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"Quick-Silver" from a Systematic Study of Highly Luminescent, Two-Coordinate, d10 Coinage Metal Complexes
Rasha Hamze1, Shuyang Shi1, Savannah C Kapper1
1Department of Chemistry , University of Southern California , Los Angeles , California 90089 , United States.
Journal of the American Chemical Society
|May 8, 2019
Summary
This study explores copper, silver, and gold complexes, revealing their physical and photophysical properties. The findings show these metal complexes exhibit high photoluminescence quantum yields and tunable emission lifetimes, crucial for advanced material applications.
Area of Science:
- Coordination Chemistry
- Photophysics
- Materials Science
Background:
- Isoelectronic and isostructural metal complexes offer a platform for systematic property investigation.
- Carbene and N-carbazolyl ligands provide tunable electronic and steric environments.
- Understanding photophysical properties is key for developing advanced luminescent materials.
Purpose of the Study:
- To systematically investigate the physical and photophysical properties of Cu, Ag, and Au complexes with N-carbazolyl and carbene ligands.
- To correlate structural features with observed photoluminescence characteristics.
- To explore the potential of these complexes in applications requiring efficient light emission.
Main Methods:
- Synthesis and crystal structure determination of metal complexes.
- Electrochemical measurements to assess electronic properties.
- Temperature-dependent photophysical studies (5-325 K) including emission lifetime and quantum yield measurements.
- Analysis of singlet-triplet energy gaps (Δ ES1-T1).
Main Results:
- All six (carbene)M(Cz) complexes exhibit high photoluminescence quantum yields (0.8-1.0).
- Emission lifetimes (τ) follow the order Ag < Au < Cu, with silver complexes showing significantly shorter lifetimes.
- Room temperature emission is attributed to E-type delayed fluorescence (TADF), governed by Δ ES1-T1, which varies between metal ions.
Conclusions:
- The choice of metal ion (Cu, Ag, Au) has a limited impact on electrochemical properties and CT energies but significantly influences emission lifetimes.
- The energy difference between singlet and triplet excited states (Δ ES1-T1) is a critical factor in determining emission rates.
- These metal complexes demonstrate promising characteristics for applications in optoelectronics and lighting due to their efficient and tunable photoluminescence.
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