A presente tese tem como objetivo principal a investigação do processo de intercalação e esfoliação do hexaniobato lamelar em soluções de hidróxidos de tetraalquilamônios e, também, do emprego das partículas do niobato na preparação de materiais híbridos com polissacarídeos. O material de composição H2K2Nb6O17 foi suspenso em soluções aquosas contendo diferentes concentrações dos hidróxidos de tetrametilamônio (TMA+), tetraetilamônio (TEA+) e tetrapropilamônio (TPA+). Após o tempo de reação foram separadas duas frações: o sólido depositado no recipiente e o sobrenadante turvo contendo as partículas não depositadas de características coloidais. Os resultados de difratometria de raios X, análise termogravimétrica, análise elementar, espectroscopia vibracional no infravermelho e Raman mostram que o processo de intercalação é promovido segundo a ordem: TMA+ > TEA+ > TPA+, isto é, a intercalação é facilitada para íons pouco volumosos. Já o processo de esfoliação do hexaniobato é promovido na ordem inversa: TPA+ » TEA+ > TMA+, ou seja, quanto mais volumoso o íon tetraalquilamônio, maior a extensão do processo de separação das lamelas. A formação das partículas cilíndricas, presentes em maior quantidade nas amostras tratadas com soluções de TPA+ e TBA+, é favorecida pelo aumento do tamanho da cadeia carbônica e da concentração das soluções do hidróxido. Além dos processos de intercalação ou esfoliação, observou-se o processo de formação de gel na etapa de remoção de eletrólitos na lavagem dos sólidos depositados. O entumescimento das lamelas empilhadas de hexaniobato é favorecido para amostras intercaladas com íons TEA+; possivelmente esses íons possuem a melhor relação entre hidrofilicidade e tamanho, promovendo a formação de gel. O composto contendo íons TEA+ intercalados no hexaniobato ácido foi empregado na preparação de material híbrido contendo o polissacarídeo quitosana intercalado na matriz inorgânica, com o objetivo de modificar a superfície do hexaniobato para promover a compatibilização com o amido e a formação de nanocompósitos. Filmes de amido desestruturado contendo partículas de hexaniobato foram preparados por casting. Para alcançar alto grau de dispersão da partícula inorgânica no polímero, três tipos de partículas de hexaniobato foram empregadas: (i) partículas esfoliadas com n-butilamina, (ii) partículas altamente hidratadas de TEA+-hexaniobato e (iii) partículas modificadas pela intercalação com quitosana. As técnicas de difratometria de raios X, análise termogravimétrica acoplada à espectrometria de massa, espectroscopia vibracional no infravermelho e microscopia eletrônica de varredura sugerem que nos filmes transparentes e flexíveis obtidos, a matriz lamelar se encontra preferencialmente na forma intercalada. Os resultados preliminares de análise dinâmico-mecânica sugerem a seguinte tendência no comportamento mecânico dos filmes: a adição do hexaniobato torna os filmes de amido mecanicamente mais resistentes e as amostras sem o plastificante glicerol apresentam maior resistência e menor deformação que aquelas com glicerol. / The main aim of this Thesis is the investigation of intercalation and exfoliation processes occurring when the layered material H2K2Nb6O17 is suspended in alkaline solutions containing tetramethylammonium (TMA+), tetraethylammonium (TEA+) or tetrapropylammonium (TPA+) cations, as well as the employment of the hexaniobate particles in the preparation of hybrid materials with polysaccharides. After the reaction using different concentrations of the tetraalkylammonium hydroxide solutions, two fractions were separated: the deposited solid (i.e. the sediment at bottom of the flasks) and the opaque supernatant containing particles with colloidal characteristics. Experimental data from X-ray diffractometry (XRD), mass spectrometry coupled thermogravimetric analyses (TG-MS), elemental analysis, vibrational infrared (IR) and Raman spectroscopies show that intercalation reaction is promoted in the order TMA+ > TEA+ > TPA+ while exfoliation process is facilitated in the inverse order: TPA+ » TEA+ > TMA+. Development of particles with stick-like shapes is observed when H2K2Nb6O17 is kept mainly in the solutions containing the larger TPA+ and TBA+ ions. Samples containing intercalated TEA+ ions form a gel-like system when washed to remove the non-intercalated ions dissolved in water. Experimental data suggest that the gel phase constituted by long-range swelled particles. This fact was interpreted as a consequence of the intermediate characteristics (surface polarity and ion radius) of the TEA+ ions compared to the others ions investigated in this study. The hexaniobate material intercalated with TEA+ ions was used to prepare a hybrid material having the chitosan polymer intercalated into the inorganic matrix in order to compatibilize