L-arginina fosfatada monohidratada (LAP) é um cristal semiorgânico altamente transparente com propriedades atrativas para conversão de freqüência. É facilmente crescido a partir de solução aquosa e apresenta casamento de fase para todos os processos não-lineares onde o KDP é casável em fase. Apresenta alto limiar de dano, excelente qualidade óptica, é menos higroscópico que o KDP e dispositivos não-lineares podem ser facilmente fabricados a partir deles. Neste trabalho apresentamos os resultados de diversos ensaios para avaliar a sua estabilidade térmica, mecânica e química. Concluiu-se que o cristal de LAP é estável para temperaturas inferiores à 100&#176C. Quando o material for submetido à processos que envolvem geração de grande quantidade de calor, tais como processamento do material por corte ou tomeamento (diamond tuming), ou em sistemas com lasers de alta intensidade, recomenda-se não exceder o limite de 100&#176C para assegurar que as propriedades do material não sejam alteradas / L-arginine phosphate monohydrate (LAP) is a highly transparent semiorganic crystal with atractive properties for frequency conversion. It is easily grown from aqueous solution, and it is phase matchable for alI nonlinear processes where KDP is phase matchable. lt has high damage threshold, exceHent optical quality, is less hygroscopic than KDP, and are easily fabricated into nonlinear devices. In this work we present the results of several tests to evaluate its thermal, mechanical, and chemical stabilities. It was found that LAP crystals are stable under temperatures up to 100&#176C. If this material is submited to processes involving the generation of considerable amount of heat, e.g. during cutting or diamond turning or due to high power lasers, it is recommended not to exceed the 100&#176C limit to ensure that crystal properties remain unchanged

Este trabalho trata da caracterização eletroóptica de cristais orgânicos, a saber: L-arginina fosfatada, L-alanina e L-treonina. O aspecto teórico que envolve este efeito nestes cristais é descrito, discutindo a forma de manifestação do efeito em cada um dos grupos de simetria cristalina aos quais pertencem. Além disso, discutimos e observamos a ocorrência de efeitos de natureza piezoelétrica durante o processo de caracterização eletroóptica. / This work reports on the electrooptical characterization of organic crystals, namely: L-arginine phosphate monohidrate, Lalanine and L-threonine. We describe the theoretical aspect in these crystals discussing how the effect occurs according to the symmetry groups of each one. Furthermore, we discuss and observe the occurrence of piezoelectric effects during the electrooptical characterization.

Este trabalho trata da caracterização eletroóptica de cristais orgânicos, a saber: L-arginina fosfatada, L-alanina e L-treonina. O aspecto teórico que envolve este efeito nestes cristais é descrito, discutindo a forma de manifestação do efeito em cada um dos grupos de simetria cristalina aos quais pertencem. Além disso, discutimos e observamos a ocorrência de efeitos de natureza piezoelétrica durante o processo de caracterização eletroóptica. / This work reports on the electrooptical characterization of organic crystals, namely: L-arginine phosphate monohidrate, Lalanine and L-threonine. We describe the theoretical aspect in these crystals discussing how the effect occurs according to the symmetry groups of each one. Furthermore, we discuss and observe the occurrence of piezoelectric effects during the electrooptical characterization.

L-arginina fosfatada monohidratada (LAP) é um cristal semiorgânico altamente transparente com propriedades atrativas para conversão de freqüência. É facilmente crescido a partir de solução aquosa e apresenta casamento de fase para todos os processos não-lineares onde o KDP é casável em fase. Apresenta alto limiar de dano, excelente qualidade óptica, é menos higroscópico que o KDP e dispositivos não-lineares podem ser facilmente fabricados a partir deles. Neste trabalho apresentamos os resultados de diversos ensaios para avaliar a sua estabilidade térmica, mecânica e química. Concluiu-se que o cristal de LAP é estável para temperaturas inferiores à 100&#176C. Quando o material for submetido à processos que envolvem geração de grande quantidade de calor, tais como processamento do material por corte ou tomeamento (diamond tuming), ou em sistemas com lasers de alta intensidade, recomenda-se não exceder o limite de 100&#176C para assegurar que as propriedades do material não sejam alteradas / L-arginine phosphate monohydrate (LAP) is a highly transparent semiorganic crystal with atractive properties for frequency conversion. It is easily grown from aqueous solution, and it is phase matchable for alI nonlinear processes where KDP is phase matchable. lt has high damage threshold, exceHent optical quality, is less hygroscopic than KDP, and are easily fabricated into nonlinear devices. In this work we present the results of several tests to evaluate its thermal, mechanical, and chemical stabilities. It was found that LAP crystals are stable under temperatures up to 100&#176C. If this material is submited to processes involving the generation of considerable amount of heat, e.g. during cutting or diamond turning or due to high power lasers, it is recommended not to exceed the 100&#176C limit to ensure that crystal properties remain unchanged

