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The study of polycyclic aromatic hydrocarbons (PAHs) with curved surfaces, also known as buckybowls or fullerene fragments, represent an area which is under intense investigation by organic chemists and material scientists. This dissertation describes research that contributes to this field. The availability of multi-gram quantities of the smallest buckybowl, corannulene, has led to the synthesis of several larger systems with buckybowl subunits. Cyclotrimerization of corannulyne using palladium(0) as the catalyst is described. The resulting product, C60H24, is a highly nonplanar hydrocarbon with very interesting conformational dynamics. The X-ray crystallography of the cyclotrimer confirms the “twist” conformation with C1 symmetry. The cyclotrimer also shows three distinct corannulene bowls with very different inversion barriers as confirmed by both experiment and calculations. The bowl to bowl inversion of the corannulene bowl with the lowest inversion barrier results in pseudorotation of the cyclotrimer, which gives rise to a symmetrized 1H NMR spectrum exhibiting 12 distinct proton signals. 1H NMR line shape analysis gives an estimation of the inversion barrier at 8.5 – 8.6 kcal/mol. The tetrameric hydrocarbon C80H32 was synthesized through the Diels-Alder reaction of the cyclotrimer and 1,2-didehydrocorannulene. The six membered rings adjacent to the central ring in the cyclotrimer are activated enough to react with another corannulyne. The tetramer exhibits different conformational and optical absorption properties when compared to the cyclotrimer. The tetramer (C80H32), which is highly nonplanar and sterically congested, represents the largest fully characterized oligomer of corannulyne reported to date. This is also the first reported example of a cycloaddition reaction in which a corannulene subunit acts as a diene. A tripodal molecular receptor (C87H54O6) with three corannulene pincers and a cyclotriveratrylene tether was synthesized. The molecular receptor was evaluated by 1H NMR titration in toluene-d8 for its ability to bind fullerenes. The experiment demonstrates the formation of 1:1 inclusion complexes of the molecular receptor with fullerenes and provides the association constants of 1500 plus or minus 50 and 1180 plus or minus 30 M-1 for C60 and C70, respectively.

Gold¡¦s reputation as an inactive catalyst has been changed since the discoveries made by pioneers, including Bond, Hutchings, and Haruta. Today, exploring gold¡¦s potential to catalyze a range of heterogeneous and homogeneous reactions has been a hot topic. In this dissertation, reaction of CO and hydroxyl groups and cyclotrimerization of propanal (C2H5CHO) catalyzed by gold were studied by using temperature-programmed desorption (TPD), reflection absorption infrared spectroscopy (RAIRS), X-ray photoemission spectroscopy (XPS), low energy electron diffraction (LEED) and density functional theory (DFT) calculations. keywords: LEED, XPS, RAIRS,TPD, Gold, cyclotrimerization, propanal, CO oxidation In the first topic, CO oxidation by hydroxyl groups prepared by electron beam bombardment of physisorbed water was performed on Au(110) and Au(531). The formation of hydroxyl groups was evidenced by the observation of the desorption of D2O at 175 K and D2 at 230 K in TPD, in conjunction with the O 1s peak at 531.32 eV in XPS. The adsorption of CO on the hydroxyl-covered surface resulted in CO2 desorption at 110 K and 150 K on Au(110), and 105 K, 140 K and 180 K on Au(531). In the investigation of various D2O and CO coverages, the adsorption of CO and D2O was found to be preferred on low-coordinated Au atoms. Additionally, D2O on low-coordinated Au atoms required lower dissociation energy. This site effect was correlated with the high activity of smaller gold nanoparticles. Moreover, the mechanism for reaction of CO and hydroxyl groups was suggested to be similar to the water-gas-shift reaction due to the observation of the enhancement of D2 desorption after reaction. The second topic studied the cyclotrimerization of propanal catalyzed by gold. After exposing Au(110) to propanal at 180 K, the desorption of 2,4,6-triethyl-1,3,5-trioxane ((C2H5CHO)3) was observed at 340 K. The RAIRS and XPS studies showed that the cyclotrimerization of propanal was completed at 180 K. The same results were also detected on Au(531). However, only propanal molecular desorption was found on Au(111) suggesting that the low coordination Au atoms and the trench-like structure on Au(110) and Au(531) play key roles. On Ag(110) and Cu(110), no reaction was found indicating that the intrinsic nature of gold is also an important factor for the reaction. Investigation on Pt(110) inherited with the same (1x2) missing-row structure revealed that the decarbonylation of propanal occurred due to the stronger £b2(C,O) bonding mode. The reactions observed on Au(110), Au(531), and Pt(110) strongly suggest that the activity for the reactions may result from the relativistic effect of gold. The DFT calculations further showed the interactions between hydrogen in carbonyl groups and low-coordinated Au atoms (O=C-H¡KAu) help to gather propanal molecules and preorganize them at specific surface sites while an intracomplex reaction takes place.

