Bis[bis(12-crown-4)potassium] hexaiodotetracuprate(I)

Paulsson, Heléne; Fischer, Andreas; Kloo, Lars

doi:10.1107/s1600536804007780

Cited by 8 publications

(8 citation statements)

References 2 publications

(2 reference statements)

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“…Still, there is no doubt about the reliability of the model. The one dimensionally infinite chain is similar to that found by Kloo et al 18 and by Holt et al 10,19,20 with the counterion 12-crown-4-potassium or sodium. The structure contains two crystallographically independent [I 3 Cu 2 ] À chains, one occupying a high symmetry position (on the centre of inversion) and the other occupying a general position.…”

Section: Catena Tetrakis(tetramethylammonium) Bis(m 3 -Iodo)-m 2iodo-...supporting

confidence: 83%

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Size matters—sometimes. The [CuxIy](y−x)−(NR4)+(y−x) systems

Jalilian

Lidin

2011

CrystEngComm

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A systematic study of compounds formed by solvolysis of Cu in a solution of iodine in acetol in the presence of homotetraalkylammonium iodide has resulted in five new compounds: catena tetrakis (tetramethylammonium) bis(m 3 -iodo)-m 2 -iodo-tri-copper(I), hexakis(tetrabutylammonium) tetrakis(m 3 -iodo)-tris(m 2 -iodo)-di-iodo-hexa-copper(I) pentakis(m 3 -iodo)-tetrakis(m 2 -iodo)-di-iodohepta-copper(I), tris(tetrapentylammonium) m 6 -iodo-bis(m 3 -iodo)-hexakis(m 2 -iodo)-hexa-copper(I), hexakis(tetrahexylammonium) tetrakis(m 5 -iodo)-octakis(m 2 -iodo)-nona-copper(I)bis(m 5 -iodo)-bis(m 4iodo)-heptakis(m 2 -iodo)-octa-copper(I) and bis(tetraheptylammonium) hexakis(m 2 -iodo)-tetra-copper (I). Further the previously reported compounds catena tetraethylammonium bis(m 3 -iodo)-m 2 -iodo-dicopper(I) and catena tetrapropylammonium tetra(m 3 -iodo)-tri-copper(I) were produced by the same method. The complexity of the cuprous iodide clusters increases with increasing chain length of the counter ion. In the system with tetraheptylammonium as counter ion, the onset of crystallization was about two years! The luminescence properties that make some cuprous iodide cluster species interesting from an applications perspective are conspicuously absent in the compounds formed with the smaller tetraalkylammonium counter ions, but the compound formed with tetraheptylammonium contains the [Cu 4 I 6 ] 2À unit that shows vivid luminescence when exposed to UV light.

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Section: Catena Tetrakis(tetramethylammonium) Bis(m 3 -Iodo)-m 2iodo-...supporting

confidence: 83%

“…A, a ¼ 100.2178 (19) , b ¼ 94.2642(18) and g ¼ 94.0048 (18) . All crystals examined were twinned almost according to the twin matrix [1 0 À0.5; 0 1 À1; 0 0 À1].…”

Section: Catena Tetrakis(tetramethylammonium) Bis(m 3 -Iodo)-m 2iodo-...mentioning

confidence: 99%

Size matters—sometimes. The [CuxIy](y−x)−(NR4)+(y−x) systems

Jalilian

Lidin

2011

CrystEngComm

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“…2). The structure of the polymer is similar to those found in [K(12-crown-4) 2 ] 2n Cu 4 I 6 n , 57 The lack of the chiral ligand H 2 2 in the crystallized product clearly indicates that the latter is not the catalytically active species. Nonetheless, the data suggest that copper(I) may survive the conditions used for the asymmetric Henry reaction (entries 12-14, Table 3).…”

