Implementing novel metal-free and strongly absorbing donor–acceptorsensitizers without carboxylic acid anchoring groups are still a frontier in dye-sensitized solar cells (DSSCs). Herein, the facile synthesis of a strongly absorbingsensitizer combining three 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) anchoringmoieties with a borazine core instead of the classical cyano anchoring groups,such as tetracyanoquinodimethane (TCNQ) and tetracyanoethylene (TCNE), andthe dimethyl-phenyl amino donor group, is disclosed. This results in a 1.6-foldincrease in solar energy conversion efficiency compared to DSSCs with thereference sensitizers (TCBD-dimethyl-amino-phenyl core) and the prior art cyano-sensitizers with TCNE and TCNG anchors. The advantages of the TCBD-borazinedesign are twofold: 1) threefold increase in absorption extinction coefficient aswell as 2) a reduction in back electron transfer and aggregation behavior upon dyeadsorption onto the semiconducting electrode, resulting in 45% and 23%improvement in open-circuit voltage (V oc) and short-circuit current density (J sc ),respectively, compared to those of the prior art. Overall, this work highlights aneasy-to-design of cyano-sensitizer that results in a significant improvement ofsolar energy conversion when using borazine frameworks for the first time.
The group is led by Professor Davide Bonifazi at the Institute of Organic Chemistry in the University of Vienna.
We do research in synthetic organic chemistry to develop supramolecular architectures that, through the exploitation of their peculiar physical and structural properties, can contribute to the demonstration of key functions or basic concepts at the intersection of physical organic chemistry, materials science and biology.
Cyano‐Borazine Photosensitizers for Dye‐Sensitized Solar Cells
Assessing the energetic and environmental sustainability of organic borazines preparation: A comprehensive life cycle assessment and uncertainty analysis
Since its inception, organic synthesis has played a fundamental role in the development of society, as its efficiency is essential for the preparation of materials in several strategic sectors such as pharmaceuticals, transportation and energy. In this context, organic borazines have emerged as promising molecules useful both as doping units and organic semiconductors, particularly in the production of photovoltaics and organic transistors. However, like most “fine chemical” products, their engineering is generally complex and harmful to the environment due to the need for dangerous reagents, solvents, and harsh reaction conditions. Recent adopted advancements in the manufacturing process, including continuous-flow synthesis and the use of safer, biomass-derived solvents, have been confirmed through a comprehensive cradle-to-gate life cycle assessment (LCA). The study, compared to four batch processes from the literature, identified electricity consumption as the primary contributor to environmental and human health impacts. Additionally, it was demonstrated that adopting a continuous-flow approach, which reduces electricity consumption and leverages safer reaction media such as 2-MeTHF, characterized by an exceptional recovery rate (90%), proved to be an effective strategy, resulting in a notable 11% reduction in emissions. Furthermore, an uncertainty analysis using the Monte Carlo method revealed that energy mixes reliant on fossil fuels increase the impacts across all categories related to human health damage.
Expression of hyperconjugative stereoelectronic interactions in borazines
This paper discusses hyperconjugative stereoelectronic effects in borazines. A series of alkyl-substituted borazines were synthesized and analysed by NMR spectroscopy and X-ray diffraction. Supported by NBO analyses, the significant decreases in 1JCH coupling constant for the CH groups adjacent to the boron atoms are consistent with the presence of and interactions. These interactions lower the electrophilicity of boron atoms, enhancing moisture stability and establishing these molecules as valuable scaffolds in synthetic chemistry and materials science.
Escape from Flatland: Stereoselective Synthesis of Hexa-aryl Borazines and their sp²-Based 3D Architectures
Borazine and its derivatives can be considered critical doping units for engineering hybrid C(sp2)-based molecules with tailored optoelectronic properties. Herein, we report the first synthesis of hexaarylborazines that, bearing ortho-substituted aryl moieties, extend three-dimensionally. Using a one-pot protocol, we first form an electrophilic chloroborazole and then react it with an aryl lithium (ArLi). By selecting the appropriate ortho-substituent, we can guide the ArLi to add to the BN-core in a specific way, ultimately controlling the stereochemical outcome of the three-substitution reaction. Rationalization of the stereochemical model through computational analysis allowed us to show that when aryl lithium nucleophiles bearing rigid long-range ortho-substituents are used, i.e., stiff substituents. The ortho-substituent shields its side of the electrophilic B3N3 core, biasing the incoming ArLi to add anti at each addition step, forming the final tri-aryl borazine exclusively as cc-isomer. Leveraging this stereoselective approach, prototypical multichromophoric borazine derivatives were prepared, and we showcased how the stereochemical arrangement of these chromophores distinctly influences their redox behavior. This methodology paves the way for previously inaccessible borazines to serve as privileged precursors to transcend the conventional bidimensionality associated with graphenoid systems and pioneer the construction of new forms of three-dimensional C(sp2)-based architectures.
Die Macht der Sonne
The Bonifazi group recently participated in the documentary Die Macht der Sonne (The Power of the Sun), which explores solar energy as an inexhaustible and sustainable source of power for the future. Click the link below to watch the documentary and learn more!
DoSChem Symposium 2024
In September, some PhD students from the Bonifazi Group took part in the annual symposium organized by DoSChem, presenting their research through posters and oral talks.
The event was a great opportunity to share our latest findings and get valuable feedback from peers. It’s always exciting to discuss our work with other researchers and hear fresh perspectives that can help shape future directions.
KinderUni 2024
Today, PhD students and postdocs from the Bonifazi Group joined the exciting KinderUni event, where curiosity and science come together for young minds!
This yearly initiative allows children to explore the wonders of science through fun, hands-on experiments. This year, our team prepared engaging activities including ball games, slime-making, and crafting bouncing balls. The children loved experimenting, learning, and discovering the science behind these creations – all while having loads of fun!
We’re thrilled to have shared our passion for science with the next generation of curious minds. Looking forward to inspiring more young scientists in future editions of KinderUni!
Kindergarten activity
Spinoff Fellowship Demo Day
Congratulations to Laura who presented her IrrevoChrom FFG Spin-off Fellowship topic and spin-off project at the Demo Day in front of the Science Minister Martin Polaschek and the Head of the FFG Henrietta Egerth.
For more info: brutkasten.com/artikel/ffg-spin-off-fellowship-demoday
FFG Spin-off Fellowship awarded
The “IrrevoChrom” project is one out of total eleven recently granted FFG spin-off fellowships that will be led by FFG fellow Laura Maggini and host Davide Bonifazi at the Institute of Organic Chemistry, University of Vienna.
The FFG-funded IrrevoChrom Spin-off Fellowship will build on the patent developed in the Bonifazi group (EP application No EP22164076.6) within the framework of the Charisma Marie-Sklodowska Curie project they are coordinating, entailing the formulation of an irreversible EC matrix composed of both the chromogenic material, an anti-oxidant and electrolyte, to develop and scale-up a commercially viable and completely irreversible electrochromic ink compatible with industrial manufacturing processes.
Upon activation, this ink will provide a stark and permanent color transition (colorless to black), impossible to reverse. Thanks to the new formulations developed in this Fellowship, we will match our technology with industrial ECDs productions processes, jump starting its commercial exploitation, and develop in collaboration with Silicon Austria Labs activatable tamperproof demos.