Conselho Nacional de Desenvolvimento Científico e Tecnológico / In this work six aqua complexes of the transition metals Fe2+, Co2+, Ni2+, Cu2+, Zn2+ and Cd2+ containing the dithionate ion were synthesized and characterized through metathesis reactions in aqueous solution between BaS2O6·2H2O and the sulfate of the metal. Single crystals suitable for X-ray diffraction were obtained from the filtrates of the reactions and the structures of four complex salts, hexaaquairon(2+) dithionate hydrate, [Fe(H2O)6](S2O6)·H2O 1, hexaaquacobalt(2+) dithionate, [Co(H2O)6](S2O6) 2, hexaaquanickel(2+) dithionate, [Ni(H2O)6](S2O6) 3 and hexaaquazinc(2+) dithionate [Zn(H2O)6](S2O6) 5, and of two coordination polymers, catena-poli-[trans-tetraaquacopper-μ-dithionato-κ2O,O ] ([Cu(H2O)4(S2O6)]) 4 and catena-poli-[trans-tetraaquacadmium-μ-dithionato-κ2O,O ] ([Cd(H2O)4(S2O6)]) 6, all in triclinic system, space group P1 ‾ . The products were characterized by infrared spectroscopic, thermogravimetric, single crystal X-ray diffraction and powder Xray diffraction analyses. The Hirshfeld surface and the electron density were mapped with a cutoff 0.002 e− au−3 and basis 6-31G** for 1 to 5 and basis 3-21G* to 6, both basis in the Hartree-Fock method, revealing 79% and 75% of the contacts O···H, 19% and 11% of contacts H···H and 2% and 9% of the contacts O···O, for salts and complex coordination polymers, respectively. With the Hirshfeld surface, it was also possible to determine the volume of the molecules, determining the distorted cubic packing, according to the rules of Pauling. / Neste trabalho foram sintetizados e caracterizados seis aquacomplexos dos metais de transição Fe2+, Co2+, Ni2+, Cu2+, Zn2+ e Cd2+, contendo o íon ditionato, através de reações de metátese em solução aquosa entre BaS2O6·2H2O e o sulfato do metal. Monocristais apropriados para a difração de raios X foram obtidos a partir dos filtrados das reações, sendo as estruturas de quatro sais complexos, ditionato de hexaaquaferro(2+) hidrato, [Fe(H2O)6](S2O6)·H2O 1, ditionato de hexaaquacobalto(2+), [Co(H2O)6](S2O6) 2, ditionato de hexaaquaníquel(2+), [Ni(H2O)6](S2O6) 3 e ditionato de hexaaquazinco(2+), [Zn(H2O)6](S2O6) 5 e de dois polímeros de coordenação, catena-poli-[trans-tetraaquacobre-μ-ditionato-κ2O,O ] ([Cu(H2O)4(S2O6)]) 4 e catena-poli-[trans-tetraaquacádmio-μ-ditionato-κ2O,O ] ([Cd(H2O)4(S2O6)]) 6, todos resolvidos em sistema triclínico, grupo espacial P1 ‾ . Os produtos foram caracterizados por espectroscopia de infravermelho, análise termogravimétrica, difração de raios X de monocristal e difração de raios X em pó. A superfície de Hirshfeld e a densidade eletrônica foram mapeadas com ponto de corte 0,002 e− au−3 e bases 6-31G** para 1 a 5 e bases 3-21G* para 6, ambas as bases em nível Hartree-Fock, revelando 79% e 75% de contatos O···H, 19% e 11% de contatos H···H e 2% e 9% de contatos O···O, para os sais complexos e polímeros de coordenação, respectivamente. Com a superfície de Hirshfeld também foi possível determinar o volume das moléculas, determinando o empacotamento cúbico distorcido, segundo as regras de Pauling.

