Periodic Reporting for period 1 - KETOCYAN (Upgrading Cyanines dyes: Non-Kekulé ketocyanines and related patterns)
Berichtszeitraum: 2020-08-01 bis 2022-07-31
The goal of KETOCYAN project is to develop a library of novel diradicaloid dyes (so-called non-Kekulé ketocyanines), as well as related highly persistent radical species. Most of these exotic molecules have long been disregarded unrealistic propositions due to their unusual structures; however, they are expected to possess intriguing physical and chemical properties, with potential in the fields of optoelectronics and photoredox chemistry. The development of unorthodox organic functionalities mostly aims at academic breakthroughs, but as history has proven itself in countless ways the discovery of unconventional molecules paves the way to major technological advances and potentially commercially uses.
The study of a first set of precursors indicated the key role of steric hindrance in the viability of the targets. These preliminary results opened two research lines.
The first one covered the design of unprecedented versions of dyes, known as “Stenhouse salts”. And allowed for the observation and spectroscopic characterization for the first time of an electronically non-stabilized non-Kekulé ketocyanine at low temperature. A seminal paper on this work is of imminent submission during the first trimester of 2022.
Electrochemical investigations of other precursors also unveiled a second research line, providing promising guidelines for the isolation of targeted dyes at room temperature. Closely related models were also used for a side study, which was part of the training of the fellow in electrochemistry. This work unveiled critical misconceptions in the mechanism of important biomimetic radical transformations. (see: L. Delfau, S. Nichilo, F. Molton, J. Broggi, E. Tomás-Mendivil,* D. Martin* Angew. Chem. Int. Ed. 2021, 60, 26783-26789.).
The first one covered the design of unprecedented versions of dyes, known as “Stenhouse salts”. And allowed for the observation and spectroscopic characterization for the first time of an electronically non-stabilized non-Kekulé ketocyanine at low temperature. A seminal paper on this work is of imminent submission during the first trimester of 2022.
Electrochemical investigations of other precursors also unveiled a second research line, providing promising guidelines for the isolation of targeted dyes at room temperature. Closely related models were also used for a side study, which was part of the training of the fellow in electrochemistry. This work unveiled critical misconceptions in the mechanism of important biomimetic radical transformations. (see: L. Delfau, S. Nichilo, F. Molton, J. Broggi, E. Tomás-Mendivil,* D. Martin* Angew. Chem. Int. Ed. 2021, 60, 26783-26789.).
This action has contributed to look beyond the edge of modern organic chemical knowledge and intuition by introducing unconventional and original compounds with unusual electronic structures. The study supports the hypothesis that the isolation of room temperature stable non-Kekulé ketocyanine dyes is feasible. It also brings alternative synthetic strategies for the development of original dyes. The discovery of such compounds may or may not lead to future applications; however, the novel molecules and concepts that are/will be publish open a research line of promising future.
The action had an impact in different spheres of academy and society. Undergraduate and graduate students among other has benefited from the expertise brought by the fellow, through direct supervision, but also by discussing ideas throughout the daily work. Public engagement activities with high school students by sharing basic concepts in chemistry and his enthusiasm have become part of the action. The integration within the institution has been successfully accomplished and the action has undoubtedly contributed to his recruitment as a permanent researcher where he is committed to science and outreach.
The action had an impact in different spheres of academy and society. Undergraduate and graduate students among other has benefited from the expertise brought by the fellow, through direct supervision, but also by discussing ideas throughout the daily work. Public engagement activities with high school students by sharing basic concepts in chemistry and his enthusiasm have become part of the action. The integration within the institution has been successfully accomplished and the action has undoubtedly contributed to his recruitment as a permanent researcher where he is committed to science and outreach.