New Cu(<scp>i</scp>) halide complexes showing TADF combined with room temperature phosphorescence: the balance tuned by halogens

Baranov, Andrey Yu.; Berezin, Alexey S.; Samsonenko, Denis G.; Mazur, Anton S.; Tolstoy, Peter M.; Plyusnin, Viktor F.; Kolesnikov, Ilya E.; Artem’ev, Alexander V.

doi:10.1039/d0dt00192a

Cited by 50 publications

(39 citation statements)

References 47 publications

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“…Such a behavior of combined TADF and phosphorescence is not very frequently observed [ 48 ], but see refs. [ 50 , 51 , 83 , 86 , 114 ]. Mostly, however, the TADF channel dominates strongly [ 48 ].…”

Section: Resultsmentioning

confidence: 99%

“…Thus, they may be regarded as singlet and triplet harvesting materials. This effect of combined TADF-phosphorescence emission, suited for decreasing the overall emission decay time, has already been addressed in the literature [ 50 , 51 , 82 , 83 , 84 , 85 , 86 , 87 , 88 , 89 ]. In particular, Cu(I) and Ag(I) dimers, in which the metal centers are linked by P∩N ligands can show this effect [ 34 , 50 , 87 , 90 , 91 , 92 , 93 , 94 , 95 ] and very probably also the complexes reported recently [ 96 ].…”

Section: Introductionmentioning

confidence: 99%

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P∩N Bridged Cu(I) Dimers Featuring Both TADF and Phosphorescence. From Overview towards Detailed Case Study of the Excited Singlet and Triplet States

et al. 2021

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We present an overview over eight brightly luminescent Cu(I) dimers of the type Cu2X2(P∩N)3 with X = Cl, Br, I and P∩N = 2-diphenylphosphino-pyridine (Ph2Ppy), 2-diphenylphosphino-pyrimidine (Ph2Ppym), 1-diphenylphosphino-isoquinoline (Ph2Piqn) including three new crystal structures (Cu2Br2(Ph2Ppy)3 1-Br, Cu2I2(Ph2Ppym)3 2-I and Cu2I2(Ph2Piqn)3 3-I). However, we mainly focus on their photo-luminescence properties. All compounds exhibit combined thermally activated delayed fluorescence (TADF) and phosphorescence at ambient temperature. Emission color, decay time and quantum yield vary over large ranges. For deeper characterization, we select Cu2I2(Ph2Ppy)3, 1-I, showing a quantum yield of 81%. DFT and SOC-TDDFT calculations provide insight into the electronic structures of the singlet S1 and triplet T1 states. Both stem from metal+iodide-to-ligand charge transfer transitions. Evaluation of the emission decay dynamics, measured from 1.2 ≤ T ≤ 300 K, gives ∆E(S1-T1) = 380 cm−1 (47 meV), a transition rate of k(S1→S0) = 2.25 × 106 s−1 (445 ns), T1 zero-field splittings, transition rates from the triplet substates and spin-lattice relaxation times. We also discuss the interplay of S1-TADF and T1-phosphorescence. The combined emission paths shorten the overall decay time. For OLED applications, utilization of both singlet and triplet harvesting can be highly favorable for improvement of the device performance.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

P∩N Bridged Cu(I) Dimers Featuring Both TADF and Phosphorescence. From Overview towards Detailed Case Study of the Excited Singlet and Triplet States

et al. 2021

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“…Such a behavior of combined TADF and phosphorescence is not very frequently observed [48], but see refs. [50,51,81,84,112]. Mostly, however, the TADF channel dominates strongly [48].…”

Section: Luminescence Properties Of Cu2x2(pn)3 Complexes With X = Cl Br I An Overviewmentioning

confidence: 99%

P^N bridged Cu(I) Dimers Featuring both TADF and Phosphorescence. From Overview Towards Detailed Case Study of the Excited Singlet and Triplet States.

Hofbeck¹,

Niehaus²,

Fleck³

et al. 2021

Preprint

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We present an overview over eight brightly luminescent Cu(I) dimers of the type Cu2X2(PN)3 with X = Cl, Br, I and P^N = 2-diphenylphosphino-pyridine (Ph2Ppy), 2-diphenylphosphino-pyrimidine (Ph2Ppym), 1-diphenylphosphino-isoquinoline (Ph2Piqn) including three new crystal structures (Cu2Br2(Ph2Ppy)3, 1-Br, Cu2I2(Ph2Ppym)3, 2-I, and Cu2I2(Ph2Piqn)3, 3-I). However, we mainly focus on their photo-luminescence properties. All compounds exhibit combined thermally activated delayed fluorescence (TADF) and phosphorescence at ambient temperature. Emission color, decay time, and quantum yield varies over large ranges. For deeper characterization, we select Cu2I2(Ph2Ppy)3, 1-I, showing a quantum yield of 81 %. DFT and SOC-TDDFT calculations provide insight into the electronic structures of the singlet S1 and triplet T1 states. Both stem from metal+iodide-to-ligand charge transfer transitions. Evaluation of the emission decay dynamics, measured from 1.2 ≤ T ≤ 300 K, gives ∆E(S1-T1) = 380 cm-1 (47 meV), a transition rate of k(S1→S0) = 2.25×106 s-1 (445 ns), T1 zero-field splittings, transition rates from the triplet substates, and spin-lattice relaxation times. We also discuss the interplay of S1-TADF and T1-phosphorescence. The combined emission paths shorten the overall decay time. For OLED applications, utilization of both singlet and triplet harvesting can be highly favorable for improvement of the device performance.