Submitted by Maike Costa (maiksebas@gmail.com) on 2017-06-19T14:00:05Z No. of bitstreams: 1 arquivototal.pdf: 7342318 bytes, checksum: dc68cd00ebae607f5275182f51548710 (MD5) / Made available in DSpace on 2017-06-19T14:00:05Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 7342318 bytes, checksum: dc68cd00ebae607f5275182f51548710 (MD5) Previous issue date: 2016-12-02 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / This dissertation has as its central point the characterization through the density functional theory (DFT) of the orthorhombic perovskite CaSnO3 belonging to the space group Pbnm, using Gaussian type orbitals. At first, the bulk of the material was explored with the most diverse solids simulation techniques, focusing on the structural evaluation under pressure and frequency calculations, as well as its intensities (Raman and Infrared spectra) evaluated by the newly implemented (In Crystal program) Coupled-Perturbed Hartree-Fock/Kohn- Sham (CPHF/KS). Following, the bulk was again exploited under pressure, including various exchange-correlation type formulations within the DFT theory, as well as the use of routines recently implemented in the Crystal program as: Elastic constants under pressure, directional seismic velocity analysis and quasi-harmonic approximation (QHA). The latter is of great physical, mineralogical and geophysical interest due to its description of a material under conditions of high temperatures and pressures simultaneously. To further explore the possible catalytic properties of the material, the studies the defects, including oxygen vacancies and doping with copper, was carried out focusing on the energy differences and electronic charge analysis, the last, taking into account the Mulliken technique and Hirshfeld-I (available only to developers at present). Those calculation where performed at PBE and PBE0 level (for the doping with Cu only PBE0), with RHF and UHF formulations for the open shell and spin polarized cases. The used supercell (2x2x2) presented an adequate size to work with. The oxygen vacancy formed has the tendency to reduce the Sn neighbors, that form a mid gap close to the Valence Band, and presenting as the most stable formulation the RHF and Singlet (UHF). The oxygen vacancy is here characterized as been a neutral one. In the doping cases, where the tin atom is substituted by a coper one, the most stable case was when the Cu was near the vacancy (first neighbor). To finish the studies on this perovskite, the surface (001) is studied. The surface terminated in -CaO is a bit more stable than the -SnO2 one, however, the first one, using the applied methodology, presented some problems when adsorbing gases, hence been discarded in favor of the -SnO2 one. The CO and NH3 gases are adsorbed over the -SnO2 terminated surface, to evaluate it, charge density maps, density of states (DOS) and Raman intensity where used. The results showed that the CO adsorption is weak, but has a visible response in the Raman spectra. In the NH3 case the adsorption is strong and can be assigned as a chemisorption. In the last, an intense Raman peak appear and it is assigned to a bond between the hydrogen and the surface oxygen and it appear about 3098 cm−1. / Esta tese tem como ponto central a caracterização através da teoria do funcional da densidade (DFT) da perovskita ortorrômbica CaSnO3 pertencente ao grupo espacial Pbnm, pela ótica de orbitais Gaussianos. No primeiro momento, o bulk do material foi explorado com as mais diversas técnicas de simulação de sólidos, com enfoque na avaliação estrutural sob pressão e a frequência, bem como suas intensidades (espectros Raman e no Infravermelho) avaliadas pelo recém implementado (no programa Crystal) Coupled- Perturbed Hartree-Fock/Kohn-Sham (CPHF/KS). Em seguida, o bulk foi novamente explorado sob pressão, incluindo diversas formulações do tipo troca-correlação dentro da teoria do funcional da densidade (DFT), bem como o uso das rotinas recentemente implementadas no programa Crystal como: constantes elásticas sob pressão, análise da velocidade sísmica direcional e a aproximação quase-harmônica (QHA). Esta última é de grande interesse físico, mineralógico e geofísico pela descrição de um material em condições de elevadas temperaturas e pressões simultaneamente. Para explorar as possíveis