Notre étude a pour objet la conception, la synthèse ainsi que l’étude structurale d’architectures supramoléculaires obtenues par auto-assemblage, en se basant sur les concepts de la tectonique moléculaire. Cette branche de la chimie supramoléculaire s’occupe de la conception et la synthèse de molécules organiques appelées tectons, du grec tectos qui signifie constructeur. Le tecton est souvent constitué de sites de reconnaissance branchés sur un squelette bien choisi. Les sites de reconnaissance orientés par la géométrie du squelette peuvent participer dans des interactions intermoléculaires qui sont suffisamment fortes et directionnelles pour guider la topologie du cristal résultant. La stratégie envisagée utilise des processus d'auto-assemblage engageant des interactions réversibles entre les tectons. L’auto-assemblage dirigé par de fortes interactions intermoléculaires directionnelles est largement utilisé pour fabriquer des matériaux dont les composants doivent être positionnés en trois dimensions (3D) d'une manière prévisible. Cette stratégie peut également être utilisée pour contrôler l’association moléculaire en deux dimensions (2D), ce qui permet la construction de monocouches organisées et prédéterminées sur différents types des surfaces, tels que le graphite.Notre travail a mis l’accent sur le comportement de la fonction amide comme fonction de reconnaissance qui est un analogue du groupement carboxyle déjà utilisé dans plusieurs études précédentes. Nous avons étudié le comportement d’une série de composés contenant un noyau plat conçu pour faciliter l'adsorption sur le graphite et modifiés par l'ajout de groupes amide pour favoriser la formation de liaisons hydrogène entre les molécules ainsi adsorbées. La capacité de ces composés à former de monocouches organisées à l’échelle moléculaire en 2D a été examinée par microscopie à effet tunnel, etleur organisation en 3D a également été étudiée par cristallographie aux rayons X. Dans notre étude, nous avons systématiquement modifié la géométrie moléculaire et d'autres paramètres afin d'examiner leurs effets sur l'organisation moléculaire. Nos résultats suggèrent que les analyses structurales combinées en 2D et 3D constituent un important atout dans l'effort pour comprendre les interactions entre les molécules adsorbées et l’effet de l’interaction avec la surface du substrat. / Our study involves the design, synthesis and structural analysis of supramolecular architectures obtained by self-assembly, based on the concepts of molecular tectonics. This branch of supramolecular chemistry explores the properties of molecules called tectons,from the Greek word tectos, meaning builder. Tectons typically incorporate sites of recognition connected to well-chosen skeletons with defined geometries. The sites of recognition, oriented by the geometry of the skeleton, can participate in intermolecular interactions that are sufficiently strong and directional to control the topology of the resulting assembly. This strategy is thereby based on self-assembly processes involving reversible interactions between tectons. Self-assembly directed by strong directional intermolecular interactions is widely used to produce materials whose components must be positioned in three dimensions (3D) in a predictable way. This strategy can also be used to control molecular association in two dimensions (2D), thereby allowing the construction of predictably organized and predetermined nanopatterns on various surfaces, such as graphite.Our work has focused on the behavior of the amide groups as primary sites of intermolecular interaction. These groups are analogues of carboxyl groups, which have been widely used in previous studies of directed molecular assembly. We have studied the 3D and 2D association of compounds with flat cores designed to favor the formation of sheets and to facilitate adsorption on graphite, modified by the addition of amide groups to promote the formation of intermolecular hydrogen bonds. The ability of these compounds to form predictably ordered 2D nanopatterns has been examined by scanning tunneling microscopy, and their organization in 3D has also been investigated by X-ray crystallography. In our study, we have systematically altered molecular geometry and other parameters to examine their effect on molecular organization. Our results suggest that combined structural analyses in 2D and 3D are an important asset in the effort to understand why molecules aggregate in particular ways and how these preferences can be altered by underlying surfaces.

La chimie supramoléculaire est un domaine qui suscite depuis quelques années un intérêt grandissant. Le domaine s’appuie sur les interactions intermoléculaires de façon à contrôler l’organisation moléculaire et ainsi moduler les propriétés des matériaux. La sélection et le positionnement adéquat de groupes fonctionnels, utilisés en combinaison avec un squelette moléculaire particulier, permet d’anticiper la façon dont une molécule interagira avec les molécules avoisinantes. Cette stratégie de construction, nommé tectonique moléculaire, fait appel à la conception de molécules appelées tectons (du mot grec signifiant bâtisseur) pouvant s’orienter de façon prévisible par le biais d’interactions faibles et ainsi générer des architectures supramoléculaires inédites. Les tectons utilisent les forces intermoléculaires mises à leur disposition pour s’orienter de façon prédéterminée et ainsi contrecarrer la tendance à s’empiler de la manière la plus compacte possible. Pour ce faire, les tectons sont munies de diverses groupes fonctionnels, aussi appelés groupes de reconnaissance, qui agiront comme guide lors de l’assemblage moléculaire. Le choix du squelette moléculaire du tecton revêt une importance capitale puisqu’il doit permettre une orientation optimale des groupes de reconnaissance. La stratégie de la tectonique moléculaire, utilisée conjointement avec la cristallisation, ouvre la porte à un domaine de la chimie supramoléculaire appelé le génie cristallin. Le génie cristallin permet l’obtention de réseaux cristallins poreux soutenus par des interactions faibles, pouvant accueillir des molécules invitées. Bien que toutes les interactions faibles peuvent être mises à contribution, le pont hydrogène est l’interaction prédominante en ce qui a trait aux réseaux cristallins supramoléculaires. La force, la directionnalité ainsi que la versatilité font du pont hydrogène l’interaction qui, à ce jour, a eu le plus grand impact dans le domaine du génie cristallin. Un des groupements de reconnaissance particulièrement intéressants en génie cristallin, faisant appel aux ponts hydrogène et offrant plusieurs motifs d’interaction, est l’unité 2,4-diamino-1,3,5-triazinyle. L’utilisation de ce groupement de reconnaissance conjointement avec un cœur moléculaire