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Operando XAS and UV-Vis Characterization of the Photodynamic Spiropyran-Zinc Complexes
A V Chernyshev1, A A Guda2, A Cannizzo3
1Institute of Physical and Organic Chemistry , Southern Federal University , Stachka Avenue, 194/2 , 344090 Rostov-on-Don , Russia.
The Journal of Physical Chemistry. B
|January 19, 2019
Summary
Photochromic spiropyrans form stable, colored complexes with Zn ions, enabling metal ion detection. Upon light exposure, Zn ions are rapidly released from the spiropyran complex, as directly observed spectroscopically.
Area of Science:
- Coordination Chemistry
- Photochemistry
- Spectroscopy
Background:
- Photochromic spiropyrans (SPP) are known for their light-responsive properties.
- Complexation with metal ions can alter the optical and electronic characteristics of SPP ligands.
- Understanding the dynamics of metal-ion binding and release is crucial for developing responsive materials.
Purpose of the Study:
- To characterize the thermal and photoinduced processes of spiropyran complexation with Zn ions.
- To investigate the structural and electronic changes upon complex formation using spectroscopy.
- To directly observe the photorelease dynamics of Zn ions from the spiropyran complex.
Main Methods:
- UV-vis spectroscopy
- X-ray absorption spectroscopy (XAS) in operando regime
- Pump-flow-probe spectroscopy
Main Results:
- Spiropyrans form stable, colored complexes with Zn ions (λmax = 525 nm) with high molar absorptivity.
- The Zn-spiropyran complex exhibits fluorescence and photochromic behavior.
- Operando XAS revealed significant changes in the Zn local atomic structure upon complexation.
- Direct spectroscopic evidence shows Zn ion photorelease from the complex within 20 μs after light irradiation.
Conclusions:
- Spiropyran-Zn complexes are effective for monitoring Zn ion concentration due to their distinct spectral properties.
- Light irradiation triggers rapid Zn ion release from the spiropyran complex.
- This study provides the first direct spectroscopic observation of Zn photorelease from spiropyran complexes.
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