. Single crystal XRD analysis of A evidenced that all ligands interact through noncovalent interactions, as hydrogen bonds and  interaction. EPR and magnetic susceptibility measurements strongly suggest the existence of magnetic interaction between the copper(II) centres. In addition, magnetic susceptibility measurement varying temperature revealed a ferromagnetic exchange (J = 3.26 cm-1) stronger than those observed for analogous complexes. Thermal decomposition of A starts at 55 °C with the loss of two water molecules, succeed by the loss of the organic ligands (136 – 900 °C). Product B and C showed similar structures and were obtained in 97 and 99 % of yield, respectively, from the reaction of CoCl2·6H2O or Mn2Cl2·4H2O with Hdhb, in water at 70° C. Single crystal XRD analysis revealed that dhb ion remains as counterion of the aqua complexes, probably due the stabilization of the free carboxylate by two intramolecular charge-assisted hydrogen bonds. The crystal lattice of B and C is also stabilized by  interactions and intermolecular hydrogen bonds from both coordinated and crystallization water molecules. According to TGA curves, the thermal decomposition of B and C starts with the loss of water molecules below 55° C, and a complete weight-loss of organic ligands occurs above 600° C for both complexes. The correlation between the nature of all products obtained with synthetic conditions revealed that the structure and degree of aggregation depends on the coordination ability of the ligand to the metallic ion and on the noncovalent interactions in the free ligands and complexes formed.

CAPES; Fundação Araucária / A análise conformacional abrange os aspectos da determinação de estruturas geométricas moleculares, energias relativas de confôrmeros e das interações que controlam as estabilidades estruturais. Neste sentido, as preferências conformacionais dos compostos 3-aminopropanol (1), 3-N-metilaminopropanol (2), 3-N,N-dimetilaminopropanol (3), 3-aminobutanol (4), 3-Nmetilaminobutanol (5) e 3-N,N-dimetilaminobutanol (6) foram avaliadas experimentalmente através de espectroscopias de Infravermelho (IV) e Ressonância Magnética Nuclear (RMN), e teoricamente por cálculos usando a Teoria do Funcional de Densidade (DFT). O estudo destes compostos foi importante porque irá melhorar a compreensão das interações que ocorrem nestas moléculas em diferentes ambientes químicos, uma vez que existe uma ampla gama de amino álcoois com aplicações biológicas e sintéticas. Diante disso, os cálculos teóricos mostraram que a ligação de hidrogênio intramolecular (LHI) O-H ...N governa a estabilidade e a preferência conformacional dos compostos 1-6. A LHI favorece uma conformação do tipo pseudo-cadeira de seis membros com substituintes em posições pseudo-equatoriais e pseudo-axiais, os quais apresentam interações repulsivas que também contribuem expressivamente para a estabilidade conformacional, principalmente dos compostos 4-6. Os resultados experimentais obtidos através do IV mostraram que os deslocamentos para o vermelho da banda da ligação OH foram de 193, 225 e 256 cm-1 para os compostos 1, 2 e 3, respectivamente. Estes resultados foram surpreendentes e indicaram que a força da LHI aumenta nesta ordem apesar do efeito estérico também aumentar. Uma primeira metodologia, para calcular a fração molar experimental de confôrmeros com LHI (XLHI) para compostos acíclicos 1,3-dissubstituídos por RMN de 1H, foi proposta neste trabalho. Os resultados de XLHI foram muito interessantes e mostraram que em solventes apolares tais como CCl4 os confôrmeros com LHI são predominantes no equilíbrio conformacional (XLHI = 0,70, 0,69 e 0,78 para os compostos 1-3). Já em solventes polares como DMSO-d6, os valores de XLHI foram bem menores (0,10, 0,08 e 0,08 para os compostos 1-3), indicando uma mudança no equilíbrio conformacional de confôrmeros que faziam LHI para confôrmeros que não tinham este tipo de interação. As análises por Teoria Quântica de Átomos em Moléculas e Interações Não Covalentes evidenciaram, caracterizaram e quantificaram a intensidade da LHI nos compostos 1-6. Estes resultados foram concordantes com os dados experimentais e indicaram que tanto as LHI quanto as interações estéricas influenciam de forma significativa na estabilidade conformacional de todos os compostos estudados. / The conformational analysis covers aspects of the determination of molecular geometric structures, relative energies of conformers and interactions that control structural stabilities. In this sense, the conformational preferences of the compounds (1), 3-N-methylaminopropanol (2), 3-N,N-dimethylaminopropanol (3), 3-aminobutanol (4), 3-N-methylaminobutanol (5) and 3-N,N-dimethylaminobutanol (6) are evaluated experimentally through Infrared (IR) and Nuclear Magnetic Resonance (NMR) spectroscopies and theoretically by calculations using the Density Functional Theory (DFT). The study of these compounds was important because it will improve the understanding of the interactions that occur in these molecules in different chemical environments, since there is a wide range of