en forme de croix d’Onsager, qui défavorise l’empilement compact, permet l’obtention de valeurs de porosités élevées, comme c’est le cas pour le 2,2’,7,7’-tétrakis(2,4-diamino-1,3,5-triazin-6-yl)-9,9’-spirobi[9H-fluorène]. Nous présentons ici une extension du travail effectué sur les cœurs spirobifluorényles en décrivant la synthèse et l’analyse structurale de molécules avec une unité dispirofluorène-indénofluorényle comme cœur moléculaire. Ce cœur moléculaire exhibe les mêmes caractéristiques structurales que le spirobifluorène, soit une topologie rigide en forme de croix d’Onsager défavorisant l’empilement compact. Nous avons combiné les cœurs dispirofluorène-indénofluorényles avec différents groupements de reconnaissance de façon à étudier l’influence de l’élongation du cœur moléculaire sur le réseau cristallin, en particulier sur le volume accessible aux molécules invitées. / Supramolecular chemistry is a field of rapidly increasing interest in recent years. The field uses weak intermolecular interactions to control molecular organisation and therefore modulate the properties of materials. Adequate selection and positioning of functional groups, combined with a carefully selected molecular core to which the groups are attached, allows for the creation of molecules with a high degree of predictability in the way they will interact with their neighbours. This approach to the design and construction of materials, called molecular tectonics, is based on subunits called tectons (derived from the Greek word for builder), which use weak interactions to organise themselves in a predictable manner and generate novel supramolecular architectures. In favorable cases, the interactions can counter the general tendency shown by molecules to pack together in a compact manner. Instead, specific functional groups direct molecular recognition and help guide the process of auto-assembly. At the same time, the molecular core of the tecton is also of capital importance as it must allow an optimal orientation of the recognition groups. The molecular tectonics approach, used jointly with crystallisation, opens the door to new opportunities in crystal engineering. For example, crystal engineering now allows the logical creation of porous crystalline networks that can accept guest molecules. Although any type of weak interaction can hold such networks together, the hydrogen bond is favored for constructing porous supramolecular networks. The strength, directionality and versatility of the hydrogen bond accounts for its special importance in the domain of crystal engineering. A recognition group of particular interest in crystal engineering is the 2,4-diamino-1,3,5-triazinyl unit. This unit forms hydrogen bonds according to various standard motifs. The use of this recognition group, joined to molecular cores specifically designed to inhibit close packing, such as Onsager crosses, allows for the construction of supramolecular networks with high porosity, as shown by the behaviour of 2,2’,7,7’-tetrakis(2,4-diamino-1,3,5-triazin-6-yl)-9,9’-spirobi[9H-fluorene]. We present here an extension of previous studies of spirobifluorenyl cores by describing the synthesis and structural analysis of molecules with related dispirofluorene-indenofluorenyl cores. This new core offers the same characteristics as the spirobifluorenyl core, namely rigid topology and an Onsager cross molecular shape which are known to inhibit close packing. We have combined this core with a variety of recognition groups to verify the influence of the molecular core on the crystalline networks generated, particularly on the volume accessible to guest molecules.

Crystal engineering is defined as “the understanding of intermolecular interactions in the context of crystal packing and in the utilisation of such understanding in the design of new solids with desired physical and chemical properties”. If crystals are the supramolecular equivalents of molecules, then crystal engineering is the supramolecular equivalent of organic synthesis. The subject considers both crystal structure analysis and design of new structures with targeted properties. The concept of “Supramolecular Synthons” was introduced by G. R. Desiraju in this context, for the rational design of structures. Supramolecular synthons are the smallest reducible structural units that contain geometrical and chemical information required for recognition between functional groups in molecular solids. Crystal engineering has grown very fast after the introduction of this idea in 1995 and engineered solids were found to be useful for application in many diverse fields, from structural chemistry to drug design. Because of the great significance of supramolecular synthons, their identification and analysis in terms of crystallographic, spectroscopic, and computational methods is essential. Single crystal X-ray diffraction (SCXRD) is a widely used technique for the identification of synthon structure. But the technique has its own limitations like requirement of good quality, suitably sized single crystals, longer times associated with the process which further restricts high throughput analysis. Practically, there is no other way for identification of synthons on a regular basis. In this situation a simple, accurate, and fast method will be of significance; not only for basic studies, but also to scan different solid state phases in pharmaceutical industries. Due to this reason, I have studied IR spectroscopy to find marker bands for different synthons in the first part of the thesis. In chapter 2, I have analyzed a variety of C–H···X based weak synthons. For identification of each synthon, two sets of compounds were taken. In one set the synthon exists and in the other set it does not. Comparison and verification of IR characteristics helps to establish marker bands. Such markers are used to get information on synthon patterns in compounds with unknown crystal structures. The next challenge is whether or not such an IR method can distinguish different geometries of a same interaction. To address this question, different geometries of NO2···I halogen bonded synthons are investigated in chapter 3. This synthon exists in three geometries P, Q and R based on angular and distance criteria. The identification process is divided into five steps. The first step identifies IR signatures from very similar compounds, but with different topologies. The second step verifies earlier features and establishes IR marker bands. In the next step a graded IR protocol is formulated for stepwise discrimination of unknown systems. Such a graded method is applied for clarification of synthon ambiguities and in the identification of synthons in new compounds. Till now synthon information from crystal structures is used as a basis for IR study. Spectroscopy provides