PhotoRedOx · Spectroscopic and Computational Elucidation of Transition Metal Photoredox Mechanisms
„Хоризонт 2020“ — Действия „Мария Склодовска-Кюри“
- Период
- 2021-08-01 → 2024-07-31
- Финансиране от ЕС
- 255 756 €
- Участници
- 2
- Схема
- MSCA-IF
Линиите свързват координатора с партньорите.
Накратко на български
Механизмите на фоторедокс катализата с преходни метали се анализират чрез примери с комплекси на никел. По-доброто разбиране на тези процеси помага за създаването на нови катализатори и оптимизиране на производството на сложни молекули за лекарства.
Кратко обяснение, генерирано от езиков модел по текста на CORDIS. Оригиналът е по-долу.
Резултати накратко
Spectroscopic and Computational Elucidation of Transition Metal Photoredox Mechanisms
The merge of thermal catalysis and photochemistry (i.e., photoredox catalysis) has revolutionized organic synthesis through using photons and earth-abundant transition metals instead of precious metal catalysts. Photoredox catalysis has enabled new reactive intermediates and excited states that have unlocked synthetic possibilities for complex molecules, advancing options for drug development and production. However, the mechanisms underlying these processes are not fully understood, and a deeper understanding of the fundamental concepts is necessary for the design of novel photocatalysts and optimization of reactions. In this project, a multi-disciplinary approach was used to provide new mechanistic insights underlying photoredox catalysis by combining spectroscopic and analytical techniques with computational methods. Specifically, the project aimed to understand how to efficiently harvest photons to generate transition metal excited states capable of activating inert ligand-metal bonds for complex reactivity. The focus was on experimentally and computationally quantifying ground and excited state frontier molecular orbitals and potential energy surfaces to define structure-function relationships across excited state photocatalysis. Conclusions: The project successfully provided significant mechanistic insights into the photochemistry of Ni(II)–bipyridine complexes. Key findings include the identification of the mechanism for excited-state Ni-C bond homolysis, the impact of ligand structure on photochemical stability and reactivity, and the pathways for oxidative addition and dimerization of Ni(I) intermediates. These discoveries have deepened our understanding of how to control excited-state potential energy surfaces and how ligand design can tune catalytic reactivity. The results offer a foundation for developing more efficient and selective photocatalysts, which have potential applications in green chemistry and sustainable synthesis.
Текст от CORDIS, на английски · Данни: CORDIS, © Европейски съюз
Цел на проекта
Photoredox catalysis is an emerging and powerful methodological approach for accomplishing bond constructions in organic chemistry and utilizes photosensitizers to convert photon energy into chemical potential to drive photo-induced C–C/C–X couplings and C–H bond activations. Given catalysis can be light-activated, this methodology is considered environmentally friendly and sustainable. To date, the three main modes of action are: 1) single electron transfers (SETs) to initiate radical coupling reactions; 2) SETs to simultaneously generate free radicals and activate transition metal catalysis (i.e., dual photoredox); and 3) energy transfer to or direct excitation of a transition metal catalyst. While the number and complexity of bond transformations is rapidly increasing, there are few spectroscopic or computational studies of photoredox mechanisms, largely due to the complexity and interplay between excited state dynamics and reactive intermediates. The applicant will use a variety of high-level spectroscopies spanning 10 orders of magnitude in photon energy and 15 orders of magnitude in time to observe molecular events from femtoseconds after light absorption to individual steps in the reaction. Experimental data guide ligand design to tune ground and excited state structure, regioselectivity, or alter reactivity for new bond constructions. Together, the methodologies allow to evaluate energetics of reaction coordinates, define mechanisms, estimate redox activity of intermediates, and map excited state potential energy surfaces to define key electronic contributions from frontier molecular orbitals. This work will be communicated at local, national, and international seminars and conferences. Major findings will be disseminated via publication in high-impact scientific journals. Importantly, the applicant’s training at the host institution and the returning phase will be invaluable for accomplishing his goal to obtain a position at a major European University.
Оригинален текст от CORDIS (на английски).
Участници
- USTAV ORGANICKE CHEMIE A BIOCHEMIE, AV CR, V.V.I. · PRAHA 6КоординаторЧехия
- CALIFORNIA INSTITUTE OF TECHNOLOGYCORP · PasadenaСъединени щати
Връзки
Данни: CORDIS, © Европейски съюз