Auswahl der wissenschaftlichen Literatur zum Thema „Naphtalène diimides“

G-quadruplexes are four-stranded nucleic acids structures that can form in guanine-rich sequences. Following the observation that G-quadruplexes are particularly abundant in genomic regions related to cancer, such as telomeres and oncogenes promoters, several G-quadruplex-binding molecules have been developed for therapeutic purposes. Among them, naphthalene diimide derivatives have reported versatility, consistent selectivity and high affinity toward the G-quadruplex structures. In this review, we present the chemical features, synthesis and peculiar optoelectronic properties (absorption, emission, redox) that make naphtalene diimides so versatile for biomedical applications. We present the latest developments on naphthalene diimides as G-quadruplex ligands, focusing on their ability to bind G-quadruplexes at telomeres and oncogene promoters with consequent anticancer activity. Their different binding modes (reversible versus irreversible/covalent) towards G-quadruplexes and their additional use as antimicrobial agents are also presented and discussed.

Electrochromism of organic compounds is a well-known phenomenon; however, nowadays, most research is focused on anodic coloring materials. Development of efficient, cathodic electrochromic materials is challenging due to the worse stability of electron accepting materials compared with electron donating ones. Nevertheless, designing stable cathodic coloring organic materials is highly desired—among other reasons—to increase the coloration performance. Hence, four phthalimide derivatives named 1,5-PhDI, 1,4-PhDI, 2,6-PhDI and 3,3′-PhDI were synthesized and analyzed in depth. In all cases, two imide groups were connected via naphthalene (1,5-PhDI, 1,4-PhDI, 2,6-PhDI) or 3,3′-dimethylnaphtidin (3,3′-PhDI) bridge. To observe the effect of chemical structure on physicochemical properties, various positions of imide bond were considered, namely, 1,5- 1,4- and 2,6-. Additionally, a compound with the pyromellitic diimide unit capped with two 1-naphtalene substituents was obtained. All compounds were studied in terms of their thermal behavior, using differential calorimetry (DSC) and thermogravimetric analysis (TGA). Moreover, electrochemical (CV, DPV) and spectroelectrochemical (UV–Vis and EPR) analyses were performed to evaluate the obtained materials in terms of their application as cathodic electrochromic materials. All obtained materials undergo reversible electrochemical reduction which leads to changes in their optical properties. In the case of imide derivatives, absorption bands related to both reduced and neutral forms are located in the UV region. However, importantly, the introduction of the 3,3′-dimethylnaphtidine bridge leads to a noticeable bathochromic shift of the reduced form absorption band of 3,3′-PhDI. This indicates that optimization of the phthalimide structure allows us to obtain stable, cathodic electrochromic materials.

Fast and sensitive quantification of drugs as emerging pollutants in water bodies is a pressing need in contemporary society, to prevent serious environmental concerns that could negatively impact on human health. This explains the surge of interest in this field, and the need to identify highly selective sensing systems. Addressing this issue, in this work we synthesized two D‐glucamine functionalized fluorophores bearing self‐assembling cores, as 1,8‐naphthalimide and naphthalene diimide. We studied their self‐assembly in water solution, and characterized the aggregated formed by determining their stability constant, their morphology and size by scanning electron microscopy, resonance light scattering and dynamic light scattering, as well their solid‐state emission ability. Then, we studied their sensing ability, in water, towards pharmaceutically active compounds such as ciprofloxacin, nalidixic acid, carbamazepine and diclofenac sodium salt, by fluorescence investigation. Data collected show that the self‐assembling ability is significantly affected by the fluorophore structure, which in turn also determines sensing ability. In particular, the naphtalene diimide‐based probe was the most sensitive, with LOD as low as 0.01 mM in the presence of nalidixic acid, which is in line and competitive with more complex sensing systems, recently reported in the literature.