chemical information on intermolecular interactions. Is it possible to use such chemical information for crystal engineering? Chapter 4 deals with this aspect. Here, IR investigation is performed on the acid···amide heterodimer synthon. The initial analysis shows contradictory outcomes for synthon formation. According to IR, the N–H···O interaction is significantly destabilized in this synthon. Why then does the acid···amide synthon form? It is found that the answer lies in the higher stability of the other interaction, O–H···O, in the synthon. In other words, dimer formation will be preferred when the O‒H···O interaction is favoured. This is possible when the acidity of H-atom and the basicity of carbonyl O-atom is high. Based on this, a combinatorial study is performed varying the chemical nature of molecules, electron donating or withdrawing. Four quadrants are generated with different combinations of the molecular nature. The result of the combinatorial study shows different acid–amide oriented synthon preferences from different quadrants. A combination of all the observed synthons creates a structural landscape for the acid–amide system. A particular synthon associated with a specific quadrant is found to be responsible for the mechanical property of the synthesized cocrystals. Analysis on the structural aspects of mechanical properties allows for the formulation of models for property engineering. Can it be possible to use these models for targeted property design, other than serendipitous results? Crystal engineering is associated with three aspects, structure analysis, structure design and property engineering. Structure analysis is the first step in any crystal engineering exercise. It also explains the way by which the subject was started in the early days to correlate structure with property. This is the first phase or generation of crystal engineering. The second generation considers rational design of crystal structure which is facilitated by the concept of the supramolecular synthon. This phase has seen in the incorporation of different synthon based strategies to build a variety of supramolecular architectures. However, there is no prediction of a property which is the ultimate aim of crystal engineering. If one can achieve a desired property by predesign, then crystal engineering will see the final and higher stage which is termed third generation crystal engineering in chapter 5. The second part of the thesis discusses work is this direction, where mechanical properties are targeted and achieved by design using models from previous work. Chapter 6 discusses the engineering of elastic crystals from initial brittle precursors. A capping based model is proposed and used to prepare systems that can adopt the desired structure type. Among many other requirements, the crystals need some structurally buffering regions to show elasticity. Type-II electrostatic halogen bonds are used to construct such buffering regions. When the crystals are obtained according to the model type, they show reversible elastic deformation. σ-Hole based halogen bonds are crucial to the synthesis. But, during the project some adverse effects were noticed/realized for the use of halogen bonds. This suggests the need for an alternative methodology. A synthon that can mimic both the geometrical and chemical nature of σ-hole based halogen bonds would be useful to replace the earlier one. A search in this respect results in π-hole oriented orthogonal synthons based on C=O···C=O and NO2···NO2 interactions. A stepwise replacement procedure is applied to see and carry forward structural modularity in the new systems. Cocrystal systems are chosen for easy replacement by changing the constituents. Halogen bonds in cocrystals of the first step are partially substituted by a π-hole mimicking synthon in the second step and completely substituted in the third step. All the structures in the different steps are found to retain the same property, namely elasticity, although they possess dissimilar synthons. These aspects are discussed in chapter 7. Chapter 8 deals with the design of hand twistable helical crystals which are known to result during natural growth. Helical shape crystals are highly impactful for application in metamaterials and lithographic techniques, but at the same time occurrence of such morphology is unpredictable. Such shape generates from the periodic bending of crystals and thus needs multiple deformation directions. Here, a multistep crystal engineering procedure is adopted to get two directionally (2D) plastically bendable crystals, starting from one directional (1D) plastic crystals. Halogen bonds again play a major role in the design. The route follows the order 1D plastic crystals → 1D elastic crystals → 2D elastic crystals → 2D plastic crystals. These 2D plastic crystals are used to obtain hand-twisted helical crystals. Here, different properties namely elastic and plastic are seen in identically structured compounds. Once again, problems in using halogens are noticed. To address the issue of halogens, chapter 9 uses halogen bond/hydrogen bond equivalence to replace halogen bonds by geometrically and chemically similar hydrogen bonds. However, the first designed molecule in this respect did not result in the desired structure. The obligations are removed by applying the molecular/supramolecular equivalence strategy on the earlier molecule. Such an attempt gives another completely hydrogen bonded system that can now adopt the model structure and show a similar 2D plasticity. Crystals of this compound are also hand twistable. Third generation crystal engineering needs predesign models for targeted property engineering. In this context some differently structured elastic crystals are compared with common brittle crystals to identify and ascertain the structural requirements. This analysis helps in constructing different models for future engineering of elastic crystals. It also tabulates the structural and interaction differences in obtaining different mechanical properties namely shearing, plastic, elastic and brittle. In summary, these two major aspects for doing crystal engineering are highlighted in my thesis. One is the identification of robust synthons and the other is the use of synthon based structure design for property engineering. The first part of the thesis discusses the IR spectroscopic method for identification of synthons and then uses the spectral information for crystal structure engineering. The second part is related to deliberate crystal property engineering and uses structure-property relationships from the previous chapters and the literature to formulate predesign models and strategy. Achieving crystal properties in this way is expected to initiate the fast progress of the third generation crystal engineering.

