Deep blue emitting Cu(<scp>i</scp>) tripod complexes. Design of high quantum yield materials showing TADF-assisted phosphorescence

Schinabeck, Alexander; Rau, N.; Klein, Marius; Yersin, Hartmut

doi:10.1039/c8dt04093a

Cited by 43 publications

(49 citation statements)

References 67 publications

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“…While for singlet harvesting, the molecules have to show efficient thermally activated delayed fluorescence (TADF) at ambient temperature. Examples are found among Cu(I), Ag(I), Au(III), W(VI) and Zn(II) complexes [ 7 , 9 , 10 , 11 , 12 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 , 50 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 , 61 , 62 , 63 , 64 , 65 ] or specifically designed organic molecules [ 66 , 67 , 68 , 69 , 70 , 71 , 72 , 73 , 74 , 75 , 76 ,…”

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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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: 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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“…Since the efficient organic-light emitting diodes (OLEDs) and light-emitting electrochemical cells (LEECs) based on Cu(I) complexes were reported by Wang group and Armaroli group (Zhang et al, 2004; Armaroli et al, 2006), respectively, luminescent Cu(I) complexes have been attracting considerable attention as the emitting materials for electroluminescent (EL) devices (Volz et al, 2014; Gneuß et al, 2015; Hofbeck et al, 2015; Kobayashi et al, 2016; Brunner et al, 2017; He et al, 2017; Huang et al, 2017; Su et al, 2017; Brown et al, 2018; Mohankumar et al, 2018; Schinabeck et al, 2018; Jia et al, 2019). According to the recent reports, most of Cu(I) complexes show thermally activated delayed fluorescence (TADF) due to small energy gaps (Δ E ST ) between the lowest singlet state (S 1 ) and the lowest triplet states (T 1 ) (Gneuß et al, 2015; Hofbeck et al, 2015; Kobayashi et al, 2016; Brunner et al, 2017; Huang et al, 2017; Su et al, 2017; Mohankumar et al, 2018; Schinabeck et al, 2018; Jia et al, 2019). As we all know, singlet and triplet excitons are formed in a ratio of 1:3 during EL device operation.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structures, and Photophysical Properties of Novel Four-Coordinate Cu(I) Complexes Supported by Chelating N-Heterocyclic Carbene Ligands

Wang

Sun

et al. 2019

Front. Chem.

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Luminescent Cu(I) complexes are promising emitting materials for electroluminescent devices due to their low cost and abundant resources, as well as high emission efficiency. It is well-known that N-heterocyclic carbenes (NHCs) are excellent ligands for transition metal complexes. To investigate the photophysical properties of Cu(I)-NHC complexes, a series of new mononuclear four-coordinate Cu(I) complexes supported by the diphosphine ligand bis[2-(diphenylphosphino)phenyl]ether (POP) and the NHC ligands, consisting of imidazolylidene and pyrimidine units, were synthesized and fully characterized. To tune the photophysical properties of these Cu(I)-NHC complexes, the NHC ligands were attached with electron-withdrawing/donating groups (fluorine, chlorine, methyl and methoxyl) at the pyrimidine unit. All of these Cu(I)-NHC complexes adopt the typical distorted tetrahedral configuration. The electron-donating groups can lead to shorter Cu–N bond distances and longer Cu–C bond distances compared to the electron-withdrawing groups. Theoretical calculation results show that the highest occupied molecular orbitals are mainly distributed on the Cu(I) ion, POP, and carbene unit, while the lowest unoccupied molecular orbitals are mostly located on the pyrimidine unit of NHC ligands. The lowest energy electronic transitions of these Cu(I)-NHC complexes are mainly the metal-to-ligand charge transfer transition and ligand-to-ligand charge transfer transition. These Cu(I)-NHC complexes in solid state show tunable emissions from 530 to 618 nm with efficiencies of 0.5–38.1% at room temperature. The photophysical behaviors of these complexes at 298 and 50 K match well with the thermally activated delayed fluorescence (TADF) characteristics.

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

Abstract: Triplet and singlet harvesting in combination with enhancing the emitter rigidity leads to a landmark value of the photoluminescence quantum yield for dissolved Cu(i) complexes.

Cited by 43 publications

References 67 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

Synthesis, Structures, and Photophysical Properties of Novel Four-Coordinate Cu(I) Complexes Supported by Chelating N-Heterocyclic Carbene Ligands

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

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