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The synthesis of highly porous organic polymers with predefined porosity has attracted considerable attention due to their potential in a wide range of applications. Porous organic polymers (POPs) offer novel properties such as permanent porosity, adjustable chemical nature, and noteworthy thermal and chemical stability. These remarkable properties of the POPs make them promising candidates for use in gas separation and storage. The emission of carbon dioxide (CO2) from fossil fuel combustion is a major cause of global warming. Finding an efficient separation and/or storage material is essential for creating a cleaner environment. Therefore, the importance of the POPs in the field is undeniable. Along these pursuits, several porous polymers have been synthesized with different specifications. The first class of porous polymers are called Covalent Organic Frameworks (COFs). They possess highly ordered structures with very high surface areas and contain light elements. COFs based on B-O, C-N, and B-N bonds have been reported so far. In particular, COFs based on B-O bond formation are well investigated due to the kinetically labile nature of this bond which is essential for overcoming the crystallization problem of covalent networks. Along this line, triptycene-derived covalent organic framework (TDCOF-5) has been synthesized through a condensation reaction between 1, 4-benzenediboronic acid and hexahydroxytriptycene which leads to the formation of boronate ester linkage. TDCOF-5 has the highest H2 uptake under 1 atm at 77K (1.6%) among all known 2D and 3D COFs derived from B–O bond formation and moderate CO2 uptake (2.1 mmol g-1) with Qst values of 6.6 kJ mol-1 and 21.8 kJ mol-1, respectively. The second class of porous structures discussed herein is diazaborole linked polymers (DBLPs). They are constructed based on B-N bond formation and possess amorphous structures due to the lack of the reversible bond formation processes. At this scope, 2, 3, 6, 7, 14, 15-hexaaminotriptycene (HATT) hexahydrocloride was synthesized and reacted with different boronic acid derivatives to produce three different porous polymers under condensation reaction conditions. DBLP-3, -4 and -5 have very high surface areas; 730, 904, and 986 m2 g-1, and offer high CO2 uptake (158.5, 198, and 171.5 mg g-1) at 1 bar and 273 K, respectively. DBLPs have much higher CO2 uptake capacity when compared to almost all reported B-N and B-O containing porous polymers in the field. In addition to high CO2 capacity, DBLPs showed remarkable CO2/N2 and CO2/CH4 selectivity, when the Henry`s law of initial slope selectivity calculations were applied. In general, DBILPs exhibit high selectivities for CO2/N2 (35-51) and CO2/CH4 (5-6) at 298 K which are comparable to those of most porous polymers.

Plastics or polymers are thought to behave oppositely from metals. Ideally, polymers behave as insulators while metals conduct electricity. Shirakawa and coworkers discovered conductive polymers in 1977.1 These conductor polymers have been extensively studied, discovering that charge transfer oxidative doping of polyacteylene could increase its conductivity by 12 orders of magnitude. Polyacetylene, although showing promise as an organic conductor, because it is highly air-sensitive and oxidizes when exposed to molecular oxygen, therefore making this an unattractive use for commercial products. Attention has been focused on heterocylic aromatic polymers such as polythiophene and polypyrrole, in efforts to produce conductive polymers that are air-stable, tractable, and have a low band gap. The lone-pair electrons of the sulfur and nitrogen atoms tend to stabilize the positive charges of the p-doped polymers through resonance. 2 By using Shirakawas’ idea of using polypyrrole as the focus point of our research and expanding upon that by the addition of a rhenium metal to an organic compound, (1,2-C5H3(CNR)2) and this should offer some new and interesting chemical properties. These new properties are; new optical properties, new electronic properties, improved physical properties, and a reversible electrochemical shift. This research will help in the field of organometallic semiconductors in applications such as OLED’s, and electrochromic windows.3-6

Microporous organic polymers (MOPs) are porous materials. Owing to their high surface area, tunable pore sizes and high physicochemical stability, they are studied for applications including gas capture and separation and heterogeneous catalysis. In this thesis, a series of imine/azo-linked MOPs were synthesized. The MOPs were examined as potential CO2 sorbents and as supports for heterogeneous catalysis. The MOPs were synthesized by Schiff base polycondensations and oxidative couplings. The porosities of the imine-linked MOPs were tunable and affected by a range of factors, such as the synthesis conditions, monomer lengths, monomer ratios. All the MOPs had ultramicropores and displayed relatively high CO2 uptakes and CO2-over-N2 selectivities at the CO2 concentrations relevant for post-combustion capture of CO2. Moreover, the ketimine-linked MOPs were moderately hydrophobic, which might increase their efficiency for CO2 capture and separation. The diverse synthesis routes and rich functionalities of MOPs allowed further post-modification to improve their performance in CO2 capture. A micro-/mesoporous polymer PP1-2, rich in aldehyde end groups, was post-synthetically modified by the alkyl amine tris(2-aminoethyl)amine (tren). The tethered amine moieties induced chemisorption of CO2 on the polymer, which was confirmed by the study of in situ infrared (IR) and solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. As a result, the modified polymer PP1-2-tren had a large CO2 capacity and very high CO2-over-N2 selectivity at low partial pressures of CO2. Pd(II) species were incorporated in the selected MOPs by means of complexation or chemical bonding with the imine or azo groups. The Pd(II)-rich MOPs were tested as heterogeneous catalysts for various organic reactions. The porous Pd(II)-polyimine (Pd2+/PP-1) was an excellent co-catalyst in combination with chiral amine for cooperatively catalyzed and enantioselective cascade reactions. In addition, the cyclopalladated azo-linked MOP (Pd(II)/PP-2) catalyzed Suzuki and Heck coupling reactions highly efficiently. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 4: Accepted. Paper 7: Manuscript.</p>

