Sky-blue thermally activated delayed fluorescence (TADF) based on Ag(<scp>i</scp>) complexes: strong solvation-induced emission enhancement

Artem’ev, Alexander V.; Shafikov, Marsel Z.; Schinabeck, Alexander; Антонова, О. В.; Berezin, Alexey S.; Bagryanskaya, I. Yu.; Plusnin, P. E.; Yersin, Hartmut

doi:10.1039/c9qi01069f

Cited by 45 publications

(42 citation statements)

References 62 publications

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“…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 ]. To evaluate the class of materials of Cu 2 X 2 (P∩N) 3 complexes (with X = Cl, Br, I), we study eight compounds with respect to their crystal structures and, especially, their emission properties at T = 300 K and 77 K, respectively.…”

Section: Introductionmentioning

confidence: 91%

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: 91%

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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“…The highenergy (HE) shoulders, with λmax ≈ 280 nm, are nearly the same for both compounds, while the lowenergy (LE) ones maximize at ≈350 nm for 1 and at ≈390 nm for 2. Considering the literature data [38], the HE absorption band can be attributed to intraligand π-π * and n-π * transitions. The LE band is FT-IR spectra of solid 1 and 2 are in agreement with sc-XRD data, showing characteristic vibrations of the ligand L along with stretching vibrations of the counter-ions (Figure S1).…”

Section: Synthesis and Characterizationmentioning

confidence: 74%

“…The high-energy (HE) shoulders, with λ max ≈ 280 nm, are nearly the same for both compounds, while the low-energy (LE) ones maximize at ≈350 nm for 1 and at ≈390 nm for 2. Considering the literature data [38], the HE absorption band can be attributed to intraligand π-π * and n-π * transitions. The LE band is likely associated with promotions of MLCT kind, which is typical for emissive Ag(I) complexes [22][23][24][25][26][27][36][37][38][39][40].…”

Section: Synthesis and Characterizationmentioning

confidence: 74%

“…Considering the literature data [38], the HE absorption band can be attributed to intraligand π-π * and n-π * transitions. The LE band is likely associated with promotions of MLCT kind, which is typical for emissive Ag(I) complexes [22][23][24][25][26][27][36][37][38][39][40].…”

Section: Synthesis and Characterizationmentioning

confidence: 74%

“…On account of highly electron-donating ligands, the silver d 10 orbitals begin to contribute to HOMO and near-HOMO, while the π-acceptors facilitate charge transfer from the metal. As a result, (M + L')LCT excited states can be generated, thereby inducing thermally activated delayed fluorescence (TADF) in Ag(I) compounds [22][23][24][25][26][27][36][37][38][39][40][41][42]. In the context of OLED application, it is relevant to note that the (M + L')LCT emission of Ag(I) benefits over that of Cu(I) analogues since the former (i) is shorter in the lifetimes [36,41,42], and (ii) generally appears in the higher energy domain [36,37,39,[43][44][45].…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Thermochromic Luminescence of Ag(I) Complexes Based on 4,6-Bis(diphenylphosphino)-Pyrimidine

et al. 2020

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Two Ag(I)-based metal-organic compounds have been synthesized exploiting 4,6-bis(diphenylphosphino)pyrimidine (L). The reaction of this ligand with AgNO3 and AgBF4 in acetonitrile produces dinuclear complex, [Ag2L2(MeCN)2(NO3)2] (1) and 1D coordination polymer, [Ag2L(MeCN)3]n(BF4)2n (2), respectively. In complex 1, µ2-P,P′-bridging coordination pattern of the ligand L is observed, whereas its µ4-P,N,N′,P′-coordination mode appears in 2. Both compounds exhibit pronounced thermochromic luminescence expressed by reversible changing of the emission chromaticity from a yellow at 300 K to an orange at 77 K. At room temperature, the emission lifetimes of 1 and 2 are 15.5 and 9.4 µs, the quantum efficiency being 18 and 56%, respectively. On account of temperature-dependent experimental data, the phenomenon was tentatively ascribed to alteration of the emission nature from thermally activated delayed fluorescence at 300 K to phosphoresce at 77 K.

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Aggregation‐Induced Emission in a Flexible Phosphine Oxide and its Zn(II) Complexes—A Simple Approach to Blue Luminescent Materials

Kirst

Knechtel

Gensler

et al. 2023

Adv Funct Materials

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Easily accessible blue-emitting materials are in the focus of ongoing research, as they still lack the efficiency and lifetime of their red and green counterparts. The new multidentate phosphine oxide ligands and two respective ZnCl 2 complexes presented here combine a straightforward synthesis with high yields and show interesting luminescent properties. The free ligand exhibits blue luminescence in the crystalline state, but not in amorphous films or diluted solution. In contrast, the Zn(II) complexes shows intense blue luminescence in the crystalline state as well as in amorphous thin films and in solution. Fluorescence lifetime imaging microscopy measurements show luminescence lifetimes of 3-6 ns indicative of fluorescence. By combining the experimental data with quantum chemical calculations, we propose a model where the conformation of the molecule is restricted, either via the crystal environment, aggregation, or the steric fixation by the coordinating central atom, blocking the nonradiative relaxation from the excited into the ground electronic state. However, this nonradiative relaxation is still possible in the gas phase via elongation of a PC bond. These results may provide a general mechanism to explain the luminescence properties in a whole class of organic phosphine oxides.

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Sky-blue thermally activated delayed fluorescence (TADF) based on Ag(i) complexes: strong solvation-induced emission enhancement

Abstract: Remarkable solvation-induced emission enhancement is discovered on a new Ag(i) complex showing sky-blue thermally activated delayed fluorescence (TADF).

Cited by 45 publications

References 62 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 and Thermochromic Luminescence of Ag(I) Complexes Based on 4,6-Bis(diphenylphosphino)-Pyrimidine

Aggregation‐Induced Emission in a Flexible Phosphine Oxide and its Zn(II) Complexes—A Simple Approach to Blue Luminescent Materials

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