amino alcohols with biological and synthetic applications. In view of this, theoretical calculations showed that the O-H···N intramolecular hydrogen bonding (IHB) governs the stability and the conformational preference of compounds 1-6. The IHB favors the formation of a chair like six member ring with substituents at pseudo-equatorial-axial positions, which exhibit repulsive interactions that also contribute significantly to the conformational stability, especially of compounds 4-6. The IR experimental results showed a OH band red shift of 193, 225, and 256 cm-1 for compounds 1, 2 and 3, respectively. These results were surprising and indicated that the strength of IHB increases in this order although the steric effect also increases. A first methodology for calculating the experimental molar fraction of hydrogen-bonded conformers (XIHB), in any solvent by 1H NMR, was proposed to attend 1,3-disubstituted acyclic compounds. The XIHB results showed that in non-polar solvents, such as CCl4 solvent, the hydrogen-bonded conformers predominate in the conformational equilibria (XIHB = 0.70, 0.69 and 0.78 for compounds 1-3). In polar solvents, such as DMSO-d6, the XIHB values decrease (0.10, 0.08 and 0.08 in compounds 1-3) indicating a change in conformational equilibria from hydrogenbonded conformers to non-hydrogen-bonded conformers. Quantum Theory of Atoms in Molecules and Non-Covalent Interactions analysis evidences, characterizes and quantifies the strength of IHB in compounds 1-6. These results agreed with the experimental data and indicated that both IHB and steric interactions significantly influence the conformational stability of all compounds studied.

A organização e a estabilidade de compostos de coordenação, no estado sólido, pode ser correlacionada com os ligantes diretamente coordenados a íons metálicos e com as interações não covalentes estabelecidas entre os ligantes e solventes de cristalização. O presente trabalho avaliou a influência dos pré ligantes ácido 2,6-dihidróxibenzoico (Hdhb), ácido benzoico (Hbzt), ácido oxálico (H2ox) e 2,2’-bipiridina (bipi), capazes de realizar interações não covalentes, em sua reatividade frente a sais de cobre(II), cobalto(II) e manganês(II). Foram avaliadas diferentes combinações de ligantes para cada íon metálico e condições de reação, gerando um total de dez produtos caracterizados por DRX de monocristal. Dentre eles, os complexos [Cu2( ox)(bzt)2(bipi)2(H2O)2] (A), [Co(H2O)6](dhb)2·2H2O (B) e [Mn(H2O)6](dhb)2·2H2O (C) são inéditos. Estes produtos foram avaliados em sua composição elementar, analisados por técnicas difratométricas (DRX de pó e de monocristal) e espectroscópicas (IV, Raman, RPE e Uv/Vis). Os dados estruturais foram correlacionados com as propriedades espectroscópicas, termogravimétricas e magnéticas. O produto A foi obtido em 90 % de rendimento a partir da reação de Cu(CH3COO)2·H2O com os pré-ligantes Hbzt, H2ox e bipi, em metanol a 70 °C. A análise por DRX de monocristal revelou que em A todos os ligantes contribuem para a manifestação de interações não covalentes do tipo ligações de hidrogênio e interação . A análise por RPE e medidas de susceptibilidade magnética à temperatura ambiente indicaram a existência de interação magnética entre os centros de cobre(II). Medidas de susceptibilidade magnética com variação de temperatura revelaram uma interação ferromagnética (J = 3,26 cm-1) mais forte que a apresentada por complexos análogos. Medidas termogravimétricas mostraram que a decomposição de A se inicia em 55 °C com a perda de 2 H2O, seguida da perda dos ligantes orgânicos entre 136 e 900 °C. Os produtos B e C, de estruturas análogas, foram obtidos em 97 e 99 % de rendimento, respectivamente, a partir da reação de CoCl2·6H2O ou MnCl2·4H2O com o pré-ligante Hdhb, em água a 70 °C. A análise por DRX de monocristal revelou que não ocorreu a coordenação do íon dhb, provavelmente devido a estabilização do carboxilato livre por duas ligações de hidrogênio intramoleculares assistidas por carga. A rede cristalina de B e C também é estabilizada por interações  e por ligações de hidrogênio intermoleculares formadas a partir das águas coordenadas e de cristalização. A decomposição térmica de B e C se inicia com a perda de moléculas de água a temperaturas inferiores a 55 °C e a perda total da parte orgânica ocorre acima de 600 °C. Os compostos obtidos neste trabalho evidenciaram que a estrutura e o grau de agregação dos compostos são dependentes da habilidade de coordenação do ligante ao íon metálico e das interações não covalentes nos ligantes livres e nos complexos formados. / The organization and stability of coordination compounds could be correlated to structural features, as the number and nature of ligands coordinated to the metallic ions and with noncovalent interactions established between the ligands and with crystallization solvents. The present work evaluated the influence of the pre-ligands 2,6-dihydroxybenzoic acid (Hdhb), benzoic acid (Hbzt), oxalic acid (H2ox), and 2,2' bipyridine (bipi), capable to perform noncovalent interactions, in its reactivity to