For many applications of industrial relevance, solids providing enhanced porosity such as activated carbons or zeolites have been the key drivers of progress in the past century. Albeit these materials marked an entire era of research, scientists have contributed immense effort to mimic porosity in an artificial way. A rich field to address this challenge is polymer chemistry. Especially covalent triazine frameworks (CTFs), which are exclusively built up from organic matter connected by covalent bonds, have proliferated in the last 10 years and provide remarkable chemical and thermal stability. Within this thesis, a salt templating method for the synthesis of mesoporous CTF materials was developed that applies binary salt mixtures of ZnCl2 (the conventional reaction medium) in combination with alkali halides. In contrast to existing synthetic concepts that induce mesoporosity via high temperature treatment (up to 700 °C), salt templating was conducted at moderate temperatures (300 – 450 °C) and significantly avoided carbonisation as well as nitrogen loss. By applying this new method, salt templated materials with a four-fold increased total pore volume (CTF 1_LiCl: 2.1 cm3 g-1 vs. conventional CTF-1: 0.5 cm3 g-1) and an almost complete retention of the specific surface area (1320 m2 g-1 vs. 1440 m2 g-1) could be synthesised. Another aspect of this thesis dealt with a novel approach to generate CTF materials in a solvent-free, time-efficient and scalable manner. To this end, a mechanochemical synthesis route was developed that makes use of the Friedel-Crafts alkylation to generate CTF materials from cyanuric chloride, serving as triazine node, and electron-rich aromatic compounds as linker molecules. By this method, permanently porous materials (up to 570 m2 g-1) could be synthesised from various monomers with different length and geometry. The syntheses could be conducted within two hours and on a gram scale, thus significantly exceeding known methods in terms of time-efficiency and scalability. Besides these synthetic concepts, three other chapters covered the area of potential applications for CTF materials. To this end, novel CTF materials were synthesised and assessed towards their suitability for use in energy storage systems such as lithium sulfur battery or supercapacitor. In analogy to SPAN, a sulfur containing conductive poly(acrylonitrile) polymer, CTFs containing covalently bound sulfur (S@CTF) were anticipated as promising cathode material in the lithium sulphur battery. Following the synthesis of a variety of different materials, a particular focus was set on determining the impact of sulfur attachment on the porosity and on illustrating the bonding situation of sulfur within the porous host matrix. Elemental analysis revealed that the highest sulfur loadings (33 w%) were obtained for the CTF samples obtained at the lowest synthesis temperature (500 °C). These findings were in agreement with nitrogen adsorption experiments that showed a reduced porosity after sulfur attachment for each material and the largest percental drop of the total pore volume for those samples with the highest sulfur loadings. XPS investigations suggested the presence of C-S species in the sulfur treated materials and supported the formation of covalently bound sulfur. Whereas the synthesis of S@CTF materials was successful, the electrochemical characterisation in a carbonate-based electrolyte revealed a substantial capacity loss after only a few cycles, which was probably due to a loss of active material and underlined that confinement of sulfur might be the key to obtain cathodes with increased cycling stability. In this thesis, a novel pyridine-based CTF material was synthesised, which showed beneficial nitrogen doping and a tuneable porosity by careful choice of the reaction temperature (Scheme 3b). An in-depth characterisation by means of argon physisorption, X-ray photoelectron and Raman spectroscopy was conducted. Thereby, the structural changes upon thermal treatment were carefully investigated and interpreted. The non-purified CTFs – still containing large amounts of ZnCl2 – were directly processed into supercapacitor electrodes. Herein, ZnCl2 was serving two purposes: it acted as a porogen during the CTF synthesis (surface areas up to 3100 m2 g-1 were obtained) and as a precursor for an in situ generated aqueos electrolyte. It was demonstrated that this methodology bypasses extensive washing and more importantly, the findings gained from the electrochemical characterisation matched the structural indications from the XPS experiments. Thus, without purifying the material in advance, this method allowed for estimating the materials’ properties based on its behaviour as supercapacitor. In the last part, a purely CTF-based organocatalyst that benefits from a monomer bearing a catalytically active functionality was synthesised by introducing a charged cationic imidazolium moiety into a microporous covalent triazine framework. A finely adjusted synthetic protocol enabled the structural retention of the thermally labile imidazolium motif, whose successful integration was proven by an in-depth structural characterisation, applying solid-state 1H MAS NMR, XPS and FT-IR spectroscopy. If applied as heterogeneous organocatalyst, the imidazolium-based CTF was active in the carbene-catalysed Umpolung reaction, thus providing clear evidence of an intact structure.