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“…Luminescent transition metal complexes with binuclear Cu I halide core structures have been extensively studied in the last few years, as they show remarkable photophysical properties and are very promising candidates for organic light-emitting diodes (OLEDs). [1][2][3][4][5][6][7][8][9][10][11] Al arge varietyo fb inuclear systemsw ith a butterfly-shaped Cu 2 I 2 core unit and quantum yields of nearly 100 %h ave been developed. These systemsa re capable of thermally activated delayed fluorescence( TADF) so that almost all excitons are harvested via the singlet state through reverse intersystem crossing already at room temperature.…”

Section: Introductionmentioning

confidence: 99%

Investigation of Luminescent Triplet States in Tetranuclear Cu^I Complexes: Thermochromism and Structural Characterization

Boden

Martino‐Fumo

Busch

et al. 2021

Chemistry A European J

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To develop new and flexible Cu I containing luminescent substances, we extendo ur previousi nvestigations on two metal-centered species to four metal-centered complexes. These complexes could be ab asis for designing new organic light-emitting diode (OLED) relevant species. Both the synthesis and in-depth spectroscopic analysis, combined with high-level theoretical calculations are presentedo na series of tetranuclearC u I complexes with ah alide containing Cu 4 X 4 core (X = iodide, bromideo rc hloride) and two 2-(diphenylphosphino)pyridineb ridging ligandsw ith am ethyl group in para (4-Me) or ortho (6-Me) positiono ft he pyridine ring. The structure of the electronic ground state is characterized by X-ray diffraction,N MR, and IR spectroscopy with the support of theoretical calculations. In contrast to the para system, the complexes with ortho-substituted bridging ligandss how ar emarkable and reversible temperature-dependent dual phosphorescence. Here, we combine for the first time the luminescence thermochromism with time-resolved FTIR spectroscopy.T hus, we receive experimental data on the structures of the two triplets tates involved in the luminescence thermochromism. The transient IR spectra of the underlying triplet metal/halide-to-ligandc harget ransfer (3 M/XLCT) and cluster-centered (3 CC) states were obtained and interpreted by comparison withc alculated vibrational spectra. The systematic ands ignificant dependence of the bridging halides was analyzed.

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New Cu(i) halide complexes showing TADF combined with room temperature phosphorescence: the balance tuned by halogens

Abstract: A series of Cu(i) halide complexes showing thermally activated delayed fluorescence (TADF) combined with room temperature phosphorescence are reported.

Cited by 50 publications

References 47 publications

P∩N Bridged Cu(I) Dimers Featuring Both TADF and Phosphorescence. From Overview towards Detailed Case Study of the Excited Singlet and Triplet States

P∩N Bridged Cu(I) Dimers Featuring Both TADF and Phosphorescence. From Overview towards Detailed Case Study of the Excited Singlet and Triplet States

P^N bridged Cu(I) Dimers Featuring both TADF and Phosphorescence. From Overview Towards Detailed Case Study of the Excited Singlet and Triplet States.

Investigation of Luminescent Triplet States in Tetranuclear Cu^I Complexes: Thermochromism and Structural Characterization

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New Cu(i) halide complexes showing TADF combined with room temperature phosphorescence: the balance tuned by halogens

Abstract: A series of Cu(i) halide complexes showing thermally activated delayed fluorescence (TADF) combined with room temperature phosphorescence are reported.

Cited by 50 publications

References 47 publications

P∩N Bridged Cu(I) Dimers Featuring Both TADF and Phosphorescence. From Overview towards Detailed Case Study of the Excited Singlet and Triplet States

P∩N Bridged Cu(I) Dimers Featuring Both TADF and Phosphorescence. From Overview towards Detailed Case Study of the Excited Singlet and Triplet States

P^N bridged Cu(I) Dimers Featuring both TADF and Phosphorescence. From Overview Towards Detailed Case Study of the Excited Singlet and Triplet States.

Investigation of Luminescent Triplet States in Tetranuclear CuI Complexes: Thermochromism and Structural Characterization

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Investigation of Luminescent Triplet States in Tetranuclear Cu^I Complexes: Thermochromism and Structural Characterization