Search

Shape, and particularly, curvature is a powerful and underexplored tool in chemical systems that will be exploited in this Thesis through different projects. To this aim, this Thesis is structured in 4 different Chapters that revolve around the same core structure: a saddle-shaped nitrogen containing macrocycle that we have termed carpyridine as a result of its constituents: carbazole and pyridine. Chapter 1 shows the influence that the saddle shape has on the self-assembling capabilities of this macrocycle when substituted with alkyl chains on the carbazoles. The restriction of the translational and rotational movements within a stack of carpyridines has resulted in two-dimensional supramolecular polymers in the form of sheets with micrometer lengths and molecular thicknesses in the absence of strong directional interactions. The elucidation of the composition of these nanosheets resulted in loosely packed columns driven by pi–pi interactions between monomers that associate laterally through Van der Waals interactions to form the two-dimensional surface. We term this process Shape-Assisted Self-Assembly. Chapter 2 contains the findings from further alkyl substitution on the para positions of the pyridines as a follow-up to Chapter 1. This results in tighter column formation and avoidance of lateral association between columns. A one-dimensional supramolecular polymer is then obtained, allowing for characterization of this new assembly both on surface and in solution. The self-assembly mechanism has been elucidated with different spectroscopic techniques, resulting in thermodynamic parameters comparable to those obtained from hydrogen-bonded systems. Chapter 3 entails the efforts in substituting one of the para positions of the pyridines with a hydrophilic sidechain, namely a triethyleneglycol. This affords an amphiphilic compound for which the self-assembly behavior can be studied in aqueous mixtures. Different morphologies like micelles or vesicles can be formed b

Two-dimensional (2D) materials are a key target for many applications in the modern day. Self-assembly is one approach that can bring us closer to this goal, which usually relies upon strong, directional interactions instead of covalent bonds. Control over less directional forces is more challenging and usually does not result in as well-defined materials. Explicitly incorporating topography into the design as a guiding effect to enhance the interacting forces can help to form highly ordered structures. Herein, we show the process of shape-assisted self-assembly to be consistent across a range of derivatives that highlights the restriction of rotational motion and is verified using a diverse combination of solid state analyses. A molecular curvature governed angle distribution nurtures monomers into loose columns that then arrange to form 2D structures with long-range order observed in both crystalline and soft materials. These features strengthen the idea that shape becomes an important design principle leading towards precise molecular self-assembly and the inception of new materials.

Bottom-up approaches are one strategy geared towards designing novel two-dimensional materials. Supramolecular polymerization has proven to be an effective way of obtaining these architectures due to the increasing control and tunability offered by different functional groups, which are not afforded by conventional polymerization. In this short review, we highlight examples of supramolecular assemblies held together by well-known non-covalent interactions, as well as new approaches that are becoming more relevant in recent years.

Self-assembly and molecular recognition are critical processes both in life and material sciences. They usually depend on strong, directional non-covalent interactions to gain specificity and to make long-range organization possible. Most supramolecular constructs are also at least partially governed by topography, whose role is hard to disentangle. This makes it nearly impossible to discern the potential of shape and motion in the creation of complexity. Here, we demonstrate that long-range order in supramolecular constructs can be assisted by the topography of the individual units even in the absence of highly directional interactions. Molecular units of remarkable simplicity self-assemble in solution to give single-molecule thin two-dimensional supramolecular polymers of defined boundaries. This dramatic example spotlights the critical function that topography can have in molecular assembly and paves the path to rationally designed systems of increasing sophistication.

[ES] Ego se cimienta en la exploración del ser a través de la simbología del ombligo, para muchos cicatriz del origen de desconexión vital y la creación de un nuevo individuo independiente. Este vestigio corporal nos permite retornan al origen/ónfalo del yo en búsqueda de respuestas que tienen que ver con quiénes somos y dónde se encuentra nuestra esencia. Este proyecto, pues, no es sino un proceso de búsqueda de identidad por medio del lenguaje de la joyería, nuestro propio cuerpo y arquetipos universales., [EN] Ego is based on the exploration of being through navel symbology, which is sometimes seen as the scar of the origin of vital disconnection and the creation of a new independent human. This corporal trace allows us to go back to the origin/omphalos of the self, in order to find answers that have to do with who we are and where our essence is. To sum up, this project is an identity quest through jewellery, our own body and universal archetypes.

