Using charged porphyrins, a researcher of Kanazawa University and collaborative researchers of Ritsumeikan University created stacked ion and radical pairs revealing fascinating new properties
π-Stacked ion and radical pairs are extremely useful for the creation of new electronic materials. Yet, the study of these has been limited due to multiple difficulties in their creation and characterization. A new study by researchers from Japan uses charged porphyrins to synthesize and study π-electronic ion pairs. Their findings can lead to the creation of novel materials and new types of batteries and memory devices.
Ions are created when an atom or molecule either loses or gains electrons, thus gaining a charge. When two oppositely charged ions are combined, it can lead to the creation of an ion pair. The influence of different ion pairs on the physical properties of the material they are present in has been widely studied as it can lead to the creation of new functional electronic materials.
Of particular interest is the study of π-electronic ion pairs for their ability to employ intermolecular interactions to produce dimension-controlled assemblies. These are useful for creating new electronic materials. These interactions (known as “iπ−iπ interactions”) cause the stacking of ions into π-stacked ion pairs (π-sips). Controlling the electronic state of these π-sips can create π-stacked radical pairs (π-srps). Both of these have attractive properties for the creation of electronic materials, but have not been studied much owing to the difficulties in preparation and structure determination.
To solve this problem, a team of researchers led by Professor Hiromitsu Maeda of Ritsumeikan University, Japan, synthesized and studied π-sips and π-srps using charged porphyrins. This study was subsequently published in the Journal of The American Chemical Society. According to Prof. Maeda, “The charged porphyrins investigated in this study are different from and more advantageous than porphyrin derivatives with an electronically neutral core and peripheral charged substituents. We found that porphyrins with metal ions can be used for the creation of π-sips and π-srps and thus help us study their structure and properties.”
The researchers first used the theory of hard and soft acids and bases to perform ion-pair metathesis and synthesize porphyrin ion pairs at a yield ranging from 59% to 85%. These were then characterized using spectrometry and single-crystal X-ray analyses. The researchers found that the porphyrin ions formed solid-state assemblies and π-sips in solutions. Moreover, the introduction of electron-donating and electron-withdrawing groups activated the anions and cations, respectively. This activation of cations and anions leads to the ability to control electronic states of the π-sips and thus to the creation of π-srps. The creation of π-srps occurred through electron transfer due to solvent polarity and photoexcitation. The researchers also observed temperature-dependent spin distribution changes in π-srps. “The spin−spin interactions are influenced by the stacking structure of hetero π-electronic systems, which are characteristic of π-srps derived from π-sips,” comments Prof. Maeda.
“Investigating the properties of ion pairs as discrete chemical species is crucial for the development of functional materials. These new materials will have multiple different applications in fields like nanomagnetism, catalytic reactions, and ferroelectrics, thus creating new types of batteries and memory devices,” he concludes.
|Title of original paper:||π‑Stacked Ion Pairs: Tightly Associated Charged Porphyrins in Ordered Arrangement Enabling Radical-Pair Formation|
|Journal||Journal of The American Chemical Society|
|Latest Article Publishing Date||November 15 2022|
|Method of Research||Experimental Study|
|Subject of Research||Not Applicable|
|COI Statement||The authors declare no competing financial interest|
This work was supported by JSPS KAKENHI grant numbers JP18H01968 and JP22H02067 for Scientific Research (B), JP20J22745 for JSPS Fellows, and JP20H05863 for Transformative Research Areas (A) “Condensed Conjugation” and the Ritsumeikan Global Innovation Research Organization (R-GIRO) project (2017−22 and 2022−27).
Image Title: Studying π-Electronic Ion Pairs Using Porphyrins
Image Caption: A new study by researchers from Japan presents the study of stacked electronic pairs using charged porphyrins that form solid-state assemblies and solution-state stacked ion pairs.
Image Credit: Hiromitsu Maeda from Ritsumeikan University
License Type: Original Content