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Thesiszafar.Pdf (1.989Mb) Synthesis and metalation of expanded porphyrins and their building blocks Presented by Hadiqa Zafar In partial fulfillment of the requirements for graduation with the Dean’s Scholars Honors Degree in the Department of Chemistry. Jonathan L. Sessler (Supervising Professor) Date I grant the Dean’s Scholars Program permission to post a copy of my thesis on the Texas ScholarWorks. Synthesis and metalation of expanded porphyrins and their building blocks. Department: Chemistry . Hadiqa Zafar Date . Jonathan L. Sessler Date Table of Contents Page 1: Abstract Page 2-6: Porphyrin Chemistry Background Page 7-10: Amethyrin56 Page 11-15: Oligoheterocycles146 Page 16-17: Terpyrrole121 Page 18: Conclusion Pages 19-26: Bibliography Abstract Porphyrin and related tetrapyrrolic macrocycles, collectively porphyrinoids, are versatile ligands that allow access to a multitude of coordination modes. Judicious modification of the porphyrin core, as well as the pendant substituents, have extended the coordination chemistry of porphyrinoids to include systems that are able to stabilize f-block element complexes with concomitant access to new structures with possible utility. Here our group’s efforts to prepare porphyrinoid ligands and their building blocks, that can serve as tools to study and apply f-element metal coordination chemistry are described, including the background of the topic, selected syntheses, and application of these species in the chemical and medical sciences. My thesis research spans three projects, including the synthesis and characterization of an amethyrin-uranyl complex displaying aromatic character, the iterative synthesis of tuneable α,α’-linked oligoheterocycles displaying fluorescent properties, and the gram-scale synthesis of a bench-stable 5,5”-unsubsituted terpyrrole. The reaction between amethyrin and non-aqueous uranyl silylamide (UO2[N(SiMe3)2]2) under anaerobic conditions affords a bench-stable uranyl complex. UV-Vis spectroscopy, cyclic voltammetry, as well as proton NMR spectroscopic analyses provide support for the conclusion that all six pyrrole subunits participate in coordination of the uranyl dication and that, upon complexation, the amethyrin-core undergoes a 2-electron oxidation to yield a formal 22 π-electron aromatic species. The controlled synthesis of oligoaromatics can provide materials of utility across a wide range of the chemical sciences. Here, we describe the preparation of higher order oligoheterocycles via a tandem Suzuki cross-coupling protocol. This has allowed for the iterative construction of fluorescent α,α’-linked penta- and septaheterocyclic systems. Modification of the terminal moiety allowed for fine-tuning of the emission features. The controlled preparation of higher order oligopyrrolic species holds broad utility across the chemical and material sciences. Here, we describe the gram-scale synthesis of a bench-stable terpyrrole in excellent yield from commercially available and easily prepared precursors via a tandem Suzuki cross-coupling with in situ deprotection. The solution and solid state stability as well as UV-vis, fluorescence, and x-ray crystallographic analysis of the new 5,5”-unsubstituted terpyrrole are also detailed. 1 Background The f-block elements have played a starring role in chemistry in spite of occupying a less-than- prominent position within the periodic table.1 Initial interest in these elements was driven by academic curiosity and a desire to complete the periodic table.2 Subsequently, industrial applications and wartime efforts spurred further research.3 Early academic programs sought to expand potential applications by elucidating fundamental reactivity patterns, molecular structure, and coordination chemistry.4-9 The resultant studies revealed marked differences between the f- block elements and transition metal or main group species, allowing for useful applications across the chemical,10-15 medical,16-18 and material science fields.19-21 Recent advances, driven by the preparation of new diverse ligand sets, have continued to drive progress in f-element chemistry and revealed unique new utilities.22-24 Tetrapyrrolic ligands, notably the porphyrins and corroles, as well as the ostensibly related phthalocyanines, support remarkable coordination chemistry (Figure 1).25-27 Transition metal and main group complexes have proven invaluable as metalloprotein cofactor models,28 new materials,29 supramolecular constructs,30 pharmaceuticals,31 and catalysts.32 The inherent ability of these ligands to yield stable metal complexes stimulated f-element porphyrin research. Not surprisingly, a diverse array of lanthanide-containing systems found practical use as NMR shift reagents, luminescent heme protein models, optical materials, and