Terahertz (THz) spectroscopy is an emerging technology with promising applications in imaging, homeland security, and material detection and quantification. Frequencies in the THz region can be generated by optical rectification of ultrafast near-infrared laser pulses in the presence of a nonlinear optical (NLO) materials such as organic crystals. Non-centrosymmetric organic THz generating crystals such as DAST, HMQ-TMS, and OH1 have received special attention due to the strong generated fields on the order of MV/cm. The cation of these organic salts is designed by connecting electron-donating with electron-accepting groups via a highly planar aromatic system. To improve the performance of organic crystals for THz generation, the molecular hyperpolarizability (β) can be optimized by introducing modifications in the architecture of these push-pull chromophores. However, the large dipole moments associated with molecules that have a large β promote the formation of NLO inactive centrosymmetric molecular alignments in the crystal state. This dissertation provides important insights into the design of new push-pull chromophores that feature a) higher β values compared with state-of-the-art organic crystals, and b) non-centrosymmetric molecular packing in the crystalline state. The first strategy presented on this dissertation relates to the introduction of a triple bond instead of a double bond in the cation of DAST to improve the β parameter. The newly designed 4DEP core was combined with different anions to promote non-centrosymmetric molecular packing with almost ideal arrangements for THz generation. However, large single crystals were difficult to obtain and high THz generation was not achieved. The second strategy presented in this dissertation raises the value of β by extending the π-conjugation length in different cations with dimethylamino and methoxy electron-donating groups. A new molecular cation, 6MNEP, was found to have large β value combined with ideal non-centrosymmetric molecular packing. Combining these two factors, a ~ 75% higher performance for THz generation is expected for 6MNEP compared with DAST. Currently, we are testing different crystallization techniques to grow large single crystals of 6MNEP. In addition to the strategies developed to increase the β parameter value, we also introduce a new molecular modification to induce non-centrosymmetric packing in organic salt THz generating crystals. This is achieved by substituting a methyl by an ethyl group in the quaternary nitrogen of hydrogen-bonded crystals. We showed the applicability of this method for changing molecular packing in the crystal state from centrosymmetric to non-centrosymmetric in two different molecular cations. We also demonstrated the generation of strong THz fields in the novel NLO crystal EHPSI-4NBS.