The thesis entitled “Organic fluorine in crystal engineering: Consequences on molecular and supramolecular organization” consists of six chapters. The main theme of the thesis is to address the role of substituted fluorine atoms in altering the geometrical and electronic features in organic molecules and its subsequent consequences on crystal packing. The thesis is divided into three parts. Part I deals with compounds that are liquids under ambient conditions, crystal structures of which have been determined by the technique of in situ cryocrystallography. Part II demonstrates the utilization of in situ cryocrystallography to study kinetically trapped metastable crystalline phases that provide information about crystallization pathways. In part III, crystal structures of a series of conformationally flexible molecules are studied to evaluate the consequences of fluorine substitution on the overall molecular conformation. The genesis and stabilization of a particular molecular conformation has been rationalized in terms of variability in intermolecular interactions in the crystalline state. Part I. In situ cryocrystallography: Probing the solid state structures of ambient condition liquids. Chapter 1 discusses the crystal structures of benzoyl chloride and its fluorinated analogs. These compounds have been analysed for the propensity of adoption of Cl···O halogen bonded dimers and catemers. The influence of conformational and electronic effects of sequential fluorination on the periphery of the phenyl ring has been quantified in terms of the most positive electrostatic potential, VS,max (corresponding to σ-hole) on the Cl-atom. It is shown that fluorine also exhibits “amphoteric” nature like other heavier halogens, particularly in presence of electron withdrawing groups. Although almost all the derivatives pack through C–H···O, C–H···F, C–H···Cl, Cl···F, C–H···π and π···π interactions, the compound 2,3,5,6-tetrafluorobenzoyl chloride exhibited a not so commonly observed Cl···O halogen bonded catemer. On the other hand, the proposed Cl···O mediated dimer is not observed in any of the structures due to geometrical constraints in the crystal lattice. Chapter 2 presents the preferences of fluorine to form hydrogen bond (C–H···F) and halogen bonds (X···F; X= Cl, Br, I). Crystal structures of all three isomers of chloro-, bromo-and iodo-fluorobenzene have been probed in order to gain insights into packing interactions preferred by fluorine and other heavier halogens. It has been observed that homo halogen…halogen (Cl···Cl, Br···Br and I···I) contacts prevail in most of the structures with fluorine being associated with the hydrogen atom forming C–H···F hydrogen bond. The competition between homo and hetero halogen bonds (I···I vs I···F) is evident from the packing polymorphism exhibited by 4-iodo fluorobenzene observed under different cooling protocols. The crystal structures of pentafluoro halo (Cl, Br, I) benzenes were also determined in order to explore the propensity of formation of homo halogen bonds over hetero halogen bonds. Different dimeric and catemeric motifs based on X···F and F···F interactions were observed in these structures. Chapter 3 focuses on the effect of different cooling protocols in generating newer polymorphs of a given liquid. The third polymorph (C2/c, Z'=6) of phenylacetylene was obtained by sudden quenching of the liquid filled in capillary from a hot water bath (363 K) to the nitrogen bath (< 77 K). Also, different polymorphs were obtained for both 2¬fluoro phenylacetylene (Pna21, Z'=1) and 3-fluoro phenylacetylene (P21/c, Z'=3) when crystallized by sudden quenching in contrast to the generally followed method of slow cooling which results in isostructural forms (P21, Z'=1). The rationale for these kinetically stable “arrested” crystalline configurations is provided in part II of the thesis. Part II. Tracing crystallization pathways via kinetically captured metastable forms. Chapter 4 explains the utilization of the new approach of sudden quenching of liquids (detailed in chapter 3) to obtain kinetically stable (metastable) crystalline phases that appear to be closer to the unstructured liquids. Six different examples namely, phenylacetylene, 2-fluorophenylacetylene, 3-fluorophenylacetylene, 4-fluorobenzoyl chloride, 3-chloro fluorobenzene and ethyl chloroformate are discussed in this context. In each case, different polymorphs were obtained when the liquid was cooled slowly (100 K/h) and when quenched sharply in liquid nitrogen. The relationship between these metastable forms and the stable forms (obtained by slow cooling) combined with the mechanistic details of growth of stable forms from metastable forms provides clues about the crystallization pathways. Part III. Conformational analysis in the solid state: Counterbalance of intermolecular interactions with molecular and crystallographic symmetries. Chapter 5 describes the crystal structures of a series of conformationally flexible molecules namely, acetylene and diacetylene spaced aryl biscarbonates and biscarbamates. While most of the molecules adopt commonly anticipated anti (transoid) conformation, some adopt unusual cisoid and gauche conformations. It is shown that the unusually twisted conformation of one of the compounds [but-2-yne-bis(2,3,4,5,6¬pentafluorocarbonate)] is stabilized mainly by the extraordinarily short C–H···F intermolecular hydrogen bond. The strength of this rather short C–H···F hydrogen bond has been authenticated by combined single crystal neutron diffraction and X-ray charge density analysis. It has also been shown that the equi-volume relationship of H-and F-atoms (H/F isosterism) can be explored to access various possible conformers of a diacetylene spaced aryl biscarbonate. While biscarbonates show variety of molecular conformations due to absence of robust intermolecular interactions, all the biscarbamates adopt anti conformation where the molecules are linked with antiparallel chains formed with N–H···O=C hydrogen bonds. Chapter 6 presents a unique example where the commonly encountered crystallographic terms namely, high Z' structure, polymorphism, phase transformation, disorder, isosterism and isostructuralism are witnessed in a single molecular species (parent compound benzoylcarvacryl thiourea and its fluorine substituted analogs). The origin of all these phenomenon has been attributed to the propensity of formation of a planar molecular dimeric chain mediated via N–H···O [R2 (12)] and N–H···S [R2 (8)] dimers.