the hexaniobate particles with starch and a nanocomposite formation. The study of the films of starch-niobate showed that the matrix is in the intercalation form preferentially, even using different exfoliation agents and modification species (n-butylamine, TEAOH and chitosan). Films of destructured starch having hexaniobate particles were prepared by casting method. In order to reach a high level of inorganic particles dispersed in the polymer, three kinds of hexaniobate particles were used: (i) particles exfoliated with n-butylamine, (ii) hydrated particles of TEA+-hexaniobate and (iii) hexaniobate particles intercalated with chitosan. XRD, TG-MS, IR, and scanning electron microscopy (SEM) techniques suggest that hexaniobate particles are mainly in the intercalated form in the transparent and flexible obtained starch films. Preliminary dynamic mechanical analysis data indicate the following general tendency in the mechanic characteristics of the films: niobate particles make the starch films more resistant and the samples without the glycerol plasticizer present higher resistance and lower deformation than the films with glycerol.

Os fármacos antiinflamatórios não-esteróides (FAINEs) são amplamente utilizados no combate a processos inflamatórios e dores, mas apresentam restrição de uso em razão de sérios efeitos colaterais sobre o trato gastrointestinal. A atividade biológica de complexos metálicos tem sido objeto de pesquisa de grande interesse na área de metalofármacos e compostos do tipo Cu(II)-FAINEs apresentam boa atividade antiinflamatória e efeitos colaterais reduzidos em relação aos fármacos orgânicos. Nesse trabalho, com o objetivo de contribuir para ampliar os estudos sobre o desenvolvimento de alternativas aos FAINEs, foram preparados e caracterizados complexos cobre(lI) com ibuprofeno, indometacina, naproxeno, sulindaco, meloxicam. Os compostos foram imobilizados em Hidrotalcita, um hidróxido duplo lamelar (HDL) de magnésio e alumínio (Mg/AI = 3) que é biocompatível e tem uso como antiácido estomacal. As interações dos metalofármacos com o HDL geraram materiais híbridos bioinorgânicos do tipo Cu-FAINElHDL, nos quais os complexos podem estar presentes de duas maneiras: intercalados entre as Ia meias ou adsorvidos nas superfícies externas do hidróxido duplo lamelar, dependendo do solvente utilizado. A intercalação de complexos neutros é favorecida em solvente misto álcooVamida no qual a Hidrotalcita sofre esfoliação promovida por um processo de hidrólise da amida. A estabilidade alguns dos complexos e dos materiais híbridos em condições gástricas simuladas (pH e temperatura) e as atividades antiinflamatória, analgésica e ulcerogênica in vivo dos sistemas contendo indometacina (Indo) foram investigadas. A intercalação do complexo Cu-Indo no HDL favorece sua estabilização, contribuindo para potencializar a sua atividade farmacolágica. Os materiais híbridos bioinorgânicos obtidos neste trabalho apresentam propriedades interessantes com vistas a potencial aplicação como sistemas de liberação controlada de fármacos. / Non-steroidal anti-inflammatory drugs are widely consumed to treat inflammatory diseases and pain but their clinical use are limited due to serious side-effects on the gastrointestinal tract. The bioactivity of metal complexes exhibits great interest in metal-based drug research. Cu(II)-NSAID compounds show good anti-inflammatory property and decreased side-effects compared to their organic parent drugs. This work aimed to contribute for development of alternative NSAIDs. Cu-NSAlD compounds containing the drugs Ibuprofen, Indomethacin, Naproxen, Sulindac and Meloxicam were synthesized and characterized. The compounds were also immobilized on Hydrotalcite, a layered double hydroxide (LDH) of magnesium and aluminum (Mg/Al = 3), that is biocompatible and used as stomach antacid. The interactions of the copper drugs with LDH led to Cu-NSAID/LDH- bioinorganic hybrid materiais. Two kinds of complex-LDH interactions were observed by changing the solvent: intercalation between LDH layers or adsorption on the LDH external surfaces. The intercalation of neutral complexes is favored in an alcohollamide solvent mixture where Hydrotalcite undergoes exfoliation process promoted by the amide hydrolysis. The stability of some complexes and their correspondent hybrid materials under gastric conditions (pH and temperature) and also in vivo anti-inflammatory, analgesic and ulcerogenic activities for Indomethacin (Indo)-containing systems were investigated. The stabilization of the Cu-Indo structure is promoted by intercalation of the complex into the LDH layers, contributing to increase its pharmacological activity. The bioinorganic hybrid materials here investigated also exhibit interesting properties for applications as controlled drug delivery systems.