propriedades catalíticas do material o estudo de defeitos incluindo vacâncias de oxigênio e dopagens com cobre foram incluídas. As análises focam-se nas diferenças energéticas e análise de carga eletrônica, a última, levando em conta a técnica de Mulliken e a de Hirshfeld-I (disponível apenas para desenvolvedores, no presente). Os cálculos foram realizados em nível PBE e PBE0 (para o caso da dopagem apenas PBE0), nas versões RHF e UHF para os casos de camada aberta e polarização de spin. A supercélula utilizada (2x2x2) apresentou tamanho adequado para o trabalho com os defeitos. A vacância de oxigênio quando formada tende a reduzir os Sn vizinhos, que por ventura formam um mid gap próximo à banda de valência (VB), sendo a configuração mais estável a RHF ou Singleto (UHF). A vacância de oxigênio foi caracterizada como uma vacância neutra. Nos cálculos de dopagem em que o estanho é substituído pelo cobre, a situação mais estável é aquela em que o cobre encontra-se como um primeiro vizinho da vacância de oxigênio. Para conclusão do estudo dessa perovskita, a superfície 001 foi avaliada. A superfície terminada em -CaO é um pouco mais estável que a superfície -SnO2, no entanto a primeira - através da metodologia utilizada - teve problemas para adsorção dos gases, dessa forma sendo descartada para os estudos de adsorção aqui realizados. Os gases CO e NH3 estudados sobre a superfície terminada em -SnO2, na avaliação foram utilizados mapas de densidade de carga, densidade de estados (DOS) e espectros Raman. Os resultados indicaram que a adsorção com o CO é fraca, mas possui uma resposta visível no espectro Raman. Já no caso do NH3 a adsorção forte podendo configurar-se como quimissorção. Na última, há o aparecimento de um pico intenso referente à ligação hidrogênio e oxigênio da superfície em torno de 3098 cm−1.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-05-25T14:19:15Z No. of bitstreams: 1 marianadasilvacunha.pdf: 6235170 bytes, checksum: e49cfdcb2f78bafd1146dd684a809c87 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-05-25T14:48:17Z (GMT) No. of bitstreams: 1 marianadasilvacunha.pdf: 6235170 bytes, checksum: e49cfdcb2f78bafd1146dd684a809c87 (MD5) / Made available in DSpace on 2017-05-25T14:48:17Z (GMT). No. of bitstreams: 1 marianadasilvacunha.pdf: 6235170 bytes, checksum: e49cfdcb2f78bafd1146dd684a809c87 (MD5) Previous issue date: 2017-02-21 / Neste trabalho foi investigada a influência da modificação dos ligantes Hidrogeno psulfobenzoato de potássio (PSB), Ácido 1,2,4,5-benzenotetracarboxílico (BTC) e Ácido 1,5-naftalenodissulfônico tetrahidratado (1,5NDS) nas interações com a molécula de Isoniazida (INH) em três novos compostos, PSB-INH, BTC-INH e 1,5NDS-INH, e também foi realizado um estudo sobre o composto 1,5NDS-INO no qual o ligante Isoniazida sofreu uma termodecomposição, levando à formação do Ácido isonicotínico (INO). Foi realizado um estudo das ligações de hidrogênio formadas entre os ligantes através da análise de superfície de Hirshfeld e gráficos de impressão digital. Estas análises são extremamente sensíveis ao ambiente químico da molécula e são únicas para cada molécula e, dessa forma, permitem a identificação das diferenças entre os empacotamentos cristalinos no estado sólido. Foi observado que, embora a conformação da molécula de Isoniazida seja praticamente idêntica nos compostos PSB-INH, BTC-INH e 1,5NDS-INH e as principais ligações de hidrogênio presentes envolvem interações do tipo N – H···O e O – H···N, os gráficos de impressão digital são diferentes e exibem a influência da modificação dos ligantes. Nos gráficos de impressão digital obtidos as contribuições mais importantes das interações estão relacionadas aos contatos O···H e N···H, que possuem valores de 31,3% e 6,0% para o composto PSB-INH, 49,9% e 6,9% para o composto BTC-INH e 44,8% e 5,0% para o composto 1,5NDS-INH. No composto 1,5NDS-INO as principais ligações de hidrogênio são do tipo O – H···O e O – H···N e a contribuição mais importante para o gráfico de impressão digital está relacionada ao contato O···H, que contribui com 41,9% para a superfície e também ao contato H···H, que contribui com 30,5%. Este trabalho demonstrou como as análises de superfície de Hirshfeld e dos gráficos de impressão digital conseguem identificar diferenças entre as moléculas no estado sólido