copper(II), cobalt(II) and manganese(II) salts. For each metallic ion, and reaction condition were evaluated with different combinations of ligands, producing 10 different structures characterized by single crystal XRD. Among them, the complexes [Cu2( ox)(bzt)2(bipi)2(H2O)2] (A), [Co(H2O)6](dhb)2·2H2O (B), and [Mn(H2O)6](dhb)2·2H2O (C) were synthesized for the first time in this work. Those products were characterized by elemental analysis and diffractometric (powder and single crystal XRD) and spectroscopic (IR, Raman, EPR and Uv/Vis) techniques. Moreover, spectroscopic, thermogravimetric and magnetic properties of A, B and C, were attempt correlated with their structural features. Product A was obtained with 90% of yield from the reaction of Cu(CH3COO)2·H2O with the pre-ligands Hbzt, H2ox, and bipy, in methanol at 70 °C. Single crystal XRD analysis of A evidenced that all ligands interact through noncovalent interactions, as hydrogen bonds and  interaction. EPR and magnetic susceptibility measurements strongly suggest the existence of magnetic interaction between the copper(II) centres. In addition, magnetic susceptibility measurement varying temperature revealed a ferromagnetic exchange (J = 3.26 cm-1) stronger than those observed for analogous complexes. Thermal decomposition of A starts at 55 °C with the loss of two water molecules, succeed by the loss of the organic ligands (136 – 900 °C). Product B and C showed similar structures and were obtained in 97 and 99 % of yield, respectively, from the reaction of CoCl2·6H2O or Mn2Cl2·4H2O with Hdhb, in water at 70° C. Single crystal XRD analysis revealed that dhb ion remains as counterion of the aqua complexes, probably due the stabilization of the free carboxylate by two intramolecular charge-assisted hydrogen bonds. The crystal lattice of B and C is also stabilized by  interactions and intermolecular hydrogen bonds from both coordinated and crystallization water molecules. According to TGA curves, the thermal decomposition of B and C starts with the loss of water molecules below 55° C, and a complete weight-loss of organic ligands occurs above 600° C for both complexes. The correlation between the nature of all products obtained with synthetic conditions revealed that the structure and degree of aggregation depends on the coordination ability of the ligand to the metallic ion and on the noncovalent interactions in the free ligands and complexes formed.

Weak intermolecular interactions have very strong impact on the structures and properties of life giving molecules like H2O, DNA, RNA etc. These interactions are responsible for many biological phenomena. The directional preference of some of these interactions is used for designing different synthetic approaches in the supramolecular chemistry. The work reported in this Thesis comprises of investigations of weak intermolecular interactions in gas phase using home-built Pulsed Nozzle Fourier Transform Microwave (PN-FTMW) spectrometer as an experimental tool and ab-initio and Atoms in Molecules (AIM) theory as theoretical tools. The spectrometer which is coupled with a pulsed nozzle is used to record pure rotational spectra of the molecular clusters in a jet cooled molecular beam. In the molecular beam molecules/complexes are free from interactions with other molecules/complexes and thus, spectroscopy in the molecular beams provides information about the 'isolated' molecule/complex under investigation. The rotational spectra of the molecules/complexes in the molecular beam provide their geometry in the ground vibrational states. These experimental geometries can be used to test the performance and accuracy of theoretical models like ab-initio theory, when applied to the weakly bound complexes. Further the AIM theory can be used to gain insights into the nature and strength of the intermolecular interactions present in the system under investigation. Chapter I of this Thesis gives a brief introduction of intermolecular interactions. Other than hydrogen bonding, which is considered as the most important intermolecular interaction, many other intermolecular interactions involving different atoms have been observed in past few decades. The chapter summarizes all these interactions. The chapter also gives a brief introduction to the experimental and theoretical methods used to probe these interactions. In Chapter II, the experimental and theoretical methods used in this work are summarized. Details of our home-built PN-FTMW spectrometer are given in this chapter. The chapter also discusses briefly the theoretical methods like ab-initio, AIM and Natural bond orbital (NBO) analysis. We have made few changes in the mode of control of one of our delay generators which have also been described. Chapter III and Chapter V of this Thesis are dedicated to the propargyl alcohol complexes. Propargyl alcohol (PA) is a molecule of astrophysical interest. It is also important in combustion chemistry since propargyl radical is considered as the precursor in soot formation. Moreover, PA is a multifunctional molecule, having a hydroxyl (-OH) and an