A intercalação de espécies de interesse biológico e terapêutico em Hidróxidos Duplos Lamelares (HDLs) vem se mostrando uma estratégia interessante para a obtenção de sistemas de armazenamento ou carregadores de drogas. No presente trabalho foram investigadas rotas sintéticas e parâmetros experimentais para a intercalação dos ânions derivados dos fármacos ácido mefenâmico e piroxicam em HDL de Mg2+ e Al3+. Os sólidos foram caracterizados por difratometria de raios X, análises elementar e térmica, microscopia eletrônica de varredura e espectroscopia no infravermelho e Raman. Os difratogramas de raios X dos materiais híbridos HDL-mefenamato isolados por co-precipitação (pH=9-9,5) mostram, além de fase do tipo HDL, alguns picos finos e de baixa intensidade que podem estar relacionados com a presença de um sal de mefenamato. Os melhores resultados foram obtidos empregando uma relação molar ânion/Al3+ =1. Nos processos de reconstituição e troca iônica, os picos finos não são observados. Os espectros vibracionais mostram que o ácido mefenâmico está na forma desprotonada e intacto. Os ânions mefenamato se arranjam em uma bicamada no espaço interlamelar (d003 ~21-22 Å). Os híbridos HDL-piroxicamato obtidos por co-precipitação são constituídos de pelo menos duas fases. À medida que a razão ânion/Al3+ diminui, observa-se o aumento na formação de fase HDL. / Intercalation of biological and therapeutical species into Layered Double Hydroxides (LDHs) has been shown an interesting strategy to get drug storage or drug carrier systems. In this work it were investigated synthetic routes and experimental parameters for intercalation of anions derived from mefenamic acid and piroxicam drugs into LDH of Mg2+ and Al3+ composition. The isolated solids were characterized by X-ray diffractometry, elemental and thermal analysis, scanning electron microscopy and infrared and Raman spectroscopies. Besides LDH phase, XRD patterns of LDH-mefenamate hybrid materials isolated by coprecipitation (pH=9-9.5) show some narrow and low intensity peaks that can be related to a mefenamate salt phase. Improved data were obtained using an anion/Al3+ molar ratio equal 1. When employing reconstruction and ion exchange methods, narrow peaks are no observed. Vibrational spectra indicate that mefenamic acid is deprotonated and integral between the layers. Guest anions are arranged in a bylayer in the interlayer space (d003 ~21-22 Å). LDH-piroxicamate hybrid materials obtained by coprecipitation are constituted by at least two phases. An increase in LDH phase formation it is observed when the molar ratio anion/Al3+ decreases.