Dans un contexte industriel où les réactions d'oxydation sont réalisées dans des conditions qui ne satisfont pas toujours les principes de la chimie verte, notre groupe étudie des catalyseurs de structure N-hydroxyphtalimide (NHPI), pour l'oxydation aérobie de substrats organiques variés dans des conditions douces. Dans le but d'obtenir des catalyseurs plus actifs, deux familles d'analogues hautement substitués sur le noyau phtalimide ont été préparées, suivant deux nouvelles méthodologies de synthèse. La première consiste en la bis-ortho-métallation / silylation d'acides ortho-phtaliques non protégés, pour un accès très rapide à des analogues silylés du NHPI. Les premiers tests en catalyse d'oxydation aérobie montrent une influence intéressante des groupements silyles sur la stabilité de l'espèce active, via leur encombrement stérique, cela permettant une amélioration de l'activité catalytique. La seconde stratégie inclut une cyclotrimérisation [2+2+2] totalement intramoléculaire d'ène-diyne diesters, pour la construction d'un squelette bis-ortho-lactone pentacyclique innovant. Ces intermédiaires sont aisément transformés en 3,6-bis(2-hydroxyphényl)-4,5-diarylphtalimides, ces composés présentant une symétrie C2 et deux axes d'atropoisomérie. Le dédoublement des énantiomères a été effectué, dans la perspective d'obtenir des catalyseurs d'oxydation aérobie potentiellement énantiosélectifs. / In the chemical industry, oxidation reactions are not often performed in green chemistry conditions. Our group has been studying N-hydroxyphthalimides (NHPI) catalysts for the aerobic oxidation of various organic substrates in mild conditions. In order to obtain more active catalysts, two families of analogs, showing high substitution on the phthalimide core, have been prepared, following two new synthetic methodologies. The first one consists of the bis-ortho-metalation / silylation of unprotected ortho-phthalic acids, for the efficient access to silylated analogs of NHPI. Preliminary tests in aerobic oxidation catalysis show an interesting influence of the bulkiness of the silyl groups towards the active species, because of increases in catalytic activities. The second strategy includes a totally intramolecular [2+2+2] cyclotrimerization of ene-diyne diesters, affording an innovative pentacyclic bis-ortho-lactone scaffold. These intermediates are easily converted to 3,6-bis(2-hydroxyphenyl)-4,5-diarylphthalimides, which present C2 symmetry and two atropoisomeric axis. The resolution of both enantiomers has been performed, in order to access aerobic oxidation catalysts with potent enantioselective activity.

