Dipyrrins, pyrrolyldipyrrins and prodigiosenes are a closely related series of molecules: pyrrolyldipyrrins are dipyrrins with a pyrrolic substituent and prodigiosenes are a special class of pyrrolyldipyrrins with a methoxy substituent. Prodigiosenes are known for their anticancer activity, but although there have been a number of developments in their synthesis, chemical manipulation of prodigiosenes is rare. Development of a methodology for the chemical manipulation of prodigiosenes would allow a convergent synthesis of a closely related series of prodigiosenes ideal for investigations into structure activity relationships. Chemical manipulation of dipyrrins is also rare, but this is largely overcome by first converting dipyrrins to dipyrrinato complexes. The same strategy could potentially apply to pyrrolyldipyrrins and prodigiosenes, but there are very few known pyrrolyldipyrrinato complexes. Three projects were undertaken in order to investigate the chemical manipulation of dipyrrins and pyrrolyldipyrrins. The first project was to investigate the synthesis of a library of prodigiosenes by way of a convergent approach. The synthesis of a functionalized prodigiosene, with demonstrated anticancer activity, was optimized and many methods for functional group interconversion of an ester attached to the prodigiosene core were investigated. Ultimately, this method was unsuccessful in the synthesis of a library of prodigiosenes due to instability of prodigiosene intermediates. The second project was to investigate the synthesis of pyrrolyldipyrrinato complexes. A series of pyrrolyldipyrrinato tin(IV) complexes with a previously unobserved binding mode for pyrrolyldipyrrins were successfully synthesized and one complex of the series was characterized using x-ray crystallography. Although fluorescent dipyrrinato complexes, with the exception of boron difluoride complexes, are rare, all of the pyrrolydipyrrinato tin(IV) complexes were highly fluorescent with fluorescence quantum yields between 0.28 to 0.61. The third project was to develop a protection method for pyrrolyldipyrrins using dipyrrins as model compounds. A general, high yielding method was developed to remove the BF2 group from a dipyrrinato borondifluoride complex to generate a dipyrrin. Preliminary application of this deprotection methodology to prodigiosene boron difluoride complexes shows promise. This deprotection methodology allowed for the development of a new methodology for the synthesis of meso-alkyl substituted dipyrrins via meso-modification of their corresponding boron difluoride complexes.

La tectonique moléculaire est une partie de la chimie supramoléculaire traitant de la formation d’architectures périodiques mono-, bi- et tridimensionnelles générées via l’auto-assemblage de briques moléculaires complémentaires nommées tectons. Ces derniers possèdent des sites de reconnaissance basés sur des interactions non-covalentes et réversibles. Les interactions largement utilisées sont les liaisons hydrogène et les interactions de coordination. Au cours de cette thèse, les sites de liaison H utilisés sont les nucléobases (thymine, adénine, cytosine, guanine) présentes dans l'ADN et l'ARN, qui ont été introduites en périphérie de différents sites de coordination, tels que les porphyrines, les dipyrrines, les pyridines et les terpyridines. Une bibliothèque de 25 nouveaux tectons à base de nucléobases a été synthétisée et caractérisée. De plus, les tectons ont été cristallisés pour étudier leur auto-assemblage à l'état solide. En présence de cations métalliques externes, les tectons conduisent à la formation de réseaux de coordination de topologies variées associant des liaisons H additionnelles entre les nucléobases. / Molecular tectonics is a field of supramolecular chemistry dealing with the formation of 1D, 2D and 3D molecular networks generated through the self-assembly processes between complementary building blocks (tectons). The latter offer complementary sites leading to recognition patterns via non-covalent and reversible interactions. The interactions widely used are hydrogen bonds and coordination interactions. During this thesis, the H-bonding sites used are the Nucleobases (Thymine, Adenine, Cytosine, Guanine) found in the DNA and RNA, which were introduced to different coordination sites, such as porphyrins, dipyrrins, pyridines and terpyridines. A library of 25 new tectons based on nucleobases were synthesized and characterized. Furthermore, the tectons were crystalized to study their self-assembly in the solid state. In the presence of external metal cations, the tectons lead to the formation of coordination and H-bonded networks of various topology via the self-assembly of nucleobases together with the formation of coordination bonds.

Orientadores: André Luiz Barboza Formiga, Pedro Paulo Corbi / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-20T20:33:33Z (GMT). No. of bitstreams: 1 Gonsales_StelladeAlmeida_M.pdf: 5138050 bytes, checksum: 48050f171b28aaaec7dc54a01a7ee17f (MD5) Previous issue date: 2012 / Resumo: erivados de pirrol e imidazol, juntamente com seus complexos de Cu(II) e Zn(II). Após diversas tentativas de síntese do 5-fenildipirrometeno pela rota tradicional, obteve-se o produto desejado porém em baixíssimos rendimentos. Os 2-ariloilpirróis foram sintetizados com sucesso partindo-se de cloreto de ácido e pirrol, obtendo-se assim o 2-benzoil-3,5-dimetilpirrol (2-bz-pirrol) e o 2-isonicotinoil-3,5-dimetilpirrol (2-pypirrol) como produtos. Os compostos foram caracterizados por DRX de monocristal, MS, IV, UV-Vis e H e C RMN. Realizaram-se ensaios biol'ogicos com os ligantes obtidos, assim como com os complexos de Cu(II) destes ligantes. Outro ligante, tridentado, o 2,6-bis(imdazol-2-il)piridina (impy) foi sintetizado com sucesso e utilizado na síntese de um complexo inédito de cobre. Sua estrutura também foi determinada por difracão de raios X de monocristal, dentre outras técnicas, revelando uma estrutura binuclear não usual formada por uma ponte de cloreto / Abstract: In this work we present the synthesis of three new ligands derived from pyrrole and imidazole subunits, along with their Cu(II) and Zn(II) complexes. After many attempts to achieve the synthesis of 5-phenyldipyrromethene using the classical method, we obtained the desired product but in very low yields. Two 2- ariloylpyrroles have been synthesized from the acid chloride and pyrrole, achieving both 2-benzoyl-3,5-dimethylpyrrole (2-bz-pirrol) and 2-isonicotinoyl-3,5-dimethylpyrrole (2-py-pirrol) as products. These compunds were charactherized by single crystal XRD, MS, FTIR, UV-Vis and H e C NMR. Biological assays were performed with the obtained ligands and their Cu(II) complexes. Another ligand, tridentate, 2,6-bis(imdazole-2-yl)pyridine (impy) was successfully synthesized and used in the achievement of a novel Cu(II) complex. Its structure was also determined by single crystal XRD, among with other techniques, revealing an unusual chloride bridged binuclear structure / Mestrado / Quimica Inorganica / Mestre em Química