e permitiu a análise das interações intermoleculares formadas nos diferentes compostos, comprovando a importância dessas novas ferramentas para a análise estrutural. / In this work was investigated the influence of the modification of the ligands Hydrogen p-sulfobenzoate of potassium (PSB), 1,2,4,5-benzenetetracarboxylic acid (BTC) and 1,5-naphthalenedisulfonic acid tetrahydrate (1,5NDS) in interactions with the molecule of Isoniazid (INH) in three new compounds, PSB-INH, BTC-INH and 1,5NDS-INH, and also a study on the compound 1,5NDS-INO in which the Isoniazid ligand underwent a thermodecomposition, leading to the formation of isonicotinic acid (INO). A study of the hydrogen bonds formed between the ligands was carried out through Hirshfeld surface analysis and fingerprint plots. These analysis are extremely sensitive to the chemical environment of the molecule and are unique to each molecule and thus allow identification of the differences between the crystalline packages in the solid state. It was observed that, although the conformation of the Isoniazide molecule is practically identical in the compounds PSB-INH, BTC-INH and 1,5NDS-INH and the main hydrogen bonds present involve N – H ··· O and O – H ··· N, the fingerprint plots are different and exhibit the influence of the modification of the ligands. In the fingerprint plots obtained, the most important contributions of the interactions are related to the contacts O···H and N···H, which have values of 31.3% and 6.0% for the compound PSB-INH, 49.9% and 6.9% for compound BTC-INH and 44.8% and 5.0% for the compound 1.5NDS-INH. In the compound 1,5NDS-INO the main hydrogen bonds are of the O – H ··· O and O – H ··· N type and the most important contribution to the fingerprint plot is related to the contact O···H, which contributes with 41.9% to the surface and also to the H···H contact, which contributes with 30.5%. This work demonstrated how Hirshfeld surface analysis and fingerprint plots can identify differences between molecules in the solid state and allowed the analysis of the intermolecular interactions formed in the different compounds, proving the importance of these new tools for structural analysis.

Ionic liquid forming compounds often display low melting points (a lack of crystallisation at ambient temperature and pressure) due to decreased lattice energies in the crystalline state. The degree of anion-cation contact with respect to the type, strength and number of interactions is a major factor determining the lattice energies, melting point and general behaviour of ionic liquid forming salts. Intermolecular interactions between the anion and cation and the conformational states of each component of the salt are of interest since distinctive properties ascribed to ionic liquids are determined to a significant extent by these interactions. The direct insight into the spatial relationship between cation and anion provided by the analysis of crystal structures provides a basis from which features of the ionic liquid can be generally understood, since the short range order and interactions of related, non-crystalline compounds may be similar to those of the crystalline form. However, it is difficult to predict whether a particular ionic pair will produce a liquid at room temperature, due to numerous possible combinations of cations and anions and the subtleties of their interactions. Crystal engineering is the ability to assemble molecular or ionic components into the desired crystalline architecture by engineering a target network of supramolecular interactions known as synthons. In this investigation the problem of ionic liquid design is addressed using the concepts of crystal engineering in an inverse sense, the so-called anti crystal-engineering approach. A topical area in which the anti crystal-engineering concept may be of some value is that of Ionic Liquid Phases of Pharmaceutically Active Ions (Active Ionic Liquids). Thus, by using the knowledge gained of the intermolecular interactions, packing and ionic conformation which occur within ‘traditional’ ionic liquids, combined with the knowledge of which functional group combinations yield supramolecular synthons resulting in crystalline subjects, and the subsequent prevention thereof (anti crystal-engineering), appropriate ions shall be selected