<p>U radu su prvi put za proveru teorija nastajanja i gumolike elastičnosti polimernih mreža primenjeni modelni poliuretanski sistemi čiji su čvorovi veoma stabilni izocijanurat(heksahidro-1,3,5-triazin- 2,4,6-trion) prstenovi. Rad obuhvata: (1) Sintetezu nekoliko serija homogenih poli(uretan-izocijanuratnih) mreža, na bazi 2.4-TDI i poli(oksipropilen)diola, dvoetapnim postupkom u masi, tj. ciklotrimerizacijom teleheličnih diizocijanata uz katalizator Polycat 41. (2) Sintezu manje savr&scaron;enih mreža sa nekom definisanom koncentracijom visećih lanaca koja je postignuta uvodenjem monoola dietilenglikol- monometiletra u toku pripreme prepolimera. (3) Odredivanje povoljnih reakcionih uslove svih etapa sinteze uz primenu i modifikaciju postojećih analitičkih postupaka za karakterizaciju svojstava reakcionih komponenti i praćenja reakcija umrežavanja. (4) Procenu mogućih bočnih reakcija u toku nastajanja mreža jer one mogu značajno uticati na raspodelu različitih fragmenata u mrežama praćenjem koncentracija reakcionih proizvoda kod modelnih reakcija u rastvoru uz isti diol i isti katalizator i odgovarajuće mono-funkcionalne izocijanatne komponente. (5) Karakterizaciju svojstava i strukturnih parametara modelnih mreža i to primenom postupaka ekstrakcije i bubrenja, diferencijalne skanirajuće kalorimetrije, fotoelastičnih merenja, dinamičko-mehaničke spektroskopije i merenja napon-istezanje. Izborom nominalne Mn diola od 400 do 4000 postigne gustina umreženja 0.1x10^-4mol/cm³ do 10x10^-4mol/cm³ sa rasponom temperatura staklastog prelaza od -60&deg;C do +30&deg;C. Za procenu strukturnih parametara mreža primenjena je teorija granajućih procesa sa kaskadnom zamenom za slučaj nastajanja mreža ciklotrimerizacijom i dvoetapni postupak. U zavisnosti od konverzije NCO grupa u mrežama izračunate su masa po monomernoj jedinici, maseni udeo, broj po monomernoj jedinici, koncentracija po jedinici zapremine, Mn, Mw, Mz i Mw/Mn kako za elastično aktivne, osnovne i viseće lance tako i zamolekule sola. Ključni ekspehmentalni podaci koji su kori&scaron;ćeni za proveru teorija nastajanja bio sadržaj gela dobijen vi&scaron;estrukim ekstrakcijama, a za teorije gumolike elastičnosti ravnotežni modul dobijen iz fotoelastičnih merenja. Provera teorija gumolike elastičnosti se zasnivala se u nalaženje vrednosti pred- faktora 3 (tzv. faktora pamćenja) u jednačini koja daje vezu ravnotežnog modula elastičnosti i koncentracije elastično aktivnih lanaca mreže koji ukazuje na način fluktuacije cvorova mreže. Fotoelastična merenja su omogućila da se preko njih parameter pred-faktor 3 proceni pri malim deformacijama. Potvrden je koncept stvarnih mreža sa delimično potisnutim fluktuacijama čvorova uz aditivni doprinos zapletenosti lanaca modulu elastičnosti prema Langley-Graesley konceptu zarobljenih prepletaja.</p> / <p>In this thesis polymer network formation theories and rubber elasticity of polymer networks on model polyurethane systems having as a junction very stable isocyanurate(hexahidro-1,3,5-tгiazin-2,4,6- trion) rings are for the first time investigated. The work contains: (1) Synthesis of homogenious series of several poly(urethane-isocyanurate) networks based on poly(oxypropylene)diol and 2.4-TDI by two stages procedures in bulk i.e. cyclotrimerization of telechelic diisoicyanates with Polycat 41 as catalyst. (2) Synthesis of less perfect networks with some concentration of dangling chains obtained by introduction of monofunctional component diethyleneglycolmonomethylether during prepolymer formation. (3) Determination of optimal reaction conditions for both stages of the synthesis. (4) Estimation of possible side reaction during network formation because of theirs important influence on nework fragment distribution. (5) Caracterization of networks structure and properties by swelling and multiply extraction, differential scanning calorimetry, photoelastical measurements, dynamic-mechanical spectroscopy and stress-strain measurements. By using the different Mn of diols (400 - 4000) the network density from<br />0.1x10^-4mol/cm³ to 10x10^-4mol/cm³ and glass transition temperatures from -60&deg;C to +30&deg;C was achieved. For network structure determinations the theory of branching processes with cascade substitution was used. Mass per monomer unit, mass fraction, number per monomer unit, concentration per unit volume, Mn, Mw, Mz and Mw/Mn for elastically active network chains, backbone chains, dangling chains and sol molecules In the dependence on NCO groups conversion are calculated. Crucial experimental data for examination of network formation theories was the gel content and for rubber<br />elasticity theories the equilibrium modulus received from photoelastical measurement. The estimation of rubber elasticity theories was based on the analysis of the front factor 3 in the equation which gives the relation between the equilibrium modulus and concentration of elastically active network chains. It is estimated the additive contribution of chain entanglements to the equilibrium modulus, especially in the case of high networks density according to Langley-Graesley theory of trapped entanglements.</p>

The aim of my Thesis was to develop a general synthetic methodology for the preparation of long helicenes equipped with suitable functional groups that control their solubility or serve as anchoring groups for attachment to metallic surfaces, especially gold. The well-established transition metal catalyzed [2+2+2] cyclotrimerization of triynes was selected as the key scaffold-forming transformation in the synthesis of long helicenes because of its high regioselectivity, atom efficiency, functional group tolerance and general robustness. A modular approach was used for the preparation of the starting oligoynes, thus enabling a high level of their structural diversity. Individual resorcinol- based aromatic building blocks were interconnected by Sonogashira cross-coupling reactions, providing complex cyclization precursors encompassing up to twelve alkyne units pre-arranged for the multiple [2+2+2] cycloisomerization to produce three six- membered rings from each set of three neighboring alkyne units. Thus, a small series of long helicenes with up to 19 rings constituting the helical scaffold was synthesized. The quadruple cyclization leading to the longest oxahelicene prepared to date was performed in a high-temperature-high-pressure flow reactor at 250 řC in the presence of CpCo(CO)2. The set of...

4 ABSTRACT The synthesis has been described yielding a new type of rigid conjugated polymer networks which possess a high content of permanent micropores and macropores and exhibit high surface areas up to 1469 m2/g. The networks have been prepared via chain-growth coordination polymerization catalysed with insertion catalysts based on Rh complexes. This polymerization has been newly applied to bifunctional acetylenic monomers of diethynylarene type (1,4-diethynylbenzene, 1,3-diethynylbenzene and 4,4'-diethynylbiphenyl). The covalent structure of the networks consists of the polyacetylene main chains densely connected by arylene struts. The W and Mo metathesis catalysts have been revealed as inefficient for the synthesis of these networks. The increase in the polymerization temperature and time has been shown to affect positively the content and the diameter (up to 22 nm) of the mesopores in the networks. A mechanism has been proposed that explains the mesopores formation as a result of mutual knitting of small particles of the microporous polymer. The application of emulsion polymerization technique allowed to prepare texturally hierarchical polyacetylene networks possessing interconnected open macropores (diameter up to 4,8 μm) the walls of which exhibited micro/mesoporous texture. It was demonstrated...