Ce travail réalisé dans le cadre de l’initiative africaine de l’IUCr porte sur l’étude structurale par diffraction des rayons X de quelques architectures élaborées par association, via des interactions faibles, des anions {[M(C2O4)3]3-,M = Cr, Fe} et des cations complexes à base de la 2-picolylamine (amp) métaux de transition (Co2+, Cu2+ et Mn2+). L’architecture à base de l’ion Co2+ est bidimensionnelle et présente des feuillets ondulés constitués de chaines bimétalliques de chiralité différente où les deux ions complexes ([Cr(C2O4)3]3- et [Co(amp)3]3+ ) sont connectés par des liaisons hydrogène. Ces feuillets hébergent des molécules d’eau qui forment des clusters dodécamèriques aux caractéristiques nouvelles. Le composé déshydraté se réhydrate rapidement dans l’air ambiant et les deux états possèdent des couleurs différentes. Plusieurs cycles de déshydratation-réhydratation n’altèrent pas la qualité cristalline du composé. L’architecture à base des ions Cu2+ possède également des feuillets mais présente une ondulation plus forte que celle de l’architecture au cobalt. Ces couches sont constituées de chaines formées de cations dimériques [Cu2(amp)4Cl]3+ et d’anions {[M(C2O4)3]3-,M = Cr, Fe}. Les deux composés sont iso-structuraux et leur architecture présente des canaux monodimensionnels qui contiennent des molécules d’eau qui forment des clusters hexamèriques. Le composé subit des transitions de phase entre la basse température (100K) et la température de déshydratation (341K) avec une perte de la symétrie. Le composé se réhydrate plus difficilement que celui à base de l’ion cobalt(III). L’ion Mn2+ ne donne pas l’architecture escomptée mais un polymère de coordination nouveau / This work, realized under the IUCr initiative, framework involves the structural study via X-ray diffraction, of some heteromolecular architectures formed by the association through non-covalent bonds, between the tris (oxalato) chromate (III) and tris (oxalato) ferrate (III) anions {[M(C2O4)3]3-, M = Cr, Fe} and the cationic complex of the 2-picolylamine (amp) and transition metal (Co2 +, Cu2 + and Mn2 +). Co2 + ion builds two-dimensional corrugated layers made of bimetallic chiral chains where the two different complex ions ([Cr(C2O4)3]3- and [Co(amp)3]3 +) are connected by hydrogen bonds. These layers, connected by weak hydrogen interactions, host between them, water molecules which build dodecameric clusters having new characteristics. The dehydrated compound has different structure and color and is able to quickly reabsorb water molecules from surrounding to regenerate the initial compound despite that it has no pores. Several cycles of this process do not seriously affect the crystalline quality of this compound. The compound obtained with the Cu2 + ion also has a two-dimensional framework. Their layers are formed between the dimeric cation [Cu2 (amp) 4Cl]3 + and the anion {[M(C2O4)3]3-,M = Cr, Fe}. Both compounds are iso-structural; their frameworks are formed via π - - - π interactions and build 1D channels which contain water molecules forming hexameric clusters. The compound undergoes a phase transition between 100 K and the dehydration temperature (341K). During this dehydration, a loss of symmetry of the compound is recorded and rehydration process is more difficult than for cobalt(III)-framework. The use of Mn2+ ions does not give the expected architecture but a new coordination polymer

Tesis por compendio / [ES] El Proyecto de investigación aquí descrito se estructura en dos partes. La primera parte se centra en la investigación fundamental con el objetivo de crear un protocolo para la síntesis de zeolitas. La segunda parte se refiere al diseño, síntesis y caracterización de nuevas zeolitas, particularmente utiles para aplicaciones DeNOx,, pero también podría ser útil para aplicaciones MTO. La investigación fundamental sugiere un Nuevo modelo de preparación de zeolitas utilizando otras zeolitas como simiente. Este proceso se llama transformación zeolita-zeolita o también conversión interzeolita. El alto rendimiento obtenido, la rápida cristalización y la mejor utilización y rendimiento de los materiales de partida se han tenido en cuenta para mejorar el proceso en base a un proyecto de doctorado financiado por una empresa. Este método se ha ilustrado utilizando varias zeolitas como semilla, entre otras FAU y CHA, para la preparación de las dos zeolitas objetivo: AEI y AFX. En la segunda parte, la investigación se centra en el diseño de nuevas zeolitas de poro medio. Se han seleccionado tres zeolitas hipotéticas de una base de datos de 933611 estructuras. Esta selección se ha realizado utilizando descriptores específicamente diseñados en base a la aplicabilidad de estas zeolitas en procesos DeNOx zeolitas. A continuación se han buscado los agentes directores de estructura (ADE) más apropiados, con la ayuda de métodos computacionales, algunos de los cuales se han sintetizado posteriormente. El uso de dichos ADE en el gel de síntesis ha permitido la obtención de una zeolita cuya topología (ERI) ha sido identificada mediante análisis por PXRD, y cuya morfología y tamaño de cristal (particularmente pequeño) la hacen muy adecuada para su uso como catalizador en algunos procesos. El trabajo de síntesis también reveló la aparición de una nueva zeolita de alta densidad, llamada 'paracelsio-K'. Este nuevo material se ha obtenido al explorar el espacio de fases que cristalizan al utilizar 1-methyl-DABCO como ADE. La síntesis de esta zeolita tiene un especial interés porque el ADE no se incorpora en los canales de la zeolita, pero más bien influyendo en la nucleación y cristalización. La caracterización reveló que la composición del material es próxima al mineral microcline, estructuralmente cercano al paracelsio, ambos feldespatos. A diferencia de los feldespatos el paracelsio-K contiene moléculas de agua en su interior (1 molécula por cavidad) y puede describirse como el material más simple de la familia de las zeolitas que contiene cadenas del tipo 'doble-cigüeñal'. Utilizando los elementos topológicos correspondientes a esta estructura es posible generar estructuras zeolíticas ya conocidas, como GIS, APC, MER, PHI, SIV y algunas otras zeolitas hipotéticas. / [CA] El Projecte d'investigació