which may result in ionic liquid formation. The intermolecular interactions of a series of: • crystallised bis(trifluoromethanesulfonyl)amide (NTf2) and bis(methanesulfonyl)amide (NMes2) ionic liquids, • low melting N-alkyl-2-methyl-3-benzylimidazolium iodide salts with a range of alkyl chain lengths, from n=1 to 6 and including both n-butyl and s-butyl chains, • 1-methyl-1-propylpyrrolidinium chloride and, • a number of low melting salts containing trihalide and monohalide ions, in combination with typical IL organic cations namely, 1-ethyl-3-methylimidazolium, 1-ethyl-1-methylpyrrolidinium and 1-propyl-1-methylpyrrolidinium, were qualitatively investigated and/or compared using a combination of crystallographic, Hirshfeld surface and thermal analysis techniques. The NMes2 salts are known to exhibit higher glass transitions and higher viscosities than those of the NTf2 salts. The origins of these differences were analysed in terms of the importance of factors such as the C-H•••O hydrogen bond, fluorination, presence of an aromatic moiety and length of alkyl chain, using the Hirshfeld surfaces and their associated fingerprint plots. Additionally, the existence of C-F•••π and C-H•••π interactions were elucidated and the significance of anion-anion interactions was recognised. Thermal analysis of the N-alkyl-2-methyl-3-benzylimidazolium iodide salts revealed that the methyl- and (s-)butyl substituted salts have a significantly higher melting point than the rest of the series. Analysis of these crystal structures allowed examination of the influence of the substitutions on the different cation-anion and cation-cation interactions and thus the physical properties of the salts. Thermal analysis of the monohalide and trihalide salts revealed that the tribromide salts are lower melting than their monohalide analogues. Analysis of these crystal structures revealed the influence of the anions and the crystal packing on the physical properties of the salts. A series of crystalline and liquid salts were prepared from cations and anions drawn from Active Pharmaceutical Ingredients (APIs) and Generally Recognized As Safe (GRAS) materials. The solid-state structures of the crystalline salts were used as a basis for the anti-crystal engineering approach in the preparation of several “Active Ionic Liquids” (AILs). However, a side product also resulted during the synthetic route namely, methyl 9H-xanthene-9-carboxylate, a side product resulting from the API, propantheline. The results and methodology of the anti-crystal engineering procedure and the subsequent successful preparation and characterization of pharmaceutical ionic compounds are reported herein.

No description available.

It is common to use the electron density to partition a molecular system into atomic regions. The necessity for such a partitioning scheme is rooted in the unquestionable role of atoms in chemistry. Nevertheless, atomic properties are not well- defined concepts within the domain of quantum mechanics, as they are not observable. This has resulted in a proliferation of different approaches to retrieve the concept of atoms in molecules (AIM) within the domain of quantum mechanics and in silico experiments based on various flavors of model theories. One of the most popular families of models is the Hirshfeld, or stockholder, partitioning methods. Hirshfeld methods do not produce sharp atomic boundaries, but instead distribute the molecular electron density at each point between all the nuclear centers constituting the molecule. The various flavors of the Hirshfeld scheme differ mainly in how the atomic shares are computed from a reference promolecular density and how the reference promolecular density is defined. We first establish the pervasiveness of the Hirshfeld portioning by extending its information-theoretic framework. This characterizes the family of f-divergence measures as necessary and sufficient for deriving Hirshfeld scheme. Then, we developed a variational version of Hirshfeld partitioning method, called Additive Variational Hirshfeld (AVH). The key idea is finding the promolecular density, expanded as a linear combination of charged and neutral spherically-averaged isolated atomic densities in their ground and/or excited states, that resembles the molecular density as much as possible. Using Kullback-Liebler divergence measure, this automatically guarantees that each atom and proatom have the same number of electrons, and that the partitioning is size consistent. The robustness of this method is confirmed by testing it on various datasets. Considering the mathematical properties and our numerical results, we believe that AVH has the potential to supplant other Hirshfeld partitioning schemes in future. / Thesis / Doctor of Philosophy (PhD)

