Surface supported supramolecular architectures: an experimental and modeling study

The scientific community is nowadays focused on the design and the production of nm/μm-sized systems for their relevance to nanotechnology, energy production and storage, life science and environment. Advances in high performing computing and in synthetic/characterization methods make possible devising novel rational approaches to tailor properties of low-dimensional architectures of molecular networks on inorganic substrates; i.e., to control the electron transport properties of active layers and the reactivity of selected sites. As such, the self-assembly of functional architectures on appropriate surfaces is the most promising bottom-up approach to organize and integrate single molecules on solid substrates. As a consequence of the persistent progress in computational power and multiscale material modeling, new materials are less likely to be discovered by a trial-and-error approach. This points to a paradigm shift in modeling, away from reproducing known properties of known materials and towards simulating the properties of hypothetical composites as a forerunner to get real materials with desired characteristics. The interplay among multiscale material modeling, new synthetic routes and appropriate validation experiments is crucial to design the desired behavior at each length scale. In this PhD thesis we exploited integrated methodologies to provide interpretative tools about structure and functions of organic/inorganic hybrid nanostructured materials made of molecular mono-layers deposited on technological relevant substrates, suitable for applications in strategic areas such as catalysis, artificial photosynthesis, molecular electronics-magnetism and molecular recognition.