Tetranuclear Copper(I) Iodide Complexes: A New Class of X-ray Phosphors

Kirakci, Kaplan; Fejfarová, Karla; Martincik, J.; Nikl, M.; Lang, Kamil

doi:10.1021/acs.inorgchem.7b00240

Cited by 61 publications

(46 citation statements)

References 36 publications

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“…400–500 nm and a low-energy (LE) band at ca. 550–650 nm, usually ascribed to mixed metal-to-ligand and halide-to-ligand charge-transfer [ 3 (X + M)LCT] and cluster-centered ( 3 CC) transitions, respectively. ,,,− ,− Such assignment was supported by quantum chemical computations reported by Vitale el al. , and by de Angelis et al At RT or higher temperatures, the luminescence is dominated by the LE band contributed by the 3 CC state characterized by strong geometrical changes of metal-halide core relative to the ground state. A temperature decrease rigidifies the system, thus impeding such changes.…”

Section: Introductionmentioning

confidence: 90%

“…After appearance of the pioneer representatives of tetranuclear clusters of Cu 4 I 4 (Py- x ) 4 composition with luminescence depending on temperature, a huge diversity of copper(I) clusters with thermochromic behavior of luminescence have been synthesized. − Most of these compounds contain cubanelike copper-halogen core Cu 4 I 4 with a tetrahedral environment of copper ions. ,,,− , Such complexes demonstrate dual emission with a high-energy (HE) band at ca. 400–500 nm and a low-energy (LE) band at ca.…”

Section: Introductionmentioning

confidence: 99%

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Fresh Look on the Nature of Dual-Band Emission of Octahedral Copper-Iodide Clusters—Promising Ratiometric Luminescent Thermometers

et al. 2019

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For the first time, the 3(X + M)LCT origin of both the lowest excited triplet states of dual-emissive tetranuclear copper(I)-iodide complexes with the octahedral Cu4I4 core has been revealed using quantum chemical computations in contrast to the conventional assignment of the lowest-energy emission to the 3CC state. The unusual thermochromic behavior shown for dual emission from these states of Cu4I4 clusters stabilized by P,N-ligands allows optical ratiometric thermal sensing in a broad temperature range.

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Section: Introductionmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

Fresh Look on the Nature of Dual-Band Emission of Octahedral Copper-Iodide Clusters—Promising Ratiometric Luminescent Thermometers

et al. 2019

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“…Among Cu(I) NCs, copper iodide clusters, especially the cubane compound [Cu 4 I 4 L 4 ] (L = organic ligand), are the most popular luminophore, because of their abundant luminescence behavior under the influence of the interaction between metals. , According to reports, triphenylphosphine (PPh 3 )-capped Cu 4 I 4 ([Cu 4 I 4 (PPh 3 ) 4 ]) has two different isomers, namely the open-chair geometry structure and the cubane structure. − Importantly, the luminescence of copper iodide clusters is conformation-dependent: at room temperature, the cubane structure emits intense green light under UV irradiation, while the open-chair geometry structure is nonemissive . Usually, [Cu 4 I 4 (PPh 3 ) 4 ] exists in the open-chair geometry structure, which restricts the application of [Cu 4 I 4 (PPh 3 ) 4 ] in the field of luminescent materials.…”

Section: Introductionmentioning

confidence: 99%

Solvent-Induced Self-Assembly of Copper Nanoclusters for White Light Emitting Diodes

Zhou

Zhang

et al. 2021

ACS Appl. Nano Mater.

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As a type of luminescent material, copper nanoclusters (Cu NCs) are widely concerned because of their low cost, nontoxicity, and outstanding biocompatibility. However, research studies on the preparation of hydrophobic Cu NCs with high quantum yield can be improved. In this work, we first synthesized atomically precise triphenylphosphine (PPh 3 )-capped Cu NCs (Cu 4 −NCs). Second, we adopted solvent engineering strategies to trigger the self-assembly of Cu 4 −NCs into the assembly with branched structures, thereby achieving aggregation-induced emission (AIE), thermally activated delayed fluorescence (TADF), and a high absolute quantum yield of 67.05%. Moreover, we performed structural characterization and optical analysis, which revealed that the high compactness of the assembly enhances the cuprophilic interaction and suppresses the intramolecular vibration and rotation of the Cu 4 −NCs ligand, protecting the Cu core from singlet oxygen quenching. These properties lead to the emergence of TADF and AIE. By mixing the as-assembled Cu 4 −NCs with commercial phosphors, a white light emitting diode prototype can be fabricated. This research demonstrates that TADF emission and the robust luminescence structure of the Cu 4 − NCs assembly provide them a high application value and extend the research opportunities for metal NCs in optical devices.

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“…These intermolecular interactions synergistically rigidify the metal-organic framework, which favors the additional structural stability at high temperatures. [45][46][47][48][49][50][51] Both single-crystal and powder XRD patterns of bppCu 4 I 4 P 4 revealed a reversible structural transformation with changing temperature (Fig. 2a and Supplementary Fig.…”

Section: Resultsmentioning

confidence: 99%

A cluster-based phosphor against thermal quenching via dynamic metallic bonding

Miao

et al. 2022

Preprint

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The effect of dynamic chemical bonding on material properties has long been the subject of intensive investigation in the fields of chemistry and materials. Especially, the dynamic metallic bonding is uncommon because the intermetallic electronic interaction may respond to external stimuli, which potentially builds the synergistic coupling among many physical properties. Herein, we experimentally investigate a dynamic Cu‒Cu bonding interaction that dictates the thermal quenching effect of photoluminescence (PL) in a high-efficiency metal-halide cluster-based phosphor. The weakening of Cu−Cu bonding in such a phosphor system enables the release of bonding electrons from Cu(I) 3d-orbital and hence sustains the PL efficiency at high temperatures (up to 100 oC). The temperature-dependent structural, NMR and EPR measurements reveal a reversible transition from diamagnetic Cu(I) to paramagnetic Cu(II) species. The white light-emitting diodes (LEDs) incorporating the thermally stable phosphor show a rapid brightness rise even at a high bias current (1,000 mA) with color rendering index as high as 90, comparable to the commercial phosphor-based prototype LEDs (e.g., YAG:Ce3+). This work establishes a novel prototype of cluster-based phosphor featuring dynamic metallic bonding, which paves the way for exploration of phosphor-converted LEDs against thermal quenching.

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Tetranuclear Copper(I) Iodide Complexes: A New Class of X-ray Phosphors

Cited by 61 publications

References 36 publications

Fresh Look on the Nature of Dual-Band Emission of Octahedral Copper-Iodide Clusters—Promising Ratiometric Luminescent Thermometers

Fresh Look on the Nature of Dual-Band Emission of Octahedral Copper-Iodide Clusters—Promising Ratiometric Luminescent Thermometers

Solvent-Induced Self-Assembly of Copper Nanoclusters for White Light Emitting Diodes

A cluster-based phosphor against thermal quenching via dynamic metallic bonding

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