Crystal engineering is widely applied in the design of new solids with desired physical and chemical properties based on an understanding of intermolecular interactions in terms of crystal packing. The understanding of such structure-property correlations increased my interest in the modulation of macroscopic properties of solid compounds. Establishing connections between structure and macroscopic properties is a classical aspect of materials science and engineering. With the advent of the nanoindentation technique, it is now possible to make such a link between micro-level structures with mechanical properties of molecular solids - in other words, between chemistry and engineering. Nanoindentation is a quantitative probe for the assessment of mechanical behavior of small volume materials. In this technique, applied load and indenter depth penetration are measured simultaneously for a molecular crystal specimen, with high precision and resolution. From this data, one can obtain the elastic modulus and hardness of molecular crystals. Being able to accordingly assess the relative strengths of intermolecular interactions, such a technique has become relevant to the subject of crystal engineering. We have used nanoindentation to study the packing anisotropy of molecular crystals and to establish structure-property relationships. This thesis demonstrates that nanoindentation is a state-of-the-art technique to probe the mechanical properties of molecular crystals and assists the development of the subject of crystal engineering towards property design. Chapter 1 gives an overview of the development of crystal engineering from solid state organic chemistry and a brief introduction of the nanoindentation technique which has become relevant to the subject of crystal engineering to establish structure-property relationships. The study of the mechanical properties of molecular solids as a function of their crystal structures is a very active branch of crystal engineering. Chapter 2 explores the insights of well-known odd-even alternative mechanical, physical and thermal properties of α,ω-alkanedicarboxylic acids such as elastic modulus, hardness and melting temperature through nanoindentation technique. These properties are well correlated with their crystal structure packing. The odd acids were found to be softer and lower melting temperature as compared to the even ones, possibly due to the strained molecular conformations in the odd acids in easier plastic deformation. Shear sliding of molecular layers past each other during indentation is a key to the mechanism for plastic deformation in the molecular crystals. Relationships between structural features such as interplanar spacing, interlayer separation distance, molecular chain length and signatures of the nanoindentation responses, discrete displacement bursts have also been discussed in this chapter. Chapter 3 explores the use of the nanoindentation measurement as a signature response to study the microstructure that exists in a single crystal of organic solids. The analysis of microstructure through X-ray crystallography can be misleading. This is because crystal structures as determined from the single-crystal diffractometer data represent only space- and time-averaged structures. Thus, due to higher spatial resolution of the nanoindentation technique compared to X-ray diffraction (XRD) it become a local probe, which allows for discrimination between different microstructure or domains in the single crystal. Chapter 4 attempts to explore an understanding of the underlying relationship between crystal structure and the mechanical properties of molecular crystals which are relevant for the systematic design of organic solids with a desired combination of mechanical properties such as elasticity and hardness through crystal engineering. Elastic properties in molecular solids are largely determined by the isotropy of crystal packing. By using the techniques of crystal engineering, seven halogenated N-benzylideneanilines (Schiff bases) crystals have been systematically designed and observed common underlying structural features which lead to high flexibility and elasticity. Elasticity in those crystals arises from a criss-cross packing of molecular tapes in isotropic structures with energetically comparable halogen bonds (Cl···Cl or Cl···Br). The chapter also demonstrates that the solid solution strengthening can be effectively employed to engineer hardness of organic solids. High hardness can be attained by increasing lattice resistance to shear sliding of molecular layers during plastic deformation. Chapter 5 demonstrates the broad applications of mechanical properties of molecular solids in the context of the pharmaceutical industry, which can be understood through nanoindentation. Crystal engineering is applied in designing active pharmaceutical ingredients (APIs) so as to obtain materials that exhibit optimum combinations of important physicochemical properties such as solubility, dissolution rate, and bioavailability. In the context of industrial-scale pharmaceutical manufacturing, it can also be used to tune mechanical properties such as grindability and tabletability, which often determine the processing steps that are adopted. Hence, there is always interest in the crystal structure−mechanical property correlations of APIs. The study of the mechanical properties of polymorphic drugs is an important for developing an understanding of their stability in the solid state. Overall, the main aim of this thesis is to explore an understanding for establishing structure-mechanical properties correlations of molecular crystals with recent advances in the nanoindentation technique and to gain knowledge for the design and synthesis of new materials using the crystal engineering approach. Nanoindentation of molecular crystals provides insights related to crystal packing, interaction characteristics, polymorphism and topochemistry.