Section: Catalyst Screening: Copper(i) Saltssupporting

confidence: 62%

Enantioselective catalysts for the Henry reaction: fine-tuning the catalytic components

et al. 2009

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Catalysts for the asymmetric Henry reaction involving 1,6-bis(3-ethoxy-2-hydroxyphenyl)-(3S,4S)-(À)-diphenyl-2,5-diazahexane (H 2 2) and copper salts have been investigated. Conditions for the conversion of 4-nitrobenzaldehyde to 2-nitro-1-(4-nitrophenyl)ethanol by reaction with nitromethane have been optimized (5 mol% H 2 2, 10 mol% CuI, THF, 295 K and 2 hours or 273 K and 12 hours) resulting in 99% yield and 90-92% ee. These catalytic conditions are effective for other aromatic aldehydes containing electron-withdrawing substituents, and for pyridine carbaldehydes; representative aliphatic aldehydes were converted to the respective b-hydroxynitro derivatives with good enantioselectivities, and in moderate yields. These catalytic conditions were found to be ineffective for simple aromatic aldehydes or those containing electron-releasing substituents. Experimental GeneralCommercially available chemicals were of reagent grade and used without further purification. 1 H and 13 C NMR spectra Scheme 1 Structures of ligands and labeling for NMR spectroscopic assignment of H 2 2. Scheme 2 Catalytic asymmetric Henry reaction of 4-nitrobenzaldehyde and nitromethane.

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“…Typically, because of the d 10 closed shell of Cu(I), Cu(I) halides tend to have a tetrahedral geometry . Panels a–c of Figure show the crystal structure of [KC 2 ] 2 [Cu 4 I 6 ] (unit cell: a = 67.4428 Å, b = 69.0664 Å, c = 64.1181 Å, α = 14.5859°, β = 14.6371°, and γ = 15.6526°), which belongs to triclinic space group P 1̅ . It consists of sandwich-type [(12-crown-4) 2 K] + complex cations and polymeric [Cu 4 I 6 ] 2– anions.…”

Section: Results and Discussionmentioning

confidence: 99%

“…However, the peak wavelength of the excitation spectrum is located at ∼290 nm, which is in the deep ultraviolet range (200–350 nm). The same problem exists in other reported inorganic low-dimensional halide structures of copper(I), adding to the difficulty for practical LED applications. ,,, Here, we have synthesized a copper-based organic–inorganic hybrid metal halide structure and found it possesses high-efficiency luminescent emission . As revealed by density functional theory (DFT) calculations, in 1D [KC 2 ] 2 [Cu 4 I 6 ], the 1D chains composed of copper halide tetrahedra contribute to most electronic states, and the organic part forms only a 1D electronic structure with isolated [Cu 4 I 6 ] 2– in the 2D direction.…”

Section: Introductionmentioning

confidence: 97%

One-Dimensional Lead-Free Halide with Near-Unity Greenish-Yellow Light Emission

et al. 2020

Chem. Mater.

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Low-dimensional metal halides (LDMHs), especially lead-based perovskites, have recently attracted a great deal of attention for their unique structures and optoelectronic properties. However, the toxicity of lead limits their practical applications. Herein, a lead-free one-dimensional copper-based halide [KC 2 ] 2 [Cu 4 I 6 ] (C = 12-crown-4 ether) was constructed, which exhibits greenish-yellow emission (545 nm) with a near-unity photoluminescence quantum yield (∼97.8%). To the best of our knowledge, this is the highest value that has been achieved in leadfree greenish-yellow light-emitting LDMHs. Density functional theory calculations combined with comprehensive spectroscopic data revealed the characteristics of self-trapped exciton emission. Finally, we explored the application of the [KC 2 ] 2 [Cu 4 I 6 ] phosphor by fabricating the white light-emitting diode (WLED) device. The WLEDs fabricated using commercially available blue (450 nm) and ultraviolet (365 nm) as the excitation source both present excellent luminescence properties with a high color rendering index and a suitable corresponding color temperature. Our findings not only expand the library of highly efficient luminescent materials but also highlight the potential of low-dimensional copper-based halides in optoelectronics.

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Bis[bis(12-crown-4)potassium] hexaiodotetracuprate(I)

Cited by 8 publications

References 2 publications

Size matters—sometimes. The [CuxIy](y−x)−(NR4)+(y−x) systems

Size matters—sometimes. The [CuxIy](y−x)−(NR4)+(y−x) systems

Enantioselective catalysts for the Henry reaction: fine-tuning the catalytic components

One-Dimensional Lead-Free Halide with Near-Unity Greenish-Yellow Light Emission

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