Organic cation directed one-dimensional cuprous halide compounds: syntheses, crystal structures and photoluminescence properties

Yue, Cheng‐Yang; Lin, Na; Gao, Lu; Jin, Ying-Xue; Cao, Y. N.; Han, Shasha; Lian, Xi-Kai; Hu, Bing; Lei, Xiao‐Wu

doi:10.1039/c9dt01460h

Cited by 27 publications

(15 citation statements)

References 57 publications

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“…The optical bandgaps were estimated by extrapolating the absorbing edge to the linear part and follow the order of (S-PCA)CuI 2 (2.70 eV), (S-PCA)CuBr 2 (2.87 eV), and (S-PCA)CuBr 2 •0.5H 2 O (3.66 eV). These bandgaps are comparable with other Cu(I) halides, such as [Me-Py]CuI 2 (2.80 eV), 48 [H 2 DABCO]Cu 3 Br 5 (3.44 eV), 48 and (R-MBA)CuBr 2 (4.10 eV). 47 Among these compounds, (S-PCA)CuI 2 has the smallest optical bandgap, with a corresponding light yellow color.…”

Section: ■ Results and Discussionsupporting

confidence: 73%

Chiral 2D Cu(I) Halide Frameworks

Geng

Zhang

et al. 2022

Chem. Mater.

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Hybrid multifunctional materials have great potential in a wide variety of applications due to their flexible combination of organic and inorganic components. Introducing chiral organic modules into the metal halide frameworks can effectively generate multifunctional materials, achieving new functionalities with noncentrosymmetric structures. Here, by incorporating (R)-or (S)-piperidine-3-carboxylic acid (R/S-PCA) as the templating cation, we report the synthesis and characterization of three pairs of new 2D chiral hybrid Cu(I) halides, namely, (R/S-PCA)CuBr 2 , (R/S-PCA)CuBr 2 •0.5H 2 O, and (R/S-PCA)CuI 2 . These chiral Cu(I) halides crystallize in the noncentrosymmetric space group C2 and belong to a new structural type similar to layered silicates. The optical absorption edges of these chiral materials can be tuned by changing the halide or upon the absorption of water and range from 2.70 to 3.66 eV. A dynamic conversion between (R/S-PCA)CuBr 2 and (R/S-PCA)CuBr 2 •0.5H 2 O occurs through exposure to moisture or vacuum drying along with changes in the reversible bandgap and photoluminescence. Chiroptical properties such as circular dichroism, circular polarized light emission, and second harmonic generation are investigated. Density functional theory calculations (DFT) show the indirect and direct bandgap natures of these Cu(I) halides and reveal the mechanism for the broadband self-trapped exciton emission at the excited state. The fascinating structural type, chiroptical properties, and reversible hydrochromic behavior of these Cu(I)-based halides make them viable candidates for next-generation multifunctional optoelectronic materials.

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Section: ■ Results and Discussionsupporting

confidence: 73%

Chiral 2D Cu(I) Halide Frameworks

Geng

Zhang

et al. 2022

Chem. Mater.

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“…The fitted activation energies ( E a ) are 57 meV for 1 and 48 meV for 2 , which are close to those of organic hybrid metal halides (43–81 meV). 18 The decay curves of 1 and 2 obey the second-order exponential decay, further proving that Cu + /Pb 2+ ions lie in the different coordinated environments. The average lifetime of 1 increases from 6.09 μs at 300 K to 11.86 μs at 80 K (Fig.…”

Section: Resultsmentioning

confidence: 78%

Two luminescent cuprous iodides with hitherto-unknown free imidazolate sites for efficiently sensing Fe³⁺ and Cr₂O₇²⁻

2022

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“…Luminescent thermochromic materials display high sensitivity and visual emission colorimetric responses to temperature variation, making them potential candidates for temperature sensing. − Metal halides possess diverse structures and excellent luminescent properties, including long lifetimes, moderate brightness, high quantum yield, and large Stokes shifts. − Particularly, some Cu/Ag halides exhibit interesting luminescent thermochromic properties, including wavelength shift, dual emission, or a combination of both with varying temperature. ,, These advantages provide new opportunities to construct wavelength-dependent and ratiometric LTs. For examples, Li’s group designed a dual-emitting [Cu 6 L 3 (Cu 2 I 2 )–Cu 6 L 3 ] cluster with a highly sensitive ratiometric LT, which has high thermal stability and a wide sensing range (120–450 K) .…”

Section: Introductionmentioning

confidence: 99%

Luminescent Thermochromic Silver Iodides as Wavelength-Dependent Thermometers

et al. 2020

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Luminescent thermochromic materials with a dramatic shift of emission band under different temperatures are highly desirable in temperature sensing fields. However, the design of the synthesis of such compounds remains a great challenge. In this work, two new luminescent thermochromic silver iodides, (emIm)Ag3I4 (1) and (emIm)Ag2I3 (2) (emIm = 1-ethyl-3-methyl imidazole), have been synthesized under solvothermal conditions. Compound 1 features a [Ag3I4]− anionic layer, while compound 2 possesses an infinite [Ag2I3]− chain structure, both of which are charge balanced by emIm+ cations. Particularly, they display luminescent thermochromism with a significant wavelength shift of emission maximum with temperature change. They represent rare examples of infinite layered or chain silver iodides that show luminescent thermochromism. Furthermore, the results indicate that compounds 1 and 2 are promising wavelength-dependent luminescent thermometers.

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Organic cation directed one-dimensional cuprous halide compounds: syntheses, crystal structures and photoluminescence properties

Abstract: One-dimensional organic–inorganic hybrid cuprous halides exhibit strong tunable photoluminescence from cyan to red emissions with large Stokes shifts.

Cited by 27 publications

References 57 publications

Chiral 2D Cu(I) Halide Frameworks

Chiral 2D Cu(I) Halide Frameworks

Two luminescent cuprous iodides with hitherto-unknown free imidazolate sites for efficiently sensing Fe³⁺ and Cr₂O₇²⁻

Luminescent Thermochromic Silver Iodides as Wavelength-Dependent Thermometers

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Organic cation directed one-dimensional cuprous halide compounds: syntheses, crystal structures and photoluminescence properties

Abstract: One-dimensional organic–inorganic hybrid cuprous halides exhibit strong tunable photoluminescence from cyan to red emissions with large Stokes shifts.

Cited by 27 publications

References 57 publications

Chiral 2D Cu(I) Halide Frameworks

Chiral 2D Cu(I) Halide Frameworks

Two luminescent cuprous iodides with hitherto-unknown free imidazolate sites for efficiently sensing Fe3+ and Cr2O72−

Luminescent Thermochromic Silver Iodides as Wavelength-Dependent Thermometers

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Product

Resources

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Two luminescent cuprous iodides with hitherto-unknown free imidazolate sites for efficiently sensing Fe³⁺ and Cr₂O₇²⁻