therapeutics, among other applications.33 However, actinide complexes based on porphyrins and other relatively small porphyrinoids remain scarce, with only a limited set of thorium(IV) and uranium(IV) out-of-plane and double or triple-decker sandwich structures being known.34-39 Attempts at transuranic complexes have been limited to neptunium40 and americium phthalocyanine41 sandwich complexes.42 Figure 1. Tetrapyrrolic porphyrin and related congeners. A recent research focus in porphyrin chemistry has involved modification of the core via heterocycle replacement, addition of pendant substituents, and variations in the cavity size and shape.43-47 Expanded porphyrins, systems containing larger cavities, have received considerable attention in the context of this general paradigm.48-50 Judicious incorporation of appropriate chelating moieties and size complementarity has allowed for the stabilization of a number of f- element complexes. This new chemistry has yielded structures and functions inaccessible using smaller congeners, such as the porphyrins or related ligand species. Efforts toward the synthesis and use of porphyrinoid species are reviewed to provide context for this seminal work. In providing this summary, particular focus will be placed on reviewing the relevant background, outlining 2 synthetic developments, and, when applicable, discussing potential applications for amethyrin species. The synthesis of new porphyrinoid building blocks has proven instrumental in accessing previously unexplored expanded porphyrin scaffolds. Initial porphyrinoid constructs often relied upon simple pyrrole and bipyrrole frameworks. Improved synthetic methods soon allowed ready access to larger motifs, such as terpyrrole.51-53 For instance, by exploiting a Paal-Knorr cyclization with subsequent functional group manipulation and cyclization, Sessler, Weghorn, and Hiseada provided a scalable route to terpyrrole (36) and terpyrrole-based expanded porphyrins, such as amethyrin (39) (Scheme 1).54 The results of initial metalation experiments were included in this first report. Included among them was a description of a putative uranyl-amethyrin complex, as inferred from UV-vis spectroscopic and high resolution mass spectrometric studies. Scheme 1. Synthesis of terpyrrole (36) and amethyrin (39). Additional work on the actinyl coordination chemistry carried out by Sessler, Gorden, Seidel, Hannah, and Lynch, as well as Gordon, Donohoe, Tait, and Keogh from LANL, provided support for the formation of a putative neptunyl(V) complex 41 (Scheme 2).55 The resultant microcrystalline material was characterized by UV-vis, NMR, and Raman vibrational spectroscopy. The presence of an NH resonance in the 1H NMR spectrum led the authors to conclude that metalation had occurred within the cavity such that only part of the internal lacuna was occupied by this metal cation. No XRD was obtained that would have provided definitive proof of structure. In an attempt to revisit this chemistry, Brewster, Aguilar, Sessler and co-workers 2+ prepared an amethyrin-uranyl complex (42) using a non-aqueous uranyl silylamide as the UO2 source (Scheme 2).56 The resultant complex was postulated to have all six pyrrole nitrogen atoms coordinated to the metal center, as determined by NMR spectroscopy. This species was characterized by UV-vis, high-resolution mass spectrometry, NMR, and cyclic voltammetry. Again, however, no supporting single crystal X-ray diffraction structural data could be obtained. 3 Scheme 2. Synthesis and proposed structures of amethyrin-neptunyl (41) and -uranyl (42) complexes. The preliminary data obtained using amethyrin established precedence for the coordination of actinyls within such expanded systems. Sessler, Seidel, Vivian (Gorden), and Lynch, in collaboration with Scott and Keogh from LANL, would continue these efforts. They reported the synthesis and characterization of isoamethyrin (43), obtained via the oxidative cyclization of the open chain intermediate 44, as well as the corresponding uranyl (45) and neptunyl (46) complexes (Scheme 3).57 The uranyl complex was prepared using uranyl acetate dihydrate in a methanol: dichloromethane mixture containing triethylamine. The neptunyl(V) complex was prepared by adding Np(VI)O2Cl2 in 1 M HCl to a solution of isoamethyrin in methanol in the presence of triethylamine. Over the course of the reaction, either from triethylamine, a known sacrificial reductant, or methanol, the Np(VI) was found to undergo reduction to the corresponding Np(V) form. Single crystal X-ray diffraction data provided definitive proof of structure for the U(VI)O2 and Np(V)O2-isoamethyrin complexes, 45 and 46. This remains the only neptunyl-expanded porphyrin characterized by single crystal XRD to date. Scheme 3. Synthesis of isoamethyrin
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