The title compound, C20H18O3, crystallizes in the space group P21/c with one mol­ecule in the asymmetric unit of the cell. The fluorene skeleton is nearly planar and the crystal structure is composed of mol­ecular layers extending parallel to the (302) plane. Within a layer, one formyl oxygen atom participates in the formation of a Carene—H...O bond, which is responsible for the formation of an inversion symmetric supra­molecular motif of graph set R22(10). A second oxygen atom is involved in an intra­molecular Carene—H...O hydrogen bond and is further connected with a formyl hydrogen atom of an adjacent mol­ecule. A Hirshfeld surface analysis indicated that the most important contributions to the overall surface are from H...H (46.9%), O...H (27.9%) and C...H (17.8%) inter­actions.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / This study shows the influence of the molecular topology of the crystal of a series of 14 pyrazolo[1,5-a]pyrimidines. The topological data were obtained from X-ray diffraction data and energy stabilization were determined by thermal analysis and chemical computations. Topological analysis carried out was Molecular Coordination Number (NCM) using the Voronoi-Dirichlet polyhedra and Hirshfeld surface. The NCM found for the majority of compounds was 14. Furthermore, it was determined contact area and the solid angle between molecules of the first coordination sphere of the cluster. Several correlations between data were performed, where it is possible highlight the correlation between the area of contact of the cluster molecules and the interaction energy and the solid angle and interaction energy were established. These correlations showed that there is a proportionality between the data, showing that the greater the contact area, the greater the interaction energy for a series of pyrazolo[1,5-a]pyrimidine studied in this thesis. As the contact area, solid angle also presents proportionality with the calculated interaction energy. Among the atom-atom contacts present on the surface of the test compounds was observed that contacts C∙∙∙H and C∙∙∙C are key to stabilize the crystals. This result corroborates the hypothesis that the contact surface between the molecules would be the driving force for the crystalline arrangement. / Este trabalho apresenta o estudo da influência da topologia molecular na organização cristalina de uma série de 14 pirazolo[1,5-a]pirimidinas. Os dados topológicos foram obtidos por difratometria de raios-X e os dados de energia de estabilização foram determinados por análises térmicas e cálculos computacionais. Dentre as análises topológicas realizadas destaca-se a determinação do Número de Coordenação Molecular (NCM) usando o Poliedro de Voronoi-Dirichlet e a Superfície de Hirshfeld. O NMC encontrado para a maioria dos compostos foi de 14. Além disso, foi determinada a área de contato, bem como o ângulo sólido entre as moléculas da primeira esfera de coordenação do cluster. Estabeleceu-se uma serie de correlações entre os dados obtidos, entre elas, destaca-se a correlação entre esta área de contato entre as moléculas do cluster e a energia de interação, bem como a correlação ângulo sólido e energia de interação. Ambas correlações mostraram que há uma proporcionalidade entre os dados, mostrando que quanto maior a área de contato, maior a energia de interação para a série de pirazolo[1,5-a]pirimidinas estudadas nesta dissertação. Assim como a área de contato, o ângulo sólido também apresenta uma proporcionalidade com a energia de interação calculada. Dentre os contatos átomo-átomo presentes na superfície dos compostos em estudo, observou-se que os contatos C∙∙∙H e C∙∙∙C são os principais para a estabilização dos cristais estudados. Este resultado corrobora com a hipótese de que a superfície de contato entre as moléculas seria a força motriz para o arranjo cristalino.