aquí descrit s'estructura en dos parts. La primera part se centra en la investigació fonamental amb l'objectiu de crear un protocol per a la síntesis de zeolites. La segona part es refereix al disseny, síntesis i caracterització de noves zeolites, particularment útils per a aplicacions DeNOx , però també podria ser útil per a aplicacions MTO. La investigació fonamental suggereix un nou model de preparació de zeolites utilitzant altres zeolites com a llavor. Aquest procés s'anomena transformació zeolita-zeolita o també conversió interzeolita. L'alt rendiment obtingut, la ràpida cristal·lització i la millor utilització i rendiment dels materials de partida s'han tingut en compte per millorar el procés en base a un projecte de doctorat finançat per una empresa. Aquest mètode s'ha il·lustrat utilitzant diverses zeolites com a llavor, entre altres FAU i CHA, per a la preparació de les dues zeolites objectiu: AEI i AFX. A la segona part, la investigació se centra en el disseny de noves zeolites de porus mitjà. S'han seleccionat tres zeolites hipotètiques d'una base de dades de 933.611 estructures. Aquesta selecció s'ha realitzat utilitzant descriptors específicament dissenyats sobre la base de l'aplicabilitat d'aquestes zeolites en processos DeNOx zeolites. A continuació s'han buscat els agents directors d'estructura (ADE) més apropiats, amb l'ajuda de mètodes computacionals, alguns dels quals s'han sintetitzat posteriorment. L'ús d'aquests ADE al gel de síntesi ha permès l'obtenció d'una zeolita la topologia (ERI) ha estat identificada mitjançant anàlisi per PXRD, i la morfologia i mida de vidre (particularment petit) la fan molt adequada per al seu ús com a catalitzador en alguns processos. El treball de síntesi també va revelar l'aparició d'una nova zeolita d'alta densitat, anomenada 'paracelsio-K'. Aquest nou material s'ha obtingut a explorar l'espai de fases que cristal·litzen en utilitzar 1-methyl-DABCO com ADE. La síntesi d'aquesta zeolita té un especial interès perquè el ADE no s'incorpora en els canals de la zeolita, però més aviat influint en la nucleació i cristal·lització. La caracterització va revelar que la composició del material és propera al mineral microcline, estructuralment proper al paracelsio, tots dos feldspats. A diferència dels feldspats el paracelsio-K conté molècules d'aigua al seu interior (1 molècula per cavitat) i pot descriure com el material més simple de la família de les zeolites que conté cadenes del tipus 'doble-cigonyal'. Utilitzant els elements topològics corresponents a aquesta estructura és possible generar estructures zeolítiques ja conegudes, com GIS, APC, MER, PHI, SIV i algunes altres zeolites hipotètiques. / [EN] The research project described herein is structured in two parts. The first part is focused on the fundamental research with the aim of creating a toolbox for zeolite preparation. The second part deal with the design, synthesis and characterization of novel zeolites particular useful for DeNOx applications, but could be also useful for MTO applications. The fundamental research is addressing a novel approach of preparing zeolites by using other zeolites as raw materials. This process is known as zeolite-to-zeolite transformation or interzeolite conversion. The high yield obtained, fast crystallization time and the better utilization of the raw materials (e.g. parent zeolite, organic structure directing agent (OSDA)), are important benefits of interzeolite conversion technic, which answer the objectives formulated for an industrial PhD project. The method has been exemplified by using various raw materials as parent zeolites, such as FAU and CHA for the preparation of two target small pore zeolites AEI and AFX. In the second part the focus has been on the design of novel small pore zeolites. Three hypothetical frameworks have been selected by narrowing down a database containing 933611 structures. The selection has been performed by using the general descriptors for the state-of-the-art DeNOx zeolites (e.g. CHA). This was followed by finding suitable OSDAs for the selected frameworks, by using computational methods. The usage of the theoretically predicted OSDAs in synthesis gels made possible the synthesis of a novel high-silica zeolite. PXRD analysis, revealed that the zeolite has the ERI framework topology. The obtained material has a distinct particle morphology and smaller crystallites, which are key parameters for various catalytic processes. The synthesis work revealed also a novel dense zeolite, named K-paracelsian. The new material has been obtained while exploring the phase space using 1-methyl-DABCO as OSDA. The synthesis of this zeolite is especially interesting in the sense that the OSDA is not being incorporated into the zeolite channels, but rather influencing the nucleation and crystallization. Further characterization revealed a material compositionally closely related to the mineral microcline and structurally closely related to the mineral paracelsian, both of which are feldspars. In contrast to the feldspars, K-paracelsian contains intrazeolitic water corresponding to one molecule per cage and can be described as the simplest endmember of a family of dense double-crankshaft zeolite topologies. By applying the identified building principle, a number of known zeolite frameworks (e.g. GIS, APC, MER, PHI, SIV) and hypothetical zeolite topologies can be constructed. / The authors thank Haldor Topsoe A/S and Innovation Fund Denmark for financial support under the Industrial PhD programme (Case no. 1355-0174B). We thank MINECO of Spain for funding (SEV-2016- 0683 and RTI2018-101033-B-100) and ASIC-UPV for the use of computational facilities. We also thank Prof. M. M. J. Treacy for assistance with the Database of Prospective Zeolite Structures. / Boruntea, C. (2020). Design, synthesis and characterization of small-pore zeolites for industrial environmental applications [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/141094 / TESIS / Compendio