[ES] Ego se cimienta en la exploración del ser a través de la simbología del ombligo, para muchos cicatriz del origen de desconexión vital y la creación de un nuevo individuo independiente. Este vestigio corporal nos permite retornan al origen/ónfalo del yo en búsqueda de respuestas que tienen que ver con quiénes somos y dónde se encuentra nuestra esencia. Este proyecto, pues, no es sino un proceso de búsqueda de identidad por medio del lenguaje de la joyería, nuestro propio cuerpo y arquetipos universales., [EN] Ego is based on the exploration of being through navel symbology, which is sometimes seen as the scar of the origin of vital disconnection and the creation of a new independent human. This corporal trace allows us to go back to the origin/omphalos of the self, in order to find answers that have to do with who we are and where our essence is. To sum up, this project is an identity quest through jewellery, our own body and universal archetypes.

[ES] Ego se cimienta en la exploración del ser a través de la simbología del ombligo, para muchos cicatriz del origen de desconexión vital y la creación de un nuevo individuo independiente. Este vestigio corporal nos permite retornan al origen/ónfalo del yo en búsqueda de respuestas que tienen que ver con quiénes somos y dónde se encuentra nuestra esencia. Este proyecto, pues, no es sino un proceso de búsqueda de identidad por medio del lenguaje de la joyería, nuestro propio cuerpo y arquetipos universales., [EN] Ego is based on the exploration of being through navel symbology, which is sometimes seen as the scar of the origin of vital disconnection and the creation of a new independent human. This corporal trace allows us to go back to the origin/omphalos of the self, in order to find answers that have to do with who we are and where our essence is. To sum up, this project is an identity quest through jewellery, our own body and universal archetypes.

[ES] Ego se cimienta en la exploración del ser a través de la simbología del ombligo, para muchos cicatriz del origen de desconexión vital y la creación de un nuevo individuo independiente. Este vestigio corporal nos permite retornan al origen/ónfalo del yo en búsqueda de respuestas que tienen que ver con quiénes somos y dónde se encuentra nuestra esencia. Este proyecto, pues, no es sino un proceso de búsqueda de identidad por medio del lenguaje de la joyería, nuestro propio cuerpo y arquetipos universales., [EN] Ego is based on the exploration of being through navel symbology, which is sometimes seen as the scar of the origin of vital disconnection and the creation of a new independent human. This corporal trace allows us to go back to the origin/omphalos of the self, in order to find answers that have to do with who we are and where our essence is. To sum up, this project is an identity quest through jewellery, our own body and universal archetypes.

The purpose of this study is to create a data logger from ground up. The aim is to provide the device with some flexibility compared to the existing ones. Therefore, firstly an analysis of a real data logger is performed, then the implementation is carried out. In this case, an Arduino is used as a microcontroller, to which some sensors and a SIM808 module are connected. The results showed how the device met the requirements preset. Nevertheless, a conclusion reached was that in future implementations, there is still some work to be done. For instance, the prototype could be improved in terms of the communication channel. In this case, only the temperature sensor was available, for this reason the range was defined by default. Nevertheless, an improvement would be to allow the user to decide the admissible range for each sensor

Data‐driven materials discovery has become increasingly important in identifying materials that exhibit specific, desirable properties from a vast chemical search space. Synergic prediction and experimental validation are needed to accelerate scientific advances related to critical societal applications. A design‐to‐device study that uses high‐throughput screens with algorithmic encodings of structure–property relationships is reported to identify new materials with panchromatic optical absorption, whose photovoltaic device applications are then experimentally verified. The data‐mining methods source 9431 dye candidates, which are auto‐generated from the literature using a custom text‐mining tool. These candidates are sifted via a data‐mining workflow that is tailored to identify optimal combinations of organic dyes that have complementary optical absorption properties such that they can harvest all available sunlight when acting as co‐sensitizers for dye‐sensitized solar cells (DSSCs). Six promising dye combinations are shortlisted for device testing, whereupon one dye combination yields co‐sensitized DSSCs with power conversion efficiencies comparable to those of the high‐performance, organometallic dye, N719. These results demonstrate how data‐driven molecular engineering can accelerate materials discovery for panchromatic photovoltaic or other applications.