Le fullerène C60 est une molécule sphérique composée exclusivement d'atomes de carbone. Ce composé possède une surface aromatique convexe homogène et peut s'associer, entre autres, avec des molécules possédant des surfaces aromatiques par des interactions non-covalentes. Le triptycène est une molécule en forme de "Y" qui possède des surfaces aromatiques convexes. Cette molécule possède l'habileté de s'associer avec le C60 par des interactions de type π qui sont amplifiées par la complémentarité des surfaces concaves et convexes impliquées dans les arrangements cristallins. Nous avons synthétisé des dérivés triptycényles portant des groupements fonctionnels aux extrémités des bras de ce noyau de façon à étendre les cavités disponibles pour interagir avec le C60. En effet, nous avons découvert que les atomes de chlore, de brome et d'iode ainsi que les groupements méthyle permettent d'étendre les surfaces disponibles pour interagir avec les fullerènes C60 et C70. Nous avons étudié les associations entre les dérivés triptycényles et les fullerènes par l'analyse des structures cristallographiques résolues par diffraction des rayons-X. De plus, nous avons étudié les associations entre les molécules considérées par l'analyse des surfaces d'Hirshfeld entourant les fullerènes. Découlant de ces études, l'effet d'amplification des atomes de chlore, de brome et d'iode ainsi que les groupements méthyle a été employé pour identifier de nouveaux solvants aptes à solubiliser efficacement le C60. / The fullerene C60 is a spherical molecule made up exclusively of carbon atoms. The surface of this compound is homogenous, convex and aromatic. As a result, C60 can associate with other aromatic molecules via non-covalent π-stacking interactions to form supramolecular assemblies. The triptycene is a "Y"-shaped molecule with concave aromatic surfaces. This molecule can thereby interact with C60 and form crystals through amplified π-stacking interactions resulting from the concave/convex complementary arrangement. In the course of our work, we made a series of new triptycene derivatives with functional groups added to the periphery of the aromatic core. In particular, we found that methyl groups, as well as atoms of chlorine, bromine and iodine, can be placed on the extremities of the triptycene core to expand the concave cavities available to interact with C60 and C70. We studied the non-covalent interactions between fullerenes and triptycene derivatives using X-ray crystallography. Furthermore, Hirshfeld surfaces have been used to map the interaction patterns around fullerene surfaces. In addition, we have found that aromatic solvents that are properly functionalized with halogen atoms and methyl groups have a special ability to solubilize C60.

Le fullerène C60 est une molécule sphérique composée exclusivement d'atomes de carbone. Ce composé possède une surface aromatique convexe homogène et peut s'associer, entre autres, avec des molécules possédant des surfaces aromatiques par des interactions non-covalentes. Le triptycène est une molécule en forme de "Y" qui possède des surfaces aromatiques convexes. Cette molécule possède l'habileté de s'associer avec le C60 par des interactions de type π qui sont amplifiées par la complémentarité des surfaces concaves et convexes impliquées dans les arrangements cristallins. Nous avons synthétisé des dérivés triptycényles portant des groupements fonctionnels aux extrémités des bras de ce noyau de façon à étendre les cavités disponibles pour interagir avec le C60. En effet, nous avons découvert que les atomes de chlore, de brome et d'iode ainsi que les groupements méthyle permettent d'étendre les surfaces disponibles pour interagir avec les fullerènes C60 et C70. Nous avons étudié les associations entre les dérivés triptycényles et les fullerènes par l'analyse des structures cristallographiques résolues par diffraction des rayons-X. De plus, nous avons étudié les associations entre les molécules considérées par l'analyse des surfaces d'Hirshfeld entourant les fullerènes. Découlant de ces études, l'effet d'amplification des atomes de chlore, de brome et d'iode ainsi que les groupements méthyle a été employé pour identifier de nouveaux solvants aptes à solubiliser efficacement le C60. / The fullerene C60 is a spherical molecule made up exclusively of carbon atoms. The surface of this compound is homogenous, convex and aromatic. As a result, C60 can associate with other aromatic molecules via non-covalent π-stacking interactions to form supramolecular assemblies. The triptycene is a "Y"-shaped molecule with concave aromatic surfaces. This molecule can thereby interact with C60 and form crystals through amplified π-stacking interactions resulting from the concave/convex complementary arrangement. In the course of our work, we made a series of new triptycene derivatives with functional groups added to the periphery of the aromatic core. In particular, we found that methyl groups, as well as atoms of chlorine, bromine and iodine, can be placed on the extremities of the triptycene core to expand the concave cavities available to interact with C60 and C70. We studied the non-covalent interactions between fullerenes and triptycene derivatives using X-ray crystallography. Furthermore, Hirshfeld surfaces have been used to map the interaction patterns around fullerene surfaces. In addition, we have found that aromatic solvents that are properly functionalized with halogen atoms and methyl groups have a special ability to solubilize C60.