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New Cu(i) halide complexes showing TADF combined with room temperature phosphorescence : The balance tuned by halogens. / Baranov, Andrey Yu; Berezin, Alexey S.; Samsonenko, Denis G. и др.
в: Dalton Transactions, Том 49, № 10, 14.03.2020, стр. 3155-3163.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - New Cu(i) halide complexes showing TADF combined with room temperature phosphorescence
T2 - The balance tuned by halogens
AU - Baranov, Andrey Yu
AU - Berezin, Alexey S.
AU - Samsonenko, Denis G.
AU - Mazur, Anton S.
AU - Tolstoy, Peter M.
AU - Plyusnin, Viktor F.
AU - Kolesnikov, Ilya E.
AU - Artem'Ev, Alexander V.
N1 - Publisher Copyright: This journal is © The Royal Society of Chemistry. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.
PY - 2020/3/14
Y1 - 2020/3/14
N2 - A series of Cu(i) halide complexes derived from tris(2-pyridyl)phosphine (Py3P), [Cu2(Py3P)2X2] (X = Cl, Br, I), have been synthesized by a straightforward reaction in solution or through a mechanochemical route. At room temperature, the solid complexes exhibit bright dual-mode photoluminescence (λmax = 520-550 nm, τ = 14.5-20.0 μs, and ΦPL ≈ 53%), expressed by thermally activated delayed fluorescence (TADF) combined with phosphorescence (PH), originating from 1(M + X)LCT and 3(M + X)LCT excited states, respectively. Remarkably, the balance of these radiative processes at 300 K is regulated by halogen atom nature, switching from TADF-assisted phosphorescence to PH-admixed TADF. The emission of [Cu2(Py3P)2Cl2] at 300 K is largely contributed by PH (73%) admixed with the TADF fraction (27%) and [Cu2(Py3P)2Br2] also emits mainly PH (65%) admixed with the larger TADF fraction (35%). Meanwhile, for [Cu2(Py3P)2I2], the TADF channel becomes dominating (61%) and PH contribution drops to 39%. The photophysical study corroborated by (TD)DFT computations has revealed that this effect arises mainly from the narrowing of the ΔE(S1 - T1) gap of the [Cu2(Py3P)2X2] complexes in the order Cl (1500 cm-1) > Br (1250 cm-1) > I (1000 cm-1) which facilitates the TADF pathway and suppresses PH in the same order.
AB - A series of Cu(i) halide complexes derived from tris(2-pyridyl)phosphine (Py3P), [Cu2(Py3P)2X2] (X = Cl, Br, I), have been synthesized by a straightforward reaction in solution or through a mechanochemical route. At room temperature, the solid complexes exhibit bright dual-mode photoluminescence (λmax = 520-550 nm, τ = 14.5-20.0 μs, and ΦPL ≈ 53%), expressed by thermally activated delayed fluorescence (TADF) combined with phosphorescence (PH), originating from 1(M + X)LCT and 3(M + X)LCT excited states, respectively. Remarkably, the balance of these radiative processes at 300 K is regulated by halogen atom nature, switching from TADF-assisted phosphorescence to PH-admixed TADF. The emission of [Cu2(Py3P)2Cl2] at 300 K is largely contributed by PH (73%) admixed with the TADF fraction (27%) and [Cu2(Py3P)2Br2] also emits mainly PH (65%) admixed with the larger TADF fraction (35%). Meanwhile, for [Cu2(Py3P)2I2], the TADF channel becomes dominating (61%) and PH contribution drops to 39%. The photophysical study corroborated by (TD)DFT computations has revealed that this effect arises mainly from the narrowing of the ΔE(S1 - T1) gap of the [Cu2(Py3P)2X2] complexes in the order Cl (1500 cm-1) > Br (1250 cm-1) > I (1000 cm-1) which facilitates the TADF pathway and suppresses PH in the same order.
KW - ACTIVATED DELAYED FLUORESCENCE
KW - LIGHT-EMITTING-DIODES
KW - TRIPLET EXCITONS
KW - SINGLET
KW - EFFICIENCY
KW - EMITTERS
KW - PYRIDYL
UR - http://www.scopus.com/inward/record.url?scp=85081739263&partnerID=8YFLogxK
U2 - 10.1039/d0dt00192a
DO - 10.1039/d0dt00192a
M3 - Article
C2 - 32083636
AN - SCOPUS:85081739263
VL - 49
SP - 3155
EP - 3163
JO - Dalton Transactions
JF - Dalton Transactions
SN - 1477-9226
IS - 10
ER -
ID: 23805584