acetylenic (-C≡C-H) group. Both of the groups can individually act as hydrogen bond acceptor as well as donor and thus PA provides an exciting possibility of studying many different types of weak interactions. Due to internal motion of -OH group, PA monomer can exist in gauche as well as trans form. However, rotational spectra of PA-monomer show the presence of only gauche conformer. In Chapter III, rotational spectra of Ar•••PA complex are discussed. The pure rotational spectra of the parent Ar•••PA complex and its two deuterated isotopologues, Ar•••PA-D (OD species) and Ar•••PA-D (CD species), could be observed and fitted within experimental uncertainty. The structural fitting confirmed a structure in which PA is present as gauche conformer and argon interacts with both the O-H group and the acetylenic group leading to Ar•••H-O and Ar•••π interactions respectively. Presence of these interactions was further confirmed by AIM theoretical analysis. In all the three isotopologues c-type rotational transitions showed significant splitting. Splitting patterns in the three isotopologues suggest that it originates mainly due to the large amplitude motion of the hydroxyl group and the motion is weakly coupled with the carbon chain bending motion. No evidence for the complex with trans conformer of PA was found. Although, we could not observe Ar•••trans-PA complex experimentally, we decided to perform ab-initio and AIM theoretical calculations on this complex as well. AIM calculations suggested the presence of Ar•••H-O and a unique Ar•••C interaction in this complex which was later found to be present in the Ar•••methanol complex as well. This prompted us to explore different possible interactions in methanol, other than the well known O-H•••O hydrogen bonding interactions, and eventually led us to an interesting interaction which we termed as carbon bond. Chapter IV discusses carbon bonding interaction in different complexes. Electrostatic potential (ESP) calculations show that tetrahedral face of methane is electron-rich and thus can act as hydrogen/halogen bond acceptor. This has already been observed in many complexes, e.g. CH4•••H2O/HF/HCl/ClF etc., both experimentally and theoretically. However, substitution of one of the hydrogens of methane with -OH leads to complete reversal of the properties of the CH3 tetrahedral face and this face in methanol is electron-deficient. We found that CH3 face in methanol interacts with electron rich sites of HnY molecules and leads to the formation of complexes stabilized by Y•••C-X interactions. This interaction was also found to be present in the complexes of many different CH3X (X=OH/F/Cl/Br/NO2/NF2 etc.) molecules. AIM, NBO and C-X frequency shift analyses suggest that this interaction could be termed as "carbon bond". The carbon bonding interactions could be important in understanding hydrophobic interactions and thus could play an important role in biological phenomena like protein folding. The carbon bonding interaction could also play a significant role in the stabilization of the transition state in SN2 reactions. In Chapter V of this Thesis rotational spectra of propargyl alcohol dimer are discussed. Rotational spectra of the parent dimer and its three deuterated (O-D) isotopologues (two mono-substituted and one bi-substituted) could be recorded and fitted within experimental uncertainty. The fitted rotational constants are close to one of the ab-initio predicted structure. In the dimer also propargyl alcohol exists in the gauche form. Atoms in molecules analysis suggests that the experimentally observed dimer is bound by O-H•••O, O-H•••π and C-H•••π interactions. Chapter VI of the thesis explores the 'electrophore concept'. To observe the rotational spectra of any species and determine its rotational constant by microwave spectroscopy, the species should have a permanent dipole moment. Can we obtain rotational constants of a species having no dipole moment via microwave spectroscopy? Electrophore concept can be used for this purpose. An electrophore is an atom or molecule which could combine with another molecule having no dipole moment thereby forming a complex with a dipole moment, e.g. Argon atom is an electrophore in Ar•••C6H6 complex. The microwave spectra of Ar•••13CC5H6 and Ar•••C6H5D complexes were recorded and fitted. The A rotational constant of these complexes was found to be equal to the C rotational constant of 13CC5H6 and C6H5D molecules respectively and thus we could determine the C rotational constant of microwave 'inactive' 13CC5H6. This concept could be used to obtain the rotational spectra of parallel displaced benzene-dimer if it exists. We recently showed that the square pyramidal Fe(CO)5 can act as hydrogen bond acceptor. Appendix I summarizes the extension of this work and discusses interactions of trigonal bipyramidal Fe(CO)5 with HF, HCl, HBr and ClF. Our initial attempts on generating a chirped pulse to be used in a new broadband spectrometer are summarized in Appendix II. Preliminary investigations on the propargyl•••water complex are summarized in Appendix III.