Highly efficient cold-white light emission in a [Au2CuCl2(P∩N)2]PF6type salt

Hobbollahi, Elnaz; List, Manuela; Hupp, Benjamin; Mohr, Fabian; Berger, Raphael J. F.; Steffen, Andreas; Monkowius, Uwe

doi:10.1039/c7dt00180k

Cited by 23 publications

(28 citation statements)

References 35 publications

(8 reference statements)

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“…The spin−orbit-corrected TDDFT shows four peaks, while without SOC only three peaks are observed; the second peak at 3.15 eV in SO-TDDFT matches that of 3.30 eV in the experiment. Several gold nanoclusters display a prominent absorption tail such as [Au 2 CuCl 2 (P∩N) 2 ](PF 6 ), 83 wherein P∩N ligand is 2diphenylphosphano-6-methylpyridine, which has been assigned to a S 0 → T 1 transition. The inclusion of spin−orbit coupling was required to simulate all the features observed in the experimental absorption spectra of Au 25 (SR) 18 − , 84 Pt(pop-BF 2 ), 85 and [Re(imidazole)(CO) 3 (phe)] + 86 as SOC affects excited-state character, relaxation dynamics, and radiative as well as nonradiative decay pathways.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Optical Properties of the Atomically Precise C₄ Core [Au₉(PPh₃)₈]³⁺ Cluster Probed by Transient Absorption Spectroscopy and Time-Dependent Density Functional Theory

et al. 2021

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Structural isomerism of [Au9(PPh3)8]3+ has been studied experimentally, mostly concerning the symmetry of the Au9 core. Recently, the C 4 isomer of [Au9(PPh3)8]3+ has been shown to exist in solution phase while the D 2h isomer is present in the solid state [Inorg. Chem. 2017, 56, 8319–8325]. In this work, geometric, electronic, and optical properties of C 4 [Au9(PPh3)8]3+ are investigated by using the combined second-order density-functional tight-binding (DFTB2) method and time-dependent density functional theory (TD-DFT) calculations with spin–orbit coupling. Additionally, the excited-state relaxation dynamics of the [Au9(PPh3)8]3+ cluster in dichloromethane and methanol solutions are studied using femtosecond transient absorption spectroscopy. [Au9(PPh3)8]3+ is optically pumped to different excited states by using 432, 532, and 603 nm light. For all three pump wavelengths, the photoexcitation event induces an excited-state absorption (ESA) band centered at 600 nm with decay time constants of 2.0 and 45 ps, which are attributed to intersystem crossing and nonradiative relaxation of [Au9(PPh3)8]3+, respectively. On the other hand, optical pumping of [Au9(PPh3)8]3+ using 432 nm light gives rise to an additional ESA band at 900 nm. This band exhibits fast relaxation through internal conversion with a time constant of ∼0.3 ps. Our combined computational and experimental study reveals that the excitation wavelength-dependent relaxation dynamics of the [Au9(PPh3)8]3+ cluster are related to the different electron densities of the excited states of [Au9(PPh3)8]3+, consistent with it possessing molecular-like electronic states.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Optical Properties of the Atomically Precise C₄ Core [Au₉(PPh₃)₈]³⁺ Cluster Probed by Transient Absorption Spectroscopy and Time-Dependent Density Functional Theory

et al. 2021

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“…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%

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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“…Complexes of coinage metals attract increasing attention due to their rich photophysical properties resulting from a large variety of excited states. − Intense and tunable room-temperature emission of Cu, Ag, and Au complexes is shown to have promising potential for their application in a number of important technological areas, such as photoluminescent chemical sensors − and electroluminescent devices. − Additional variations of the photoluminescent properties of coinage complexes are achieved by the combination of Au I /Cu I , Au I /Ag I , or Cu I /Ag I metals in a core of a complex, which as usual gives intensive emission characterized by a high quantum yield of photoluminescence. ,,− For the controlled formation of heterometallic complexes, a specific spatial arrangement of donor atoms in the ligands is required …”

Section: Introductionmentioning

confidence: 99%

Assembly of Heterometallic AuICu₂I₂ Cores on the Scaffold of NPPN-Bridging Cyclic Bisphosphine

et al. 2021

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The row of metallocyclic dinuclear gold(I) complexes with cyclic diphosphines, namely, P-pyridylethyl-substituted 1,5-diaza-3,7-diphosphacyclooctanes, has been obtained. Further interaction of the dinuclear gold(I) complexes with copper(I) iodide gave the first examples of hexanuclear AuI/CuI complexes containing two unusual trinuclear AuICu2I2 fragments. The structures of di- and hexanuclear complexes were confirmed by NMR spectroscopy, ESI mass spectrometry, elemental analysis, and single-crystal X-ray diffraction. All of the obtained complexes are moderate emitters in the solid state. Dinuclear gold(I) complexes displayed a greenish emission with the maxima in the emission spectra at ca. 550 nm. The obtained hexanuclear heterobimetallic AuI/CuI complexes are triplet solid-state blue emitters with the maximum in the emission spectra at 463 and 484 nm. According to the TD-DFT calculations, the observed emission of all studied complexes had a triplet origin and was caused by the 3CC or 3(MLCT) T1 → S0 transitions for dinuclear and hexanuclear complexes, respectively.

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Highly efficient cold-white light emission in a [Au₂CuCl₂(P∩N)₂]PF₆type salt

Cited by 23 publications

References 35 publications

Optical Properties of the Atomically Precise C₄ Core [Au₉(PPh₃)₈]³⁺ Cluster Probed by Transient Absorption Spectroscopy and Time-Dependent Density Functional Theory

Optical Properties of the Atomically Precise C₄ Core [Au₉(PPh₃)₈]³⁺ Cluster Probed by Transient Absorption Spectroscopy and Time-Dependent Density Functional Theory

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

Assembly of Heterometallic AuICu₂I₂ Cores on the Scaffold of NPPN-Bridging Cyclic Bisphosphine

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Highly efficient cold-white light emission in a [Au2CuCl2(P∩N)2]PF6type salt

Cited by 23 publications

References 35 publications

Optical Properties of the Atomically Precise C4 Core [Au9(PPh3)8]3+ Cluster Probed by Transient Absorption Spectroscopy and Time-Dependent Density Functional Theory

Optical Properties of the Atomically Precise C4 Core [Au9(PPh3)8]3+ Cluster Probed by Transient Absorption Spectroscopy and Time-Dependent Density Functional Theory

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

Assembly of Heterometallic AuICu2I2 Cores on the Scaffold of NPPN-Bridging Cyclic Bisphosphine

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Highly efficient cold-white light emission in a [Au₂CuCl₂(P∩N)₂]PF₆type salt

Optical Properties of the Atomically Precise C₄ Core [Au₉(PPh₃)₈]³⁺ Cluster Probed by Transient Absorption Spectroscopy and Time-Dependent Density Functional Theory

Optical Properties of the Atomically Precise C₄ Core [Au₉(PPh₃)₈]³⁺ Cluster Probed by Transient Absorption Spectroscopy and Time-Dependent Density Functional Theory

Assembly of Heterometallic AuICu₂I₂ Cores on the Scaffold of NPPN-Bridging Cyclic Bisphosphine