Synthetic studies toward the preparation of several polypyrrolic macrocycles are described. The majority of the research was directed toward the synthesis of a pentapyrrolic analogue (15) of porphyrin (13). The results were surprising, as a meso-substituted porphyrin (63) was the result. In light of our findings we were able to explain our earlier failures to obtain the pentapyrrole (15) as well as the failures of previous investigators^""*". A sapphyrin (16), the pentapyrrolic analogue of corrole (2), was also prepared, for eventual comparison with our porphyrin analogue (15), and we attempted to insert into 2+ 29 xt a uranyl catxon (UC^ ). The uranyl moiety had been shown to be present in a pentapyrrolic analogue (17) of phthalocyanine (68). By a reaction analogous to that for (17), the synthesis of the five-membered analogue (18) of benzporphyrin (see Scheme 13) was attempted. That macrocycle (18), containing the uranyl ion and being .more porphyrin-like than (17) , would have provided a link between the *superphthalocyanine' (17) and the other macrocycles, (15) and (16). / Science, Faculty of / Chemistry, Department of / Graduate

The principal goal of this work was to synthesize and fully characterize a range of free / Thesis (M.Sc.)-University of KwaZulu-Natal, Pietermaritzburg, 2007.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

This work is aimed at elucidating the structures and spectroscopic properties of phosphine and b phosphonite complexes of Mn(III), Co(III) and Rh(III) porphyrins, a class of coordination compounds that has been little reported on in the literature to date. In this work, a range of novel bis(phosphine) and bis(phosphonite) complexes of the three aforementioned metals have been synthesized, crystalized and analysed by means of X-ray structure determination, 1H NMR, 13C NMR, 31P NMR as well as electronic and IR spectroscopy. [Mn(TPP)(PPh3)2](SbF6) crystallizes in the monoclinic space group P21/c and displays an extraordinarily long Mn-P bond length of 3.088(2) A. Moderate ruffling of the porphyrin ligand is observed. This complex is paramagnetic with fast proton relaxation times, and thus did not yield any useful 1H NMR data. In an attempt to crystallize [Mn(TPP){P(OPh)3}2](SbF6), a complex bearing an O-donor contamination product, [Mn(TPP){(O)PH(OPh)2} ](SbF6), was isolated and its solid state structure determined by X-ray diffraction methods. The structure of this complex has been included in this work as it displays interesting structural features and is the very first phosphonate complex of a metalloporphyrin. This compound crystallizes in the monoclinic space group P21/n and shows a significantly saddled conformation. The axial Mn-O bond length measures 2.122(3) A. The Mn-Nporph bond lengths are 1.998(6) and 2.002(3) A for the bis(phosphine) and phosphonate complexes, respectively. Since the diethyl phosphonate complex was an unintended reaction product, no further characterisation of it was undertaken. [Co(TPP)(depp)2](SbF6), where depp = diethylphenylphosphine, crystallizes in the monoclinic space group P21/c. This complex displays inversion symmetry at the metal center and the porphyrin core is effectively planar. However, [Co(TPP)(edpp)2](SbF6), where edpp = ethyldiphenylphosphine, crystallizes in the· monoclinic space group P21/n and shows a significantly ruffled conformation of the porphyrin core and displays no inversion symmetry. [Co(TPP)(deppt)2](SbF6), where deppt = diethylphenylphosphonite, also crystallizes in the monoclinic space group P21/n, but displays inversion symmetry through the central cobalt ion. As a result, this complex does not display any significant conformational deviations of the porphyrin core from planarity. The axial Co-P bond lengths are significantly shorter than that of . the equivalentbond in the manganese bis(triphenylphosphine) complex at 2.312(1) A, 2.323(10) A and 2.258(2) A for [Co(TPP)(depp)2](SbF6), [Co(TPP)(edpp)2](SbF6) and [Co(TPP)(deppt)2](SbF6), respectively. The Co-Nporph bond lengths average to 1.980(3) A, 1.972(7) A and 1.980(4) A for these three complexes, respectively. I03Rh NMR measurements of three rhodium bis(phosphine)/bis(phosphonite) porphyrins have been performed by the indirect probing of the rhodium metal center by means of the phosphorus nucleus of the coordinated axial ligand. The resulting I03Rh NMR shifts for [Rh(TPP)(edpp)2](SbF6), [Rh(TPP)(edppt)2](SbF6), where edppt = ethyldiphenylphosphonite, and [Rh(TPP)(deppt)2](SbF6) are 2558, 2413 and 2365 ppm, respectively. [Rh(TPP)(edpP)2](SbF6) crystallizes in the monoclinic space group P21/n and shows moderate ruffling of the porphyrin core. The axial Rh-P bond length is 2.401(2) A. [Rh(TPP)(edppt)2](SbF6) and [Rh(TPP)(deppt)2](SbF6) both crystallize in the monoclinic space group P21/c. The porphyrin core of [Rh(TPP)(edppt)2](SbF6) displays a moderate degree of ruffling, as observed in [Rh(TPP)(edpp)2](SbF6), yet the axial Rh-P bond length is substantially shorter at 2.361(9) A. [Rh(TPP)(deppt)2](SbF6) exhibits the shortest Rh-P bond length of the three complexes at 2.332(2) A. The porphyrin core is mostly planar. The Rh-Nporph distances average 2.034(1) A for the S4-ruffled complexes and 2.044(3) A for the planar complex, the shorter distance in the ruffled derivatives being consistent with a distortion-induced compression of the Rh(III) ion. / Thesis (M.Sc.)-University of Natal, Pietermaritzburg, 2003

