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Platinum Complexes of N,N',N″,N‴-Diboronazophenines
Hu Lei1, Shawkat M Aly1, Paul-Ludovic Karsenti1
1Département de Chimie, Université de Sherbrooke , Sherbrooke, QC J1K 2R1, Canada.
Inorganic Chemistry
|October 13, 2017
Summary
This study reports the development of novel emissive near-infrared materials by rigidifying azophenine with difluoroboranes and attaching platinum complexes. These new compounds exhibit unique charge-transfer properties and near-infrared emission.
Area of Science:
- Materials Science
- Photochemistry
- Organic Chemistry
Background:
- Azophenine is a non-emissive organic molecule.
- Rigidification and functionalization are key strategies to tune photophysical properties.
- Near-infrared (NIR) emissive materials are of significant interest for various applications.
Purpose of the Study:
- To develop novel emissive materials based on a rigidified azophenine core.
- To investigate the photophysical properties of azophenine functionalized with platinum complexes.
- To explore charge-transfer (CT) excited states and their emission characteristics.
Main Methods:
- Synthesis of rigidified azophenine derivatives.
- Functionalization with luminescent platinum-containing arms.
- Spectroscopic characterization (absorption, emission) at different temperatures.
- Density Functional Theory (DFT) computations.
Main Results:
- The rigidified azophenine derivatives exhibit low-energy charge-transfer (CT) singlet and triplet excited states with absorption bands extending to 800 nm.
- The incorporation of difluoroborane (BF2+) units renders the CT singlet state emissive in the near-infrared (NIR) region at room temperature and low temperature.
- DFT calculations predict triplet emission in the 1200-1400 nm range, though phosphorescence was not experimentally detected.
- Evidence for slow triplet energy transfer from the platinum arms to the azophenine core was observed.
Conclusions:
- Rigidification of azophenine using BF2+ units is an effective strategy to achieve NIR emission.
- The developed compounds display unique photophysical properties arising from CT interactions between the platinum arms and the azophenine core.
- These findings open avenues for the design of new NIR emitters for advanced applications.