Les propriétés des matériaux moléculaires proviennent à la fois de la structure des composantes individuelles et de la façon dont elles s’associent. Ce dernier aspect reste difficile à contrôler, malgré de grandes avancées en science des matériaux. Pour mieux comprendre la relation structure-propriétés, nous avons entrepris une étude systématique de l'hexaphénylbenzène et de ses dérivés, qui offrent une charpente symétrique et rigide. En premier lieu, nous avons attaché six groupements diaminotriazinyles sur l’hexaphénylbenzène afin de produire des réseaux tridimensionnels hautement poreux maintenus par des ponts hydrogène. En modifiant systématiquement le coeur moléculaire, nous avons excisé près du tiers de la molécule-mère, générant des réseaux supramoléculaires dont la porosité s’est élevée graduellement jusqu’à 75%, équivalant ainsi le record pour ce type de matériaux. Ensuite, nous avons étudié le comportement de l’hexakis(4-nitrophényl)benzène. Dans les structures cristallines obtenues, des interactions non-covalentes entre groupements nitro démontrent leur potentiel en chimie supramoléculaire. Le coeur moléculaire ne joue qu’un rôle secondaire dans l’empilement des molécules : seules quelques interactions C-H•••π impliquant le cycle aromatique central de l’hexaphénylbenzène sont évidentes. Cette dernière observation nous a poussés à étudier le comportement à l’état cristallin de l’hexaphénylbenzène et ses dérivés. En scrutant attentivement neuf structures cristallines de ces composés, nous avons décerné la présence récurrente d’interactions C-H•••π impliquant le cycle aromatique central. Cette association caractéristique a été exploitée pour créer des réseaux supramoléculaires maintenus par des interactions C-H•••π sélectives entre un groupement éthynyle et le cycle aromatique central de l’hexaphénylbenzène. Finalement, nous avons joint le côté sombre de l’ingénierie cristalline en utilisant nos connaissances dans le but d’empêcher la formation d’interactions directionnelles. En protégeant le cycle aromatique central de l’hexaphénylbenzène à l’aide de groupements alkyles, les interactions C-H•••π ont été pratiquement éliminées. Ces résultats offrent la possibilité de créer de nouveaux matériaux amorphes. Dans ces études, focalisées sur le système hexaphénylbenzène, nous avons mis en relief des phénomènes qui sont obscurcis dans d'autres familles de molécules. De plus, ce système a grandement facilité l’utilisation d’une approche méthodique pour explorer la relation structure-propriétés. Nos travaux nous ont amenés à des conclusions de valeur universelle en science des matériaux moléculaires. / The properties of molecular materials depend on the identity of individual components and on their organization. Unfortunately, it remains difficult to control molecular organization, despite advances in materials science. To better understand the relationship between molecular structure and collective properties, we undertook a systematic study of hexaphenylbenzene and its derivatives, which possess a rigid symmetric framework. Our first study focused on using hydrogen bonds to control self-assembly in the solid state. By installing six diaminotriazinyl groups on a hexaphenylbenzene core, we predictably obtained highly porous three-dimensional hydrogen-bonded networks. Through systematic structural modifications of the molecular core, we excised nearly a third of the parent molecule, and the porosity of the networks gradually increased, matching the record of 75% previously obtained for this type of material. We then turned to weaker interactions to control organization, as revealed by the packing of hexakis(4-nitrophenyl)benzene. In the crystal structures analyzed, non-covalent interactions between nitro groups were observed, demonstrating their potential in supramolecular chemistry. Careful examination of the structures showed that the hexaphenylbenzene moieties play only a secondary role in determining the overall packing; however, C-H•••π interactions involving the central aromatic ring of hexaphenylbenzene were also observed. To further document this unexpected behavior, we analyzed nine crystal structures of hexaphenylbenzene and derivatives, which showed that a C-H•••π recognition pattern involving the central aromatic ring occurs consistently throughout the series. This motif was used to prepare supramolecular networks based exclusively on selective and directional C-H•••π interactions involving ethynyl groups and the central aromatic ring of hexaphenylbenzene. Finally, we joined the dark side of crystal engineering by using our knowledge of supramolecular chemistry to prevent the formation of directional interactions. By installing alkyl groups near the central aromatic ring of hexaphenylbenzene, C-H•••π interactions were practically eliminated. These results were then used to devise new amorphous materials. The hexaphenylbenzene system permitted a methodical analysis of structure-property relationships in molecular materials. This particular system exposed phenomena normally obscured in other families of molecules, and our analysis of its behavior has yielded conclusions of universal value in materials science.

Combination of the compact but sterically flexible ferrocene scaffold with intermolecular binding potential and conformational variability of (2-hydroxyethyl)ammonium structural motif was utilised in the construction of solid crystalline materials. Crystallisation in systems containing ferrocenecarboxylic, 2-ferrocenylacetic, 3-ferrocenylpropionic, 3-ferrocenyl- acrylic, 3-ferrocenylacrylic, 3-ferrocenylpropiolic, ferrocene-1,1'-dicarboxylic or ferrocene- sulfonic acid with 2-aminoethanol afforded crystals of the corresponding salts. The resulting crystalline products were characterised with the usual methods (proton nuclear magnetic resonance, infrared spectroscopy, elemental analysis) and their crystal structures were determined by means of single-crystal X-ray diffraction analysis. The crystal structures of the salts mentioned above usually contain rather complicated two dimensional networks of charge-assisted hydrogen bonds. With the aim of studying potentially more simple hydrogen-bonded structures, additional crystallisation experiments were conducted in systems of ferrocenecarboxylic acid and 2-(methylamino)ethanol or 2-(dimethylamino)ethanol. These experiments yielded simple salt of the former amine and adducts of salts of both bases with ferrocenecarboxylic acid in the ratio of 1:1. The...

