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Issue 47, 2018
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Deep blue emitting Cu(I) tripod complexes. Design of high quantum yield materials showing TADF-assisted phosphorescence

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Abstract

In a previous investigation, it was shown that [Cu(tpym)(PPh3)]PF61 with tpym = tris(2-pyridyl)methane represents a deep blue emitter (λmax = 466 nm) though with a low emission quantum yield ΦPL if doped in a polymer (7%) or dissolved in a fluid solvent (≪1%). In this study, we present new tripod compounds with sterically demanding ligands: [Cu(tpym)(P(o-tol)3)]PF62 and [Cu(tpym)(P(o-butyl-ph)3)]PF63 with P(o-tol)3 = tris(ortho-tolyl)phosphine and P(o-butyl-ph)3 = tris(ortho-n-butylphenyl)phosphine. These compounds show high emission quantum yields even in a fluid solution (dichloromethane) reaching a benchmark value for 3 of ΦPL = 76%. This becomes possible due to the specific design of rigidifying the complexes. Importantly, the deep blue emission color is maintained or even further blue shifted to λmax = 452 nm (compound 3 powder). Compound 2 is characterized photophysically in detail. In particular, it is shown that the lowest excited triplet state T1 experiences very efficient spin–orbit coupling (SOC). Accordingly, the phosphorescence decay rate is as large as 5 × 104 s−1 (20 μs) belonging to the fastest T1 → S0 transition values (shortest decay times) reported so far. Investigations down to T = 1.5 K reveal a large total zero-field splitting (ZFS) of 7 cm−1 (0.9 meV). Although thermally activated delayed fluorescence (TADF) grows in at T ≥ 160 K, the phosphorescence of 2 still dominates (60%) over TADF (40%) at ambient temperature. Thus, the compound represents a singlet harvesting-plus-triplet harvesting material, if applied in an OLED.

Graphical abstract: Deep blue emitting Cu(i) tripod complexes. Design of high quantum yield materials showing TADF-assisted phosphorescence

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Publication details

The article was received on 12 Oct 2018, accepted on 29 Oct 2018 and first published on 30 Oct 2018


Article type: Paper
DOI: 10.1039/C8DT04093A
Citation: Dalton Trans., 2018,47, 17067-17076
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    Deep blue emitting Cu(I) tripod complexes. Design of high quantum yield materials showing TADF-assisted phosphorescence

    A. Schinabeck, N. Rau, M. Klein, J. Sundermeyer and H. Yersin, Dalton Trans., 2018, 47, 17067
    DOI: 10.1039/C8DT04093A

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