In a collaborative project involving the Universities of Amsterdam and Groningen, as well as Italy’s European Laboratory for Non-Linear Spectroscopy, scientists have made considerable strides in the field of photoclick chemistry. Through calculated molecular substitution, they have managed to increase the reactivity of the compound involved in the PQ-ERA reaction, a widely-used photoclick reaction.
Their findings, published in the esteemed journal Chemical Science—a flagship periodical of the Royal Society of Chemistry—demonstrate elevated photoreaction quantum yields, accelerated reaction rates, and remarkable tolerance to oxygen. The published research was distinguished as both a HOT Article and Pick of the Week.
The research contributions came from Michiel Hilbers and Wybren Jan Buma from the Molecular Photonics group at the Van ‘t Hoff Institute for Molecular Sciences, University of Amsterdam. They collaborated with Wiktor Szymanski and Nobel laureate Ben Feringa at the University of Groningen for synthetic and reaction characterization.
Credit for graphical abstract of the research: UvA HIMS / ChemSci
Photoclick chemistry is an evolution of click chemistry, which itself was honored with the Nobel Prize in Chemistry in 2022. Photoclick chemistry stands out for its capability to exert spatial and temporal control over chemical reactions. It finds a wide array of applications, such as 3D printing, bioimaging, and protein labeling.
Table of Contents
Augmentation of PQ-ERA Photoclick Reaction
One of the specific reactions in photoclick chemistry, the PQ-ERA reaction involves the light-induced photocycloaddition of 9,10-phenanthrenequinone (PQ) with electron-rich alkenes (ERA). While this reaction has been noted for its commendable kinetics and biocompatibility, the conventional PQ compounds have shown sub-optimal reactivity, thereby limiting its efficacy.
The research published in Chemical Science outlines a straightforward approach to overcome this limitation. The team discovered that incorporating a thiophene molecule at the 3-position of the PQ scaffold dramatically elevates the reactivity of the PQ triplet state, thereby augmenting the efficiency of the PQ-ERA reaction.
Studies incorporating nanosecond time-resolved spectroscopy and quantum chemical analyses were conducted by the Amsterdam Molecular Photonics group. These were complemented by femtosecond time-resolved spectroscopy studies conducted in Florence. These investigations revealed that the molecular substitution significantly elevates the number of reactive triplet states (3ππ*) during the excitation of 3-thiophene PQs. Consequently, this led to an excellent photoreaction quantum yield (FP, up to 98%), high second-order rate constants (k2, up to 1974 M−1 s−1), and a marked tolerance to oxygen in the PQ-ERA reaction framework.
The research findings offer the opportunity for further refinements, presenting an optimistic outlook for the development of rapid and efficient photoclick reactions.
Reference: “Establishing PQ-ERA photoclick reactions with unprecedented efficiency by engineering of the nature of the phenanthraquinone triplet state” by Youxin Fu, Georgios Alachouzos, Nadja A. Simeth, Mariangela Di Donato, Michiel F. Hilbers, Wybren Jan Buma, Wiktor Szymanski, and Ben L. Feringa, published on 21 June 2023 in Chemical Science.
DOI: 10.1039/D3SC01760E
Frequently Asked Questions (FAQs) about Photoclick Chemistry Advancements
What is the main focus of the research described?
The main focus of the research is the significant advancement in photoclick chemistry. Specifically, the study aims to enhance the reactivity and efficiency of the PQ-ERA reaction through molecular substitution.
Which institutions collaborated on this research?
The Universities of Amsterdam and Groningen collaborated with Italy’s European Laboratory for Non-Linear Spectroscopy to carry out this research.
Where were the findings of the research published?
The findings were published in the esteemed journal “Chemical Science,” which is a flagship periodical of the Royal Society of Chemistry. The paper was distinguished as a HOT Article and Pick of the Week.
Who were the contributing researchers from the University of Amsterdam?
Michiel Hilbers and Wybren Jan Buma from the Molecular Photonics group at the Van ‘t Hoff Institute for Molecular Sciences, University of Amsterdam, contributed to the research.
What are the applications of photoclick chemistry?
Photoclick chemistry finds a broad range of applications, including but not limited to 3D printing, protein labeling, and bioimaging.
What specific advancement was made in the PQ-ERA reaction?
A thiophene molecule was incorporated at the 3-position of the PQ scaffold, which dramatically increased the reactivity of the PQ triplet state. This led to increased efficiency in the PQ-ERA reaction.
What investigative methods were used in the study?
The study utilized nanosecond time-resolved spectroscopy and quantum chemical analyses, complemented by femtosecond time-resolved spectroscopy studies.
What does the research imply for future developments?
The research offers the opportunity for further refinements in photoclick chemistry. It presents an optimistic outlook for the development of rapid and efficient photoclick reactions, with potential applications in various fields.
When was the research published?
The research was published on 21 June 2023.
How can I access the full article?
The full article can be accessed through its DOI: 10.1039/D3SC01760E, usually available via academic databases or the journal’s website.
More about Photoclick Chemistry Advancements
- Chemical Science Journal
- Royal Society of Chemistry
- University of Amsterdam’s Molecular Photonics Group
- University of Groningen
- European Laboratory for Non-Linear Spectroscopy
- Nobel Prize in Chemistry 2022
- Van ‘t Hoff Institute for Molecular Sciences
- DOI Access for the Article
1 comment
Wow, this is really groundbreaking stuff! Looks like photoclick chemistry is on the rise and it’s gonna change a lot of industries. Kudos to the team!