In the past decade the interest in molecular electronic devices has escalated. The synthesis of molecular crystals has improved, providing single crystals or thin films with mobility comparable with or even higher than amorphous silicon. Their mechanical flexibility admits new types of applications and usage of electronic devices. Some of these organic crystals also display magnetic effects. Furthermore, the fullerene and carbon nanotube allotropes of carbon are prominent candidates for various types of applications. The carbon nanotubes, in particular, are suitable for molecular wire applications with their robust, hollow and almost one-dimensional structure and diverse band structure. In this thesis, we have theoretically investigated carbon based materials, such as carbon nanotubes, pentacene and spiro-biphenalenyl neutral radical molecular crystals. The work mainly deals with the electron structure and the transport properties thereof. The first studies concerns effects and defects in devices of finite carbon nanotubes. The transport properties, that is, conductance, are calculated with the Landauer approach. The device setup contains two metallic leads attached to the carbon nanotubes. Structural defects as vacancies and bending are considered for single-walled carbon nanotubes. For the multi-walled carbon nanotubes the focus is on inter-shell interaction and telescopic junctions. The current voltage characteristics of these systems show clear marks of quantum dot behaviour. The influence of defects as vacancies and geometrical deformations are significant for infinite systems, but in these devices they play a minor role. The rest of the studies concern molecular crystals, treated with density-functional theory (DFT). Inspired by the enhance of the electrical conductivity obtained experimentally by doping similar materials with alkali metals, calculations were performed on bundles of single-walled carbon nanotubes and pentacene crystals doped with potassium. The most prominent effect of the potassium intercalation is the shift of Fermi level in the nanotube bands. A sign of charge transfer of the valence electrons of the potassium atoms. Semi-conducting bundles become metallic and metallic bundles gain density of states at the Fermi level. In the semi-conducting pristine pentacene crystals structural transitions occur upon doping. The herringbone arrangement of the pristine pentacene molecules relaxes to a more π-stacked structure causing more dispersive bands. The charge transfer shifts the Fermi level into the lowest unoccupied molecular orbital band and turns the crystal metallic. Finally, we have studied molecular crystals of spiro-biphenalenyl neutral radicals. According to experimental studies, some of these materials show simultaneous electrical, optical and magnetical bistability. The electronic properties of these crystals are investigated by means of DFT with a focus on the possible intermolecular interactions of radical spins.

Organic crystals are found in everyday goods such as foods, drugs, dyes, and agricultural products. To better understand the solid-state behaviour of organic crystals, the study of their surfaces is crucial, as several reactions occur at the interface between the crystal surface and its immediate environment. While atomic force microscopy (AFM) is a useful tool for studying surfaces, it is not a common technique for studying organic crystals. The rst part of this report aims to address problems of imaging organic crystals by AFM which arise from the nature of the imaging technique and the material property of organic crystals. Methods of detecting and predicting the likelihood of the problems encountered in imaging organic crystals are suggested in order for a more accurate interpretation of the information obtained by this technique. The e ect of humidity on aspirin crystal surfaces is then investigated by AFM. The growth of new features on the surface is believed to be a result of the hydrolysis of aspirin molecules. Mechanisms are suggested based on the observed surface response of aspirin, where surface defects and the mobility of surface molecules are believed to be important factors a ecting reactivity. The last section investigates the solid-state photochemical reaction of anthracene, which is a reaction that should not occur according to the topochemical postulate. The surface response of anthracene crystals to UV light was studied, and the results indicate strong reactivity at sites of surface defects, which is likely due to photodimerisation. A similar mechanism that described the behaviour of aspirin surfaces was suggested for this reaction. In summary, both reactions that were studied provided a better insight towards understanding the solid-state reactivity of organic crystals. The proposed surface mechanisms imply that surface defects and the presence of humidity or solvent vapour are very likely to play a role in determining reactivity. Further studies on the origin of defects are suggested in order to better control the behaviour of organic crystals in the solid-state.

<p>The use of atomistic level simulations like molecular dynamics are becoming a key part in the process of materials discovery, optimization and development since they can provide complete description of a material and contribute to understand the response of materials under certain conditions or to elucidate the mechanisms involved in the materials behavior.</p> <p>We will discuss to cases in which molecular dynamics simulations are used to characterize and understand the behavior of materials: i) prediction of properties of small organic crystals in order to be implemented in a multiscale modeling framework which objective is to predict mechanically induced amorphization without experimental input other than</p> <p>the molecular structure and ii) characterization of temperature dependent spatio-temporal domains of high mobility torsions in several bulk polymers, thin slab and isolated chains; strikingly we observe universality in the percolation of these domains across the glass transition.</p> <p>However, as in any model, validation of the predicted results against appropriate experiments is a critical stage, especially if the predicted results are to be used in decision making. Various sources of uncertainties alter both modeling and experimental results and therefore the validation process. We will present molecular dynamics simulations to assess uncertainties associated with the prediction of several important properties of thermoplastic polymers; in which we independently quantify how the predictions are affected by several sources. Interestingly, we nd that all sources of uncertainties studied influence predictions, but their relative importance depends on the specific quantity of interest.</p>

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