Ce travail présente les études électrochimiques et structurales menées sur deux systèmes : P2/O3-NaxMn1-yFeyO2 et O’3-NaxNiO2 utilisés en tant que matériaux d’électrode positive pour batteries Na-ion.Concernant le système P2/O3-NaxMn1-yFeyO2, l’étude par diffraction des rayons X menée in situ pendantla charge de batteries a montré de nombreuses transitions structurales. Que leur structure soit de type P2ou O3, les matériaux présentent une phase distordue pour les taux d’intercalation (x) les plus élevés etune phase très peu ordonnée pour les taux d’intercalation les moins élevés. Entre ces deux étatsd’intercalation, les phases de type P2 présentent moins de transitions que les phases de type O3. Celaentraine de meilleures propriétés électrochimiques pour les phases de type P2 (meilleure capacité endécharge, meilleure rétention de capacité…). Les spectroscopies d’absorption des rayons X et Mössbauerdu 57Fe ont montré que les couples redox Mn4+/Mn3+ et Fe4+/Fe3+ sont impliqués lors du cyclage, à bas ethaut potentiel, respectivement.Concernant O’3-NaNiO2, la diffraction des rayons-X menée in situ pendant la charge de batteriesO’3-NaNiO2//Na a montré de nombreuses transitions structurales O’3 ↔ P’3 résultant du glissement desfeuillets MO2. Ces transitions s’accompagnent de mises en ordre Na+ - lacunes dans le matériau. La tailledes grains a montré avoir un intérêt majeur puisqu’elle influe sur le nombre de phases présentessimultanément dans le matériau. Lorsque la batterie est déchargée, la phase limitante Na≈0.8NiO2 estobservée et empêche le retour à O’3-NaNiO2 / This work concerns the electrochemical and structural studies carried out on two systems used aspositive electrode materials for Na-ion batteries: P2/O3-NaxMn1-yFeyO2 and O’3-NaxNiO2. Concerning theP2/O3-NaxMn1-yFeyO2 systems, in situ X-ray diffraction carried out during the charge of the batteriesshowed that both materials undergo several structural transitions. Both the P2 and O3 phases show adistorted phase for the higher intercalation rates (x) and a poorly ordered phase for the lower ones.Between these two states, P2-based materials exhibit less structural transitions than the O3-based ones.This is correlated to the better electrochemical properties the P2-based materials exhibit (better dischargecapacity, better capacity retention…). X-ray absorption and 57Fe Mössbauer spectroscopies showed thatthe Mn4+/Mn3+ and Fe4+/Fe3+ redox couples are active upon cycling, respectively at low and high voltage.Concerning O’3-NaNiO2, in situ X-ray diffraction carried out during the charge of O’3-NaNiO2//Nabatteries showed several structural transition between O’3 and P’3 structures, resulting from slab glidings.These transitions are accompanied by Na+ - vacancies ordering within the “NaO6” slabs. Upon discharge,the material does not come back to its initial state and, instead, the Na≈0.8NiO2 phase represents themaximum intercalated state. The occurrence of this limiting phase prevents O’3-NaNiO2 to be consideredas an interesting material for real Na-ion applications.

Planar two-dimensional (2-D) nanostructured indium oxide (InOx) and one-dimensional (1-D) tin oxide (SnO2) semiconductor metal-oxide layers have been utilised for gas sensing applications. Novel layered Surface Acoustic Wave (SAW) based sensors were developed consisting of InOx/SiOxNy/36°YXLiTaO3, InOx/SiNx/SiO2/36°YXLiTaO3 and InOx/SiNx/36°YXLiTaO3 The 1 µm intermediate layers of silicon oxynitride (SiOxNy), silicon nitride (SiNx) and SiO2/SiNx matrix were deposited on lithium tantalate (36°YXLiTaO3) substrates by r.f. magnetron sputtering, electron-beam evaporation and plasma enhanced chemical vapour deposition (PECVD) techniques, respectively. As a gas sensitive layer, a 100 nm thin layer of InOx was deposited on the intermediate layers by r.f. magnetron sputtering. The targeted gases were ozone (O3) and hydrogen (H2). An intermediate layer has multiple functions: protective role for the interdigital transducers' electrodes as well as an isolating effect from InOx sensing layer, thereby improving the sensor performance. The developed SAW sensors' exhibited high response magnitudes with repeatable, reversible and stable responses towards O3 and H2. They are capable of sensing concentrations as low as 20 parts-per-billion for O3 and 600 parts-per-million for H2. Additionally a conductometric type novel sensing structure of SnO2/36°YX LiTaO3 was also developed by depositing a thin layer of SnO2 nanorods by PECVD. The gas sensing performance exhibited repeatable, reversible, stable responses towards NO2 and CO. The surface morphology, crystalline structure and preferred orientation of the deposited layers were investigated by Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). A polycrystalline, oxygen deficient non-stoichiometric InOx with grain sizes of 20-40 nm was revealed. The 1-D nanostructures were characterised by Transmission Electron Microscopy (TEM) showing nanorods with needle-like shape , diameters of 10-20 nm a t the top and 30-40 nm at the base as well as a preferential growth orientation of [ ] on the LiTaO3 substrate. The developed sensors are promising for O3, H2 and CO sensing.

