Advanced Luminescent Materials for Technological Applications

This thesis focusses on the study of several luminescent materials and investigates some related technological applications. It is made of six chapters. Chapter 1 introduces a brief history, basic principles and applications of photoluminescence. Chapter 2 presents the photophysical properties of five benzoheterodiazole dyes. These molecules were incorporated in PMMA- and PDMS-based LSC-PV devices to determine the emission quantum yields, transmission, re-absorption and IPCE properties. DFT calculations were performed to investigate the structures and energy levels of these dyes. Chapter 3 concerns the preparation of a luminescent film to calibrate an ESA satellite that will monitor the fluorescence of terrestrial vegetation. ZnPc was selected as suitable dye to make the film. Ferrocene was selected as quencher to control the emission intensity. An industrial printing technology was used to produce large-area calibration sheets coated with green pigment that simulates the NIR reflectance of green plants in which the ZnPc is embedded. Photophysical properties of a series of alkynyl gold NHC complexes containing naphthalimide chromophore were studied in Chapter 4. All the compounds were studied in solution and solid state. Further investigations were carried out by incorporating these compounds in PMMA matrix to make films. XRD and DFT calculations were made to determine the structures and energy levels of the complexes. In chapter 5 we studied the photophysical properties of star-shaped molecular systems which can operate as molecular motors when attached onto surface, along with those of their related ligands/moieties in tetrahydrofuran solution. The photophysical properties of these molecular systems can show if they are suitable to operate as light-triggered molecular machines. Finally, chapter 6 concerns the photoluminescence behavior of three NHC half-sandwich Ir/Rh metal complexes. The photophysical properties of these compounds were examined in CH2Cl2 solutions and PMMA films. These complexes may prove potential candidates for organic phosphorescent materials.

Towards a sustainable approach for Cultural Heritage Conservation: developing micro-structured green materials and analytical protocols for their performance assessment

Cleaning is one of the most important and delicate procedures that are part of the restoration process. When developing new systems, it is fundamental to consider its selectivity towards the layer to-be-removed, non-invasiveness towards the one to-be-preserved, its sustainability and non-toxicity. Besides assessing its efficacy, it is important to understand its mechanism by analytical protocols that strike a balance between cost, practicality, and reliable interpretation of results. In this thesis, the development of cleaning systems based on the coupling of electrospun fabrics (ES) and greener organic solvents is proposed. Electrospinning is a versatile technique that allows the production of micro/nanostructured non-woven mats, which have already been used as absorbents in various scientific fields, but to date, not in the restoration field. The systems produced proved to be effective for the removal of dammar varnish from paintings, where the ES not only act as solvent-binding agents but also as adsorbents towards the partially solubilised varnish due to capillary rise, thus enabling a one-step procedure. They have also been successfully applied for the removal of spray varnish from marble substrates and wall paintings. Due to the materials' complexity, the procedure had to be adapted case-by-case and mechanical action was still necessary. According to the spinning solution, three types of ES mats have been produced: polyamide 6,6, pullulan and pullulan with melanin nanoparticles. The latter, under irradiation, allows for a localised temperature increase accelerating and facilitating the removal of less soluble layers (e.g. reticulated alkyd-based paints). All the systems produced, and the mock-ups used were extensively characterised using multi-analytical protocols. Finally, a monitoring protocol and image treatment based on photoluminescence macro-imaging is proposed. This set-up allowed the study of the removal mechanism of dammar varnish and semi-quantify its residues. These initial results form the basis for optimising the acquisition set-up and data processing.