This research presents a new approach to creating large, complex molecules to carry out molecular recognition and catalytic functions mimicking biological proteins. Development of new therapeutics that bind protein surfaces and disrupt protein-protein interactions was first addressed targeting the envelope transmembrane protein in HIV-1, gp41. In this work, spiroligomer inhibitors of gp41 were designed and synthesized, and then the biochemical activity was tested. Rationally designed inhibitors were developed using computational modeling with the Molecular Operating Environment software (MOE). To build the desired molecular shape according to the design, C-2 alkylation of a bis-amino acid monomer was investigated to synthesize the higher degree of bis-amino acids with various reaction conditions for access to all possible diastereomers. Based on this design and synthetic methodology, a spiroligomer targeting gp41 was built by synthesizing each monomer and then linking them together by diketopiperazine (DKP). For the biological evaluation, the gp41-5 gene was transformed into E. coli and the protein was expressed, purified, and refolded for an in vitro binding test. A direct binding, fluorescence polarization assay was used to evaluate the binding affinity of the functionalized spiroligomer to the gp41-5 protein. Its antiviral activity was assessed in collaboration with the Chaiken lab at Drexel University. In addition, investigation into how the unique structures provided by the spiroligomer backbone allow for various uses, such as functionalized struts in porous organic polymers (POPs). In the large internal space of a POP, a nucleophilic, catalytic spiroligomer was installed to increase the reaction rate for the hydrolysis of methyl paraoxon (a neurotoxin G agent stimulant). Spiroligomers were designed and synthesized with backbone DMAP moieties, and the activity of these catalysts was analyzed in collaboration with the Hupp lab at Northwestern University. / Chemistry

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Le projet de cette thèse consistait à élaborer de nouveaux matériaux donneurs d’électrons pour les cellules solaires organiques. Cette technologie photovoltaïque émergente en plein essor a d’ores et déjà atteint la limite d’efficacité lui permettant d’être industrialisée et commercialisée à grande échelle. Le faible coût de production des dispositifs photovoltaïques organiques les rendent compétitives vis-à-vis des technologies inorganiques déjà bien implantées. Mais leur plus gros avantage est surement leur légèreté et leurs propriétés mécaniques qui les rendent très souples. Elles devraient donc certainement avoir un rôle majeur à jouer dans le futur en complément des cellules solaires classiques, avec une utilisation pour des applications spécifiques. Nous avons ainsi développé des polymères en utilisant des chromophores réputés pour leurs propriétés photophysiques : les porphyrines, les BODIPY et les dicétopyrrolopyrroles. Ces différentes unités absorbent intensément la lumière, ce qui les rend adéquates pour être utilisées pour la conversion de l’énergie solaire en électricité. En concevant un design original et adapté à cette application, nous avons ainsi obtenu plusieurs nouveaux polymères prometteurs. Nous avons ensuite pu étudier leurs propriétés électrochimiques et électroniques, ainsi que leurs caractéristiques photophysiques. Pour cela nous avons utilisé de nombreux outils (caméra streak, absorption transitoire femtoseconde, etc.) afin de comprendre en détails leur propriétés d’absorption et de luminescence. Ces informations nous ont permis de pouvoir ensuite comprendre leur comportement une fois intégrés dans la couche active des dispositifs photovoltaïques. En effet, le mécanisme de fonctionnement pour la création d’un courant électrique met en jeu des transferts d’électrons ultrarapides (∼50 fs) vers un accepteur d’électron. Il est alors crucial de pouvoir comprendre et contrôler les paramètres pouvant influencer l’efficacité de ces transferts et la stabilisation des charges qui en résultent, pour pouvoir finalement mener à des rendements de conversion de l’énergie lumineuse élevés. / The aim of this thesis was to elaborate new electron donor materials for organic solarcells. This emerging photovoltaic technology is rapidly expanding, and has yet already reached the limit for its large-scale commercialization. The low manufacturing cost of organic photovoltaic devices make then competitive face to well-established inorganic technologies. Their biggest advantage is their weight and their mechanical properties which make them flexible. They should play a key role in future as a complement to classic solar cells, with their use in specific applications. We developed polymers by using different chomophores, well-known for their interesting photophysical properties: the porphyrin, the BODIPY and the diketopyrrolopyrrole. All these units intensively absorb the light, making them perfect candidates to be used to convert sunlight to electricity. By designing appropriate structures for this application, we synthesized several new promising polymers. Afterward, we studied their electrochemical and electronic properties, as well as their photophysics. We used powerful tools (streak camera, transient absorption, etc.) in order to understand in details their absorption and luminescence properties. These results enabled us to further understand their behavior once inside the active layer of photovoltaic devices. Indeed, the mechanism for the electric current creation involves ultrafast electron transfers (∼50 fs) toward electron acceptor. It is of utmost importance to understand and control parameters that could affect the electron transfer efficiency and the resulting charge stabilization, to finally lead to better power conversion efficiencies.

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