Ce travail présente, dans trois systèmes différents, l'étude de nouveaux oxydes à structures incommensurables. Le composé $Ba_6Mn_{24}O_{48}$ ($Ba_{0.25}MnO_2$) possède une structure constituée par une charpente d'octaèdres $MnO_6$ dont l'arrangement définit des tunnels de type rutile, hollandite et des tunnels plus larges appelés "double barrelled". Les phénomènes d'incommensurabilité et de diffusion diffuse rencontrés dans ce composé sont décrits et expliqués par la distribution particulière des baryum dans les tunnels hollandite et "double barrelled". L'existence d'oxydes à structures lamellaires désaccordées est démontrée avec les composés de formulation $A'_{\alpha}[(AO)_{\frac{1+x}{2}}]_n(CoO_2)$. Ils sont construits sur la succession, selon un axe d'empilement, de (n-1) couches [AO] de type $NaCl$ et d'une couche hexagonale d'octaèdres $CoO_6$ joints par les arêtes. La transition entre ces deux couches est assurée par un élément de post-transition A'. Des termes n=2, avec $A'=Tl$ ou $Hg/Pb$ et des termes n=3 avec $A'=Bi$ ont été isolés. Dans les deux cas, le cation $A$ est $Sr$ et/ou $Ca$. Les composés ($Ba_{2-3x}Bi_{3x-}$)($Fe_{2x}Bi_{1-2x}$)$O_{3-\delta}$ ($x\in$[1/3, 1/2]), dérivés de la pérovskite, présentent des structures modulées de symétrie quadratique pour $x>0.4$. En utilisant le formalisme des groupes de superespace, une étude par analyse Rietveld montre que c'est la c\oe xistence sur le m\^{e}me site A pérovskite des cations $Ba$ et $Bi$ qui est responsable du phénomène d'incommensurablité observé. La structure magnétique de ces composés, déterminée par diffraction neutronique, est de type antiferromagnétique avec ferromagnétisme faible.

<p>Thin metal films have found their use in many magnetic devices. They form pseudo two-dimensional systems, where the mechanisms for the magnetic interactions between the layers are not completely understood. Layered crystal structures have an advantage over such artificial systems, since the layers can be strictly mono-atomic without any unwanted admixture. In this study, some model systems of layered magnetic crystal structures and their solid solutions have been investigated by x-ray and neutron diffraction, Mössbauer and electron spectroscopy, heat-capacity and magnetic measurements, and first-principle electronic structure calculations, with the goal of deepening our understanding through controlled chemical synthesis.</p><p>The compounds TlCo₂S₂, TlCo₂Se₂ and their solid solution TlCo₂Se_2-xS_x, all containing well separated cobalt atom sheets, order with the moments ferromagnetically aligned within the sheets. In TlCo₂S₂, the net result is ferromagnetism, while TlCo₂Se₂ exhibits antiferromagnetism. The inter-layer distance is crucial for the long-range coupling, and it was varied systematically through Se-S substitution. The incommensurate helical magnetic structure found for TlCo₂Se₂ (x = 0) prevails in the composition range 0 ≤ x ≤ 1.5 but the pitch of the helix changes. The accompanying reduction in inter-layer distance on sulphur substitution varies almost linearly with the coupling angle of the helix. An additional competing commensurate helix (90°) appears in the medium composition range (found for x = 0.5 and 1.0).</p><p>The systems TlCo_2-xMe_xSe₂ show helical magnetic ordering for Me = Fe or Cu, while a collinear antiferromagnetic structure occurs for Me = Ni. Magnetic order is created by iron substitution for copper in the Pauli paramagnetic TlCu₂Se₂, but now with the moments perpendicular to the metal sheets.</p><p>TlCrTe₂ forms a quite different crystal structure, with intra-layer ferromagnetic alignment and net collinear antiferromagnetism. In contrast to the other phases, the values of the moments conform well to a localised model for Cr³⁺.</p>

