Synthesis, crystal, luminescent properties and electronic structures of two copper(I) halide polymers based on Cu4I4 cubane tetramers

The authors have designed and synthesized a family of high-performance inorganic-organic hybrid phosphor materials composed of extended and robust networks of one, two, and three dimensions. Following a bottomup solution-based synthetic approach, these structures are constructed by connecting highly emissive Cu 4 I 4 cubic clusters via carefully selected ligands that form strong CuN bonds. They emit intensive yellow-orange light with high luminescence quantum efficiency, coupled with large Stokes shift, which greatly reduces self-absorption. They also demonstrate exceptionally high framework-and photostability, comparable to those of commercial phosphors. The high stabilities are the result of significantly enhanced CuN bonds, as confirmed by the density functional theory (DFT) binding energy and electron density calculations. Possible emission mechanisms are analyzed based on the results of theoretical calculations and optical experiments. Two-component white phosphors obtained by blending blue and yellow emitters reach an internal quantum yield as high as 82% and correlated color temperature as low as 2534 K. The performance level of this subfamily exceeds all other types of Cu-I based hybrid systems. The combined advantages make them excellent candidates as alternative rare-earth element-free phosphors for possible use in energy-efficient lighting devices.

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A Systematic Approach to Achieving High Performance Hybrid Lighting Phosphors with Excellent Thermal‐ and Photostability

Liu

et al. 2016

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Copper Iodide Based Hybrid Phosphors for Energy‐Efficient General Lighting Technologies

Liu

2018

Adv Funct Materials

221

200

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Solid-state-lighting (SSL) technology is a new lighting technology that is rapidly replacing conventional lighting sources because it is much more energy efficient, longer lasting, and contributes significantly to the environmental protection. A main branch of SSL technology are light-emitting diodes (LEDs), and white-light LEDs (WLEDs) are of the greatest demand for general lighting and illumination applications. Current WLED devices rely heavily on rare-earth elements (REEs), which will likely suffer from cost and supply risks and environmental consequences in the near future. Crystalline inorganic-organic hybrid materials based on I-VII binary semiconductors represent a promising material class as REE-free phosphor alternatives. This article provides an brief overview of recent advancement on this material family, with a focus on the rational design, energy efficient and This article is protected by copyright. All rights reserved. 2 low cost synthesis, systematic modification and optimization of their electronic, optical and thermal properties. A particular emphasis will be made on our own progress over the past several years in developing four classes of CuI(L) structures with substantially improved performance as energy-saving lighting phosphors. General strategies for structural design, synthesis and property optimization of these materials will also be discussed.

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Making Copper(0) Nanoparticles in Glycerol: A Straightforward Synthesis for a Multipurpose Catalyst

et al. 2017

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Dedicatedt ot he Laboratoire HØtØrochimieF ondamentale et AppliquØeo nt he occasiono fi ts 50 th anniversary.Supporting information for this article is availableunder https://doi.org/10.1002/adsc.201700535.Abstract: Small zero-valent copper nanoparticles (CuNPs) have been straightforwardly preparedf rom Cu(I) andC u(II) precursors in glycerol andi nt he presence of polyvinylpyrrolidone as stabilizer. Thanks to the negligible vaporp ressure of the solvent, these original nano-systems could be directly characterized in glycerol as well as in the solids tate, exhibiting relevantly homogeneous colloidal dispersions,a lso evena fter catalysis. CuNPs coming from the well-defined coordinationc omplex di-m-hydroxobis[(N,N,N',N'-tetramethylethylenediamine)copper(II)] chloride {[Cu(k 2 -N,N-TMEDA)(m-OH)] 2 Cl 2 } have been highly efficient in C-C andC -heteroatom bond formation processes. This newc atalytic system has proved its performance in C-Nc ouplings and in the synthesis of differently substitutedp ropargylic amines throughc ross-dehydrogenative couplings, multi-component reactions such as A 3 (aldehydealkyne-amine) and KA 2 (ketone-alkyne-amine) couplings,a sw ell as in the formationo fh eterocycles such as benzofurans,i ndolizines,a nd quinolines under smoothc onditions.N os ignificant copper amount was detected in the extracted organic compounds from the catalytic phase by inductively coupled plasma-atomic emission spectroscopic (ICP-AES)analyses,p roving ah ighly efficient immobilization of copper nanoparticles in glycerol. From am echanisticp oint of view,s pectroscopic data (infrareda nd ultraviolet-visible spectra) agreew ith asurface-like catalytic reactivity.

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Synthesis, crystal, luminescent properties and electronic structures of two copper(I) halide polymers based on Cu4I4 cubane tetramers

Cited by 17 publications

References 31 publications

A Systematic Approach to Achieving High Performance Hybrid Lighting Phosphors with Excellent Thermal‐ and Photostability

A Systematic Approach to Achieving High Performance Hybrid Lighting Phosphors with Excellent Thermal‐ and Photostability

Copper Iodide Based Hybrid Phosphors for Energy‐Efficient General Lighting Technologies

Making Copper(0) Nanoparticles in Glycerol: A Straightforward Synthesis for a Multipurpose Catalyst

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