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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Toward rational design of TADF two-coordinate coinage metal complexes: understanding the relationship between natural transition orbital overlap and photophysical properties
A series of twelve two-coordinate coinage metal, Cu, Ag and Au, complexes with carbene-metal-amide structures were prepared. The complexes all display thermal assisted delayed fluorescence (TADF) emission at room temperature from interligand charge transfer (ICT) excited state with short lifetimes (less than 2 μs) and photoluminescent quantum yields that reach near unity. Owing to the involvement of the substituents in the emissive transitions and different metal ion volume, the natural transition orbital (NTO) overlap of the emissive state can be adjusted in a wide range from 0.21 to 0.41. Investigations on the relationship between the NTO overlap of the emissive state and key TADF photophysical properties demonstrated that both singlet–triplet energy gap and radiative decay rate of S 1 state increase along with the NTO overlap exponentially. Consequently, the overall TADF radiative decay rate leads to a maximum when plotted against the NTO overlap, giving the ideal zone from 0.25 to 0.30 for high TADF radiative decay rate in this class of two-coordinate coinage metal complex luminophores.
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- Award ID(s):
- 2018740
- NSF-PAR ID:
- 10334833
- Date Published:
- Journal Name:
- Journal of Materials Chemistry C
- Volume:
- 10
- Issue:
- 12
- ISSN:
- 2050-7526
- Page Range / eLocation ID:
- 4674 to 4683
- 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/10.1039/d2tc00163b
