KFU's inquiry into pillar[5]arenes shows path to artifical photosynthesis

Scientists at the Institute of Chemistry have synthesized new nanostructures for the first time, opening up an approach to assembling fluorescent carbon dioxide sensors and possible photosynthetic systems based on them. A paper saw light in ChemNanoMat.

According to the project lead, Associate Professor of the Department of Organic and Medicinal Chemistry Dmitriy Shurpik, one of the modern concepts of artificial photosynthesis is to create catalysts—supramolecular systems consisting of a receptor part and a catalytic conversion part for efficient and selective CO₂ reduction.

"In the process of photosynthesis, key stages can be distinguished: carbon dioxide fixation, its reduction and removal of reduction products. Each specific stage is the responsibility of a separate subunit of the supramolecular photosynthetic system. Copper catalysts are of particular interest in the development of photosynthetic systems because heterogeneous copper-based electrocatalysts can absorb CO₂ followed by catalytic reduction to hydrocarbons, including methane and ethane," he comments.

The researchers found that the obtained metal-supramolecular structures based on the macrocycle/copper system are able to bind CO₂, which was confirmed by a number of physical and physicochemical methods. The effect of binding of carbon dioxide molecules by the pillar[5]arene/Cu(I) complex was also studied using electrochemical methods of research, the selectivity of electron exchange and reversibility of changes in voltammetry were shown, which allows the synthesized complex to be used for selective monitoring of CO₂ in gas environments and in the development of new photosynthetic systems.

"The team consists of young scientists, graduate and undergraduate students, and has considerable experience in working with guest-host type complexes on the pillar[n]arenes platform. This work combines and extends earlier ideas and concepts of two RNF projects realized in the framework of initiative research by young scientists and is a logical continuation of them. The ambitiousness of the chosen concept is due to the experience of our team in the formation of supramolecular systems sensitive to environmental changes," notes Shurpik.

According to the scientist, this work presents the design of supramolecular fluorescent nanoparticles based on novel pyridine derivatives of pillar[5]arene and Cu(I) cations with CO₂ binding and detection function, which opens a new approach to the assembly of fluorescent CO₂ sensors and possible photosynthetic systems based on them.

"We have synthesized for the first time macrocycles based on the class of pillar[5]arenes containing thiopyridine fragments capable of selectively interacting with univalent copper ions. The obtained systems possessed fluorescent properties as well as the ability to absorb CO₂ molecules from the environment. The obtained results open wide opportunities for the development of new photosynthetic systems and new generation sorption materials," resumes Shurpik.

KFU's inquiry into pillar[5]arenes shows path to artifical photosynthesis

More information:
Metallo-Supramolecular Structures Binding CO2: Self-Assembly of Fluorescent Nanoparticles Based on Pyridine Derivatives of Pillar[5]arene and Cu(I)
onlinelibrary.wiley.com/doi/ab … .1002/cnma.202300124

Provided by Kazan Federal University