Includes bibliographical references / iv, 262, [33] leaves ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Organic Chemistry, 1991

Made available in DSpace on 2017-07-24T19:38:04Z (GMT). No. of bitstreams: 1 Rosana Balzer.pdf: 2986584 bytes, checksum: 00f13f9fc467f7bdab7c9138e783c610 (MD5) Previous issue date: 2010-08-02 / Fundação Araucária de Apoio ao Desenvolvimento Científico e Tecnológico do Paraná / The properties of compounds 5, 10, 15, 20-tetrakis (2,6 difluor-5-sulfonatophenyl) sodium porphyrin, Na4[H2(TDFSPP)], and 5, 10, 15, 20-tetrakis (2,6 difluor-5-sulfonatophenyl) sodium porphyrinate zinc (II), Na4[Zn(TDFSPP)], were investigated with the objective of using them as photosensitizers in Photodynamic Therapy (PDT). LED systems were used at different emission bands, orange, green and red for irradiation of samples. Photobleaching reactions were studied through the molecular absorption analysis UV-Visible, irradiating samples with LED systems for one hour. It was observed that compounds are photostable. Oxygen singlet generation was analyzed through the uric acid test, and it was observed that the compounds generated oxygen singlet. Zinc porphyrin presented higher efficiency in the generation of the reactive species. Aggregation at different proportions of the water/ethanol system was evaluated with UV-Visible techniques and fluorescence emission. Results indicated that there was no formation of aggregates for the compounds in the conditions analyzed. The photodynamic action of compounds was analyzed through in vitro analysis with brine shrimp Artemia salina and the microorganisms Candida albicans, Escherichia coli e Staphylococcus aureus. Through the analysis of results obtained in tests with Artemia salina, it was concluded that for both compounds and for the three LED systems, the highest percentage of death occurred in tests with association of compound and irradiation, which indicates photodynamic activity in the systems employed. Results obtained in the tests to evaluate photodynamic activity of compounds for inactivation of microorganisms revealed that lighting time did not influence the number of colony forming units (UFC). The lowest UFC values were observed for the systems with association of compounds and light, that is, there was photodynamic activity. Thus, results demonstrated that the compounds present potential to be used in Photodynamic Therapy. / Neste trabalho investigaram-se as propriedades dos compostos 5, 10, 15, 20 tetrakis (2,6-difluoro-5-sulfonatofenil)porfirina de sódio, Na4[H2(TDFSPP)], e 5, 10, 15, 20 tetrakis (2,6-difluoro-5-sulfonatofenil)porfirinato zinco (II) de sódio, Na4[Zn(TDFSPP)], visando aplicabilidade como fotossensibilizadores em Terapia Fotodinâmica (TFD). Utilizaram-se sistemas de LED em diferentes faixas de emissão, alaranjado, verde e vermelho para irradiação das amostras. As reações de fotobranqueamento foram estudadas através da análise da absorção molecular UV-Visível irradiando-se as amostras com sistemas de LED durante uma hora. Observou-se que os compostos são fotoestáveis. A geração de oxigênio singlete foi analisada através do teste de ácido úrico, observando-se, que os compostos geraram oxigênio singlete, a zinco porfirina apresentou uma maior eficiência na geração da espécie reativa. A capacidade de agregação em diferentes proporções do sistema água/etanol foi analisada com as técnicas de absorção molecular UV-Visível e emissão de fluorescência, os resultados indicaram que não ocorreu formação de agregados para os compostos nas condições analisadas. A ação fotodinâmica dos compostos foi analisada através de ensaios in vitro com o microcrustáceo Artemia salina e com os micro-organismos Candida albicans, Escherichia coli e Staphylococcus aureus. Através da análise dos resultados obtidos nos testes com Artemia salina conclui-se que para os dois compostos e para os três sistemas de LED, a maior percentagem de mortalidade ocorreu nos testes com associação do composto e irradiação. Isso indica que houve atividade fotodinâmica dos sistemas utilizados. Os resultados obtidos nos testes para avaliar a atividade fotodinâmica dos compostos para inativação de micro-organismos mostraram que o tempo de iluminação não influenciou no número de unidades formadoras de colônia (UFC) de micro-organismos. Os menores valores de UFC foram observados para os sistemas com associação de composto e iluminação, ou seja, observou-se atividade fotodinâmica. Assim, os resultados demonstram que os compostos apresentam potencial para serem aplicáveis em Terapia Fotodinâmica.