L'objectif de cette thèse était de développer des matériaux stimulables basés sur des molécules électro- et/ou photoactives. Au cours de ce projet, nous avons synthétisé et caractérisé trois molécules π-conjuguées différentes : un silsesquioxane ponté par une unité naphtalène-diimide (NDI-PS), un silsesquioxane ponté par une unité 4,4’-bipyridinium(VG-PS) et un naphtalène-diimide cationique (DaO). Des matériaux hybrides organiques/inorganiques ont été obtenus par polycondensation de trialkoxysilanes pontés avec des groupes organiques incorporant des ponts de type naphtalène-diimide(NDI-PS) et viologène (VG-PS). Les gels de polysilsesquioxane à ponts organiques présentent des caractéristiques intéressantes pour plusieurs applications, notamment des propriétés photo-/électrochromiques. Pour comprendre leurs propriétés et leur relation avec la structure du réseau tridimensionnel au sein des gels, nous avons exploré différentes voies de synthèse orthogonales, étudiant leur influence sur l'organisation des motifs organiques au sein du réseau. De plus, nous avons étudié le comportement de dérivés discrets à base de NDI en réponse à une irradiation lumineuse et démontré l'existence de phénomènes d'agrégation et/ou de réduction en fonction du dérivé NDI et des conditions expérimentales. La molécule à base de viologène (VG-PS) a été utilisée pour préparer des films électro-chromes par électrodéposition. En outre, nous avons démontré que ces films polycationiques peuvent être utilisés pour incorporer des d'espèces d'intérêt catalytique par simple échange d’ions
The objective of this thesis was to develop multi-responsive materials based on electro- and/or photoactive molecules. During this project, we synthesized and characterized three different π-conjugated molecules: naphthalene diimide-bridged silsesquioxane (NDI-PS), viologen-bridged silsesquioxane (VG-PS), and cationic naphthalene diimide (DaO). Organic/inorganic hybrid materials were obtained by polycondensation of organo-bridged trialkoxysilanes incorporating naphthalene diimide bridges (NDI-PS) and viologen bridges (VG-PS). The organo-bridged polysilsesquioxane gels exhibit interesting characteristics for numerous applications, particularly in photo-/electrochromic properties due to the presence of electroactive centers. To understand their properties and their relation to the structure of the 3D network, we explored different orthogonal synthetic routes to these gels, studying their influence on the organization of organic motifs within the network. Additionally, we investigated the photoinduced processes of discrete NDI-based derivatives, which were found to be associated with aggregation and/or radical generation depending on the NDI-based derivative and experimental conditions. VG-PS was utilized to prepare electrochromic films via electrodeposition. Furthermore, we demonstrated the incorporation of guest species of catalytic interest, such as iron(III) tetrasulfonate porphyrins, within these films
O objetivo desta tese foi desenvolver materiais multirresponsivos baseados em moléculas eletro- e/ou fotoativas. Durante este projeto, sintetizamos e caracterizamos três moléculas π-conjugadas diferentes: silsesquioxano ponteado por naftaleno-diimida (NDI-PS), silsesquioxano ponteado por viologênio (VG-PS) e naftaleno-diimida catiônica (DaO). Materiais híbridos orgânicos/inorgânicos foram obtidos por policondensação de silanos trialcoolados ponteados por grupos orgânicos incorporando pontes de naftaleno-diimida (NDI-PS) e pontes de viologênio (VG-PS). Estes géis de polisilsesquioxano com pontes orgânicas apresentam características interessantes para diversas aplicações, especialmente em propriedades foto-/eletrocrômicas devido à presença de centros foto- e eletroativos. Para entender suas propriedades e sua relação com a estrutura da rede tridimensional, exploramos diferentes rotas sintéticas ortogonais para os géis, estudando sua influência na organização de motivos orgânicos dentro da rede. Além disso, investigamos os processos fotoinduzidos de derivados discretos baseados em NDI, que foram associados à agregação e/ou geração de radicais, dependendo do derivado de NDI e das condições experimentais. O VG-PS foi utilizado para preparar filmes eletrocrômicos por eletrodeposição. Além disso, demonstramos a incorporação de espécies de hóspedes de interesse catalítico, como porfirinas de ferro(III) tetrasulfonadas, dentro desses filmes

Les travaux décris dans cette thèse rapportent la conception de Metal-Organic Frameworks (MOFs) photoactifs et leur immobilisation sur surface dans le but d’obtenir et d’étudier des SurMOFs (Surface anchored Metal-Organic Frameworks) propices aux processus photoinduits dans le cadre de la photosynthèse artificielle. Pour accomplir cela, nous avons synthétisé différents ligands photoactifs et réalisé leur immobilisation sur surface à l’aide de la croissance épitaxiale en phase liquide. Ainsi, différents SurMOFs à base de zinc(II), présentant tous une structure de type SurMOF-2, ont été préparés avec succès. Les premiers matériaux obtenus à base de ligands rylènes (naphtalène dimide : NDI et pérylène diimide : PDI) ont mis en avant de fortes interactions  entre les chromophores au sein du SURMOF, causant une perte de la luminescence. Une deuxième génération de ligands plus encombrés a été synthétisée. Ils ont conduit à des SurMOFs luminescents et siège de transferts d’énergie interligands. Ces premiers travaux ont mis en avant l’impact de la disposition des ligands dans le matériau sur les propriétés photoniques. Par ailleurs, des SurMOFs constitués de ligands dicétopyrrolopyrrole (DPP) et d’anthracène (ADP) ont été synthétisés. L’étude de leurs propriétés photoniques alliée à des calculs théoriques ont montré que le transfert d’énergie au sein de ce SurMOF ne se fait pas de manière isotrope. Enfin, un SurMOF à partir de ligand DPP portant des fonctions réactives (azoture) a été synthétisé et nous avons pu greffer différentes molécules par réaction de cyclo-addition de type Huisgen, dont un accepteur d’électron, à sa périphérie par modification post-synthétique
The aim of this thesis was the development of photoactive Metal-Organic Frameworks (MOFs) and their immobilizations on surface to obtain and study SurMOFs (Surface anchored Metal-Organic Frameworks) to investigate photoinduced processes in the context of the artificial photosynthesis. Towards this goal, we have synthesized photoactive ligands and immobilized them on surfaces using liquid phase epitaxy (LPE) in a layer-by-layer (LbL) fashion. Thus, different zinc (II) based SurMOFs, featuring a SurMOF-2 structure, were successfully prepared. The first rylene- (naphthalene diimide: NDI and perylene diimide: PDI) based SurMOFs described in this thesis showed strong  interactions between the chromophores within the MOF, causing the quenching of the luminescence. A second generation of ligands, sterically hindered, was then synthesized. They lead to luminescent SurMOFs showing efficient ligand-to-ligand energy transfer. These first results highlight the impact of linker arrangement within the material on its photonic properties. Furthermore, diketopyrrolopyrrole (DPP) and anthracene (DPA) based SurMOFs were prepared. The study of their photonic properties coupled with theoretical calculations showed that energy transfers, occurring within SurMOF-2 type materials, were not isotropic. Finally, a SurMOF, made out of a DPP ligand bearing reactive moieties (azide), was synthesized and was functionalized with different kinds of molecules, including an electron acceptor, at the periphery by post-synthetic modification using the Huisgen cycloaddtion reaction