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Halogen Bonding to Amplify Luminescence: A Case Study Using a Platinum Cyclometalated Complex.
Vasily V Sivchik1, Anastasia I Solomatina2, Yi-Ting Chen3
1Department of Chemistry, University of Eastern Finland, 80101 Joensuu (Finland).
Angewandte Chemie (International Ed. in English)
|September 26, 2015
Summary
This study shows how halogen bonding with fluorinated arenes significantly enhances the luminescence of a platinum complex. This 22-fold increase in light emission is achieved by boosting spin-orbit coupling and reducing energy loss.
Area of Science:
- Materials Science
- Photochemistry
- Supramolecular Chemistry
Background:
- Weakly luminescent platinum complexes often have limited applications.
- Enhancing luminescence quantum yield is crucial for developing advanced optoelectronic materials.
Purpose of the Study:
- To investigate the effect of halogen bonding on the luminescence properties of a platinum complex.
- To explore the mechanism behind luminescence enhancement induced by halogen bond donors.
Main Methods:
- Cocrystallization of a platinum complex [Pt(btpy)(PPh3)Cl] with fluorinated bromo- and iodoarenes.
- Crystallographic analysis to confirm halogen-bonding interactions (Pt-Cl⋅⋅⋅X-R).
- Photophysical measurements to determine emission quantum yield and energy.
- Theoretical calculations to elucidate the mechanism of luminescence enhancement.
Main Results:
- Cocrystallization led to efficient halogen-bonding interactions.
- A significant 22-fold enhancement in luminescence quantum yield (from 0.03 to 0.65) was observed.
- Emission energy remained largely unchanged, indicating structural integrity.
Conclusions:
- Halogen bonding donors effectively amplify luminescence intensity in platinum complexes.
- The enhancement is attributed to increased spin-orbit coupling via the heavy-atom effect.
- Suppression of nonradiative relaxation pathways by increasing chromophore rigidity also contributes to the improved luminescence.
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