Les propriétés des matériaux moléculaires proviennent à la fois de la structure des composantes individuelles et de la façon dont elles s’associent. Ce dernier aspect reste difficile à contrôler, malgré de grandes avancées en science des matériaux. Pour mieux comprendre la relation structure-propriétés, nous avons entrepris une étude systématique de l'hexaphénylbenzène et de ses dérivés, qui offrent une charpente symétrique et rigide. En premier lieu, nous avons attaché six groupements diaminotriazinyles sur l’hexaphénylbenzène afin de produire des réseaux tridimensionnels hautement poreux maintenus par des ponts hydrogène. En modifiant systématiquement le coeur moléculaire, nous avons excisé près du tiers de la molécule-mère, générant des réseaux supramoléculaires dont la porosité s’est élevée graduellement jusqu’à 75%, équivalant ainsi le record pour ce type de matériaux. Ensuite, nous avons étudié le comportement de l’hexakis(4-nitrophényl)benzène. Dans les structures cristallines obtenues, des interactions non-covalentes entre groupements nitro démontrent leur potentiel en chimie supramoléculaire. Le coeur moléculaire ne joue qu’un rôle secondaire dans l’empilement des molécules : seules quelques interactions C-H•••π impliquant le cycle aromatique central de l’hexaphénylbenzène sont évidentes. Cette dernière observation nous a poussés à étudier le comportement à l’état cristallin de l’hexaphénylbenzène et ses dérivés. En scrutant attentivement neuf structures cristallines de ces composés, nous avons décerné la présence récurrente d’interactions C-H•••π impliquant le cycle aromatique central. Cette association caractéristique a été exploitée pour créer des réseaux supramoléculaires maintenus par des interactions C-H•••π sélectives entre un groupement éthynyle et le cycle aromatique central de l’hexaphénylbenzène. Finalement, nous avons joint le côté sombre de l’ingénierie cristalline en utilisant nos connaissances dans le but d’empêcher la formation d’interactions directionnelles. En protégeant le cycle aromatique central de l’hexaphénylbenzène à l’aide de groupements alkyles, les interactions C-H•••π ont été pratiquement éliminées. Ces résultats offrent la possibilité de créer de nouveaux matériaux amorphes. Dans ces études, focalisées sur le système hexaphénylbenzène, nous avons mis en relief des phénomènes qui sont obscurcis dans d'autres familles de molécules. De plus, ce système a grandement facilité l’utilisation d’une approche méthodique pour explorer la relation structure-propriétés. Nos travaux nous ont amenés à des conclusions de valeur universelle en science des matériaux moléculaires. / The properties of molecular materials depend on the identity of individual components and on their organization. Unfortunately, it remains difficult to control molecular organization, despite advances in materials science. To better understand the relationship between molecular structure and collective properties, we undertook a systematic study of hexaphenylbenzene and its derivatives, which possess a rigid symmetric framework. Our first study focused on using hydrogen bonds to control self-assembly in the solid state. By installing six diaminotriazinyl groups on a hexaphenylbenzene core, we predictably obtained highly porous three-dimensional hydrogen-bonded networks. Through systematic structural modifications of the molecular core, we excised nearly a third of the parent molecule, and the porosity of the networks gradually increased, matching the record of 75% previously obtained for this type of material. We then turned to weaker interactions to control organization, as revealed by the packing of hexakis(4-nitrophenyl)benzene. In the crystal structures analyzed, non-covalent interactions between nitro groups were observed, demonstrating their potential in supramolecular chemistry. Careful examination of the structures showed that the hexaphenylbenzene moieties play only a secondary role in determining the overall packing; however, C-H•••π interactions involving the central aromatic ring of hexaphenylbenzene were also observed. To further document this unexpected behavior, we analyzed nine crystal structures of hexaphenylbenzene and derivatives, which showed that a C-H•••π recognition pattern involving the central aromatic ring occurs consistently throughout the series. This motif was used to prepare supramolecular networks based exclusively on selective and directional C-H•••π interactions involving ethynyl groups and the central aromatic ring of hexaphenylbenzene. Finally, we joined the dark side of crystal engineering by using our knowledge of supramolecular chemistry to prevent the formation of directional interactions. By installing alkyl groups near the central aromatic ring of hexaphenylbenzene, C-H•••π interactions were practically eliminated. These results were then used to devise new amorphous materials. The hexaphenylbenzene system permitted a methodical analysis of structure-property relationships in molecular materials. This particular system exposed phenomena normally obscured in other families of molecules, and our analysis of its behavior has yielded conclusions of universal value in materials science.

La conception et la préparation de réseaux moléculaires organiques et hybrides à l’état cristallin ont été envisagées par un processus itératif d’auto-assemblage entre des briques de construction moléculaires préprogrammées et complémentaires appelées tectons. Cette approche est basée sur la reconnaissance moléculaire de modules dicationiques, donneurs de liaisons hydrogène, et d’unités anioniques, accepteurs de liaisons hydrogène. Ainsi, la combinaison des tectons moléculaires de la famille des bis-benzimidazoliums, intrinsèquement luminescents, avec des anions polycyanométallates conduit à la formation de réseaux moléculaires hybrides luminescents à l’état cristallin. Il a été procédé à l'étude des propriétés photophysiques de ces réseaux à l'état solide. De même, l’association de bis-amidiniums,briques dicationiques, à des anions de type azodibenzoates mène à des assemblages cristallins possédant la propriété de photo-commutation, c’est-à-dire conduisant à une isomérisation sous stimulus lumineux. / The design and synthesis of organic and hybrid molecular networks in the crystalline state has been investigated using iterative self-assembly processes involving preprogrammed complementary molecular building blocks called tectons. This approach is based on molecular recognition events between dicationic hydrogen bond donors and anionic hydrogen bond acceptors tectons. Thus, the combination of intrinsically luminescent molecular tectons belonging to the family of cationic bis-benzimidazoliums with polycyanometallates anions leads to the formation of luminescent hybrid molecular networks in the crystalline state. Their optical properties have been studied in the solid state. Similarly, the association of bis-amidiniums, dicationic bricks, to azodibenzoates type anions leads to crystalline assemblies presenting photo-switching property, i.e. the ability to isomerise under light stimulus.