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Two-coordinate carbene-MI-amide (cMa, MI = Cu, Ag, Au) complexes have emerged as highly efficient luminescent materials for use in a variety of photonic applications, due to their extremely fast radiative rates via thermally activated delayed fluorescence (TADF) from an interligand charge transfer (ICT) process. A series of cMa derivatives were prepared to examine the variables which affect the radiative rate with the goal of understanding the parameters that control the radiative TADF process in these materials. We find that blue emissive complexes with high photoluminescence efficiency (PL > 0.95) and fast radiative rates (kr = 4 x 106 s-1) can be achieved by selectively extending the -system of the carbene and amide ligands. Of note is the role played by increasing the separation between the hole and electron in the ICT excited state. Analysis of temperature dependent luminescence data along with theoretical calculations indicate that the hole-electron separation alters the energy gap between the lowest energy singlet and triplet states (dE ST) while keeping the radiative rate for the singlet state unchanged. This interpretation provides guidelines for the design of new cMa derivatives with even faster radiative rates as well as those with slower radiative rates and thus extended excited state lifetimes.
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Luminescent Bimetallic Two-Coordinate Gold(I) Complexes Utilizing Janus Carbenes
A series of bimetallic carbene-metal-amide (cMa) complexes have been prepared with bridging biscarbene ligands to serve as a model for the design of luminescent materials with large oscillator strengths and small energy differences between the singlet and triplet states (dE ST). The complexes have a general structure (R2N)Au(:carbene—carbene:)Au(NR2). The bimetallic complexes show solvation-dependent absorption and emission that is analyzed in detail. It is found that the molar absorptivity of the bimetallic complexes is correlated with the energy barrier to rotation of the metal-ligand bond. The bimetallic cMa complexes also exhibit short emission lifetimes (t = 200-300 ns) with high photoluminescence efficiencies (PL >95%). The radiative rates of bimetallic cMa complexes are 3 to 4 times faster than that of the corresponding monometallic complexes. Analysis of temperature-dependent luminescence data indicates that the lifetime for the singlet state (τ_(S_1 )) of bimetallic cMa complexes are near 12 ns with a dE ST of 40 50 meV. The presented compounds provide a general design for cMa complexes to achieve small values for dE ST while retaining high radiative rates. Solution processed OLEDs made using two of the complexes as luminescent dopants show high efficiency and low roll-off at high luminance.
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- Award ID(s):
- 2018740
- PAR ID:
- 10474078
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- Journal of the American Chemical Society
- Volume:
- 145
- Issue:
- 36
- ISSN:
- 0002-7863
- Page Range / eLocation ID:
- 20097 to 20108
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/jacs.3c07743