Relay-assisted cooperative communications are promising solutions for error-performance improvement and cell coverage extension. In this thesis, we propose several efficient cooperative relay communication schemes. First, an efficient space-time coded cooperative relay communications scheme that employs linear precoding and transmission-pattern selection is proposed. This is built upon an existing block linear precoding technique for conventional multiple-input multiple-output systems in order to improve the diversity performance of a multihop relay network. Second, we consider several multiuser cooperative relay communication schemes employing layered modulations, such as hierarchical modulation and superposition coding. Conventional cooperative relay communication is effective in mitigating fading effects. However, additional resources, such as time slots or frequency bands are required for the relay, which reduce the overall throughput. Reduction of throughput will become more severe as the number of users increases. In order to overcome this limitation, multiuser cooperative relaying schemes that employ hierarchical modulation and superposition coding are proposed. These schemes exploit the superimposed message for users in the network and allow the system to transmit two or more independent data streams simultaneously. The proposed schemes do not require additional resources than the conventional schemes, while improving the error performance by flexibly controlling the power division coefficient of superposition coding or the distance parameter of hierarchical modulation. / Graduation date: 2012 / Access restricted to the OSU Community at author's request from Sept. 28, 2011 - Sept. 28, 2012

In the first section of the thesis graphitic carbon nitride was for the first time synthesised using the high-temperature condensation of dicyandiamide (DCDA) – a simple molecular precursor – in a eutectic salt melt of lithium chloride and potassium chloride. The extent of condensation, namely next to complete conversion of all reactive end groups, was verified by elemental microanalysis and vibrational spectroscopy. TEM- and SEM-measurements gave detailed insight into the well-defined morphology of these organic crystals, which are not based on 0D or 1D constituents like known molecular or short-chain polymeric crystals but on the packing motif of extended 2D frameworks. The proposed crystal structure of this g-C3N4 species was derived in analogy to graphite by means of extensive powder XRD studies, indexing and refinement. It is based on sheets of hexagonally arranged s-heptazine (C6N7) units that are held together by covalent bonds between C and N atoms. These sheets stack in a graphitic, staggered fashion adopting an AB-motif, as corroborated by powder X-ray diffractometry and high-resolution transmission electron microscopy. This study was contrasted with one of many popular – yet unsuccessful – approaches in the last 30 years of scientific literature to perform the condensation of an extended carbon nitride species through synthesis in the bulk. The second section expands the repertoire of available salt melts introducing the lithium bromide and potassium bromide eutectic as an excellent medium to obtain a new phase of graphitic carbon nitride. The combination of SEM, TEM, PXRD and electron diffraction reveals that the new graphitic carbon nitride phase stacks in an ABA’ motif forming unprecedentedly large crystals. This section seizes the notion of the preceding chapter, that condensation in a eutectic salt melt is the key to obtain a high degree of conversion mainly through a solvatory effect. At the close of this chapter ionothermal synthesis is seen established as a powerful tool to overcome the inherent kinetic problems of solid state reactions such as incomplete polymerisation and condensation in the bulk especially when the temperature requirement of the reaction in question falls into the proverbial “no man’s land” of classical solvents, i.e. above 250 to 300 °C. The following section puts the claim to the test, that the crystalline carbon nitrides obtained from a salt melt are indeed graphitic. A typical property of graphite – namely the accessibility of its interplanar space for guest molecules – is transferred to the graphitic carbon nitride system. Metallic potassium and graphitic carbon nitride are converted to give the potassium intercalation compound, K(C6N8)3 designated according to its stoichiometry and proposed crystal structure. Reaction of the intercalate with aqueous solvents triggers the exfoliation of the graphitic carbon nitride material and – for the first time – enables