Periodic Reporting for period 1 - ENTERPRISE (vEnturing oN heTERodoped Polycyclic aRomatIc hydrocarbonS to develop smart labEls)
Período documentado: 2021-07-01 hasta 2023-06-30
The incorporation of heteroatoms into polycyclic aromatic hydrocarbons (PAHs) is a promising and appealing approach to create hybrid graphenoid structures. These structures, when composed solely of C(sp2) atoms, may present challenges in synthesis using conventional in-solution methods and can be susceptible to chemical instability under ambient conditions. The preparation and study of extended acenes face significant limitations due to their inherent instability and low solubility. However, to overcome these challenges and unlock new possibilities, various synthetic methods and stabilisation strategies have been developed, enabling access to extended PAHs with diverse topologies. In the context of the MSCA action, the experienced researcher (Dr. Beatrice Berionni Berna) joined Prof. Davide Bonifazi's research lab at the University of Vienna, Austria. The primary focus of her work involved incorporating oxygen atoms directly into the acene backbone, starting from different building blocks (peri-xanthenoxanthene, methoxynaphthalene, and tetraarylporphyrins), resulted in pyrano-fused structures with distinct molecular geometries, electronic structures, and material properties, towards the application of the new improved structures in organic electronics, and sensing applications. The co-planarisation of the oxygen lone pair of the fused pyrano moiety with the p electronic system of the PAHs has been proven to enable a more efficient -extension, producing an electron rich set of O-fused structures with an increasing electron donating character compared to the all-carbon congener. During the action, the experienced researcher had received computational training using Vienna Scientific Cluster (VSC).
During the first stage of the project, the host institution facilitated the acquisition of a strong knowledge in the synthesis and properties of heteroatom-embedded polycyclic aromatic hydrocarbons by the experienced researcher. This phase included comprehensive work and training, leading to the synthesis and characterisation of innovative one-dimensional (1D) and two-dimensional (2D) oxygen-embedded structures. These structures underwent thorough investigation both in terms of photophysical properties and as prototypes for electrochromic smart labels, resulting in the achievement of results that were subsequently published in a scientific journal.
Furthermore, the expertise and knowledge gained by the experienced candidate were effectively combined with her strong background in porphyrinoid chemistry, leading to the design and synthesis of a novel set of oxygen-embedded porphyrins. These compounds were successfully synthesised both in solution and on an Ag(111) surface. The latter scenario facilitated the formation of well-defined lattices, as demonstrated by Atomic Force Microscopy (AFM) and Scanning Tunneling Microscopy (STM).
Furthermore, the expertise and knowledge gained by the experienced candidate were effectively combined with her strong background in porphyrinoid chemistry, leading to the design and synthesis of a novel set of oxygen-embedded porphyrins. These compounds were successfully synthesised both in solution and on an Ag(111) surface. The latter scenario facilitated the formation of well-defined lattices, as demonstrated by Atomic Force Microscopy (AFM) and Scanning Tunneling Microscopy (STM).
Results achieve during the action, comprise both computational and experimental studies and exploration of a new set of soluble and air-stable O-embedded PAH-based structures, the study of their HOMO energy level lifting as novel graphenoid to successfully develop a new set of p-type molecular semiconductors. Additionally, extra efforts were centered in expanding a previous preliminary work of Bonifazi group, exploiting the chromogenic properties of PXX-based structures to devise chromogenic materials to engineer electrochromic devices.