the access of singular (or multiple) carbon nitride sheets analogous to graphene as seen in the formation of sheets, bundles and scrolls of carbon nitride in TEM imaging. The thus exfoliated sheets form a stable, strongly fluorescent solution in aqueous media, which shows no sign in UV/Vis spectroscopy that the aromaticity of individual sheets was subject to degradation. The final section expands on the mechanism underlying the formation of graphitic carbon nitride by literally expanding the distance between the covalently linked heptazine units which constitute these materials. A close examination of all proposed reaction mechanisms to-date in the light of exhaustive DSC/MS experiments highlights the possibility that the heptazine unit can be formed from smaller molecules, even if some of the designated leaving groups (such as ammonia) are substituted by an element, R, which later on remains linked to the nascent heptazine. Furthermore, it is suggested that the key functional groups in the process are the triazine- (Tz) and the carbonitrile- (CN) group. On the basis of these assumptions, molecular precursors are tailored which encompass all necessary functional groups to form a central heptazine unit of threefold, planar symmetry and then still retain outward functionalities for self-propagated condensation in all three directions. Two model systems based on a para-aryl (ArCNTz) and para-biphenyl (BiPhCNTz) precursors are devised via a facile synthetic procedure and then condensed in an ionothermal process to yield the heptazine based frameworks, HBF-1 and HBF-2. Due to the structural motifs of their molecular precursors, individual sheets of HBF-1 and HBF-2 span cavities of 14.2 Å and 23.0 Å respectively which makes both materials attractive as potential organic zeolites. Crystallographic analysis confirms the formation of ABA’ layered, graphitic systems, and the extent of condensation is confirmed as next-to-perfect by elemental analysis and vibrational spectroscopy. / Die vorliegende Arbeit befasst sich mit der Synthese und Charakterisierung neuer Allotropen und Nanostrukturen von Karbonitriden und berührt einige ihrer möglichen Anwendungen. Alle gezeigten, ausgedehnten, kovalent verbundenen Karbonitridgerüste wurden in einem ionothermalen Syntheseprozess – einer Hochtemperaturbehandlung in einem eutektischen Salzgemisch als ungewöhnlichem Lösungsmittel – aus einfachen Präkursormolkülen erzeugt. Der Kondensationsmechanismus folgt einer temperaturinduzierten Deaminierung und Bildung einer ausgedehnten, aromatischen Einheit; des dreifach substituierten Heptazines. Die Dissertation folgt vier übergreifenden Themen, beginnend mit der Einleitung in Karbonitridsysteme und der Suche nach einem Material, welches einzig aus Kohlenstoff und Stickstoff aufgebaut ist – einer Suche, die 1834 mit den Beobachtungen Justus von Liebigs „über einige Stickstoffverbindungen“ begann. Der erste Abschnitt zeigt die erfolgreiche Synthese von graphitischem Karbonitrid (g-C3N4); einer Spezies, welche auf Schichten hexagonal angeordneter s-Heptazineinheiten beruht, die durch kovalente Bindungen zwischen C- und N-Atomen zusammengehalten werden, und welche in einer graphitischen, verschobenen Art und Weise gestapelt sind. Der zweite Abschnitt berührt die Vielfalt von Salzschmelzensystemen, die für die Ionothermalsynthese geeignet sind und zeigt auf, dass die bloße Veränderung der Salzschmelze eine andere Kristallphase des graphitischen Karbonitrides ergibt – das g-C3N4-mod2. Im dritten Abschnitt wird vom Graphit bekannte Interkallationschemie auf das g-C3N4 angewendet, um eine Kalliuminterkallationsverbindung des graphitischen Karbonitirdes zu erhalten (K(C6N8)3). Diese Verbindung kann in Analogie zum graphitischen System leicht exfoliiert werden, um Bündel von Karbonitridnanoschichten zu erhalten, und weist darüberhinaus interessante optische Eigenschaften auf. Der vierte und letzte Abschnitt handelt von der Einführung von Aryl- und Biphenylbrücken in das Karbonitridmaterial durch rationale Synthese der Präkursormoleküle. Diese ergeben die heptazinbasierten Frameworks, HBF-1 und HBF-2 – zwei kovalente, organische Gerüste.

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