Synthesis and photoluminescent properties of two 2D and 3D iodocuprates modified by a protonated ligand

Song, Jianjian; Hou, Yajie; Zhang, Lifang; Fu, Yongqi

doi:10.1039/c1ce05020f

Cited by 33 publications

(15 citation statements)

References 64 publications

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“…[53][54] To data, numerous [Cu x X y ] (y-x)-anionic clusters or 6-, etc, have also been reported and characterized. [67][68][69][70][71][72][73][74][75][76][77][78][79][80] Relatively, three-dimensional (3D) frameworks are rarely documented with limited topological networks.…”

Section: Introductionmentioning

confidence: 99%

“…However, most of the SBUs are self-condensed to form etc [67][68][69][70][71][72][73][74][76][77][78][79][80] Occasionally, these SBUs can also be interlinked to form 2D microporous layers, for example, two isomeric 2D [Cu11 I 17 ] 6-layers are composed of [Cu 3 I 7 ], [Cu 4 I 8 ], [Cu 6 I 12 ] and [Cu 12 I 22 ] units in [deDABCO] 2 [meDABCO]Cu 11 I 17 . 74 Undoubtedly, the 2D [Cu 6 I 11 ] 5-layer reported here based on trimeric [Cu 3 I 7 ] building blocks represents new microporous layer in hybrid iodocuprate chemistry.…”

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confidence: 99%

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Low-Dimensional Hybrid Cuprous Halides Directed by Transition Metal Complex: Syntheses, Crystal Structures, and Photocatalytic Properties

Lei

Yue

Zhao

et al. 2015

Crystal Growth & Design

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By using transitional metal (TM) complex cations as structure-directing agents (SDAs), a series of new hybrid cuprous halides have been solvothermally synthesized and structurally characterized. The title compounds feature abundant architectures ranging from one-dimensional (1D) chains to two-dimensional (2D) layers built from the self-condensation of [CuX4] tetrahedrons and/or [CuX3] triangles. The UV-vis diffuse-reflectance measurements reveal that the title compounds possesses semiconductor behaviors with smaller band gaps of 1.44-1.95 eV, and show highly efficient photocatalytic degradation activities over organic pollutant than N-doped P25 under visible light irradiation. 661x495mm (96 x 96 DPI) AbstractBy using transitional metal (TM) complex cations as structure-directing agents (SDAs), a series of new hybrid cuprous halides with abundant architectures ranging from one-dimensional (1D) ribbons to two-dimensional (2D) layers have been solvothermally prepared and structurally characterized.Compounds [TM(2,2-bipy) 3 ]Cu 5 I 7 (TM = Fe (1), Co(2) and Ni (3)) feature 1D [Cu 5 I 7 ] 2-chains formed by the interconnection of [Cu 5 I 10 ] units via edge-sharing. In compounds [TM(2,2-bipy) 2 I] 2 Cu 7 I 9 (TM = Mn (4), Cu(5), Ru (6)), the [Cu 5 I 9 ] units and [Cu 2 I 6 ] dimers are alternately interlinked via edge-sharing to form the 1D [Cu 7 I 9 ] 2-chains. Compound [Cu(2,2-bipy) 2 I][(Me) 2 -2,2-bipy]Cu 8 I 11 (7) contains a new 1D [Cu 8 I 11 ] 3-chain composed of complex [Cu 8 I 13 ] units based on CuI 4 tetrahedra and CuI 3 triangles. Compound [Co(2,2-bipy) 3 ]Cu 5 Br 8 (8) features 1D [Cu 5 Br 8 ] 3-anionic chain built form the interconnection of [Cu 6 Br 10 ] units and linear [Cu 4 Br 8 ] tetramers. In compound K[Mn(2,2-bipy) 3 ] 2 Cu 6 I 11 (9), the [Cu 3 I 7 ] secondary building units (SBUs) are directly interconnected to form 2D [Cu 6 I 11 ] 5-layers, which are further interconnected by K + ions via weak K-I bonds to generate a 3D [K@Cu 6 I 11 ] 4-framework with 1D large channels occupied by [Mn(2,2-bipy) 3 ] 2+ complexes. The UV-vis diffusereflectance measurements reveal that the title compounds possess semiconductor behaviors with smaller band gaps of 1.44-1.95 eV, and samples 4, 5 and 9 show highly efficient photocatalytic degradation activities over organic pollutant than N-doped P25 under visible light irradiation.

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Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

Low-Dimensional Hybrid Cuprous Halides Directed by Transition Metal Complex: Syntheses, Crystal Structures, and Photocatalytic Properties

Lei

Yue

Zhao

et al. 2015

Crystal Growth & Design

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“…Both Cu(5) and Cu(10) atoms were coordinated by three I anions to form Cu(5)I 3 and Cu(10)I 3 triangles as shown in Figure . The mean Cu–I bond length of the four‐coordinate copper ions was 2.678 Å, which was in the range of those found in similar complexes such as [Cu 4 I 5 (DABCOH + )CH 3 CN] [2.6260(7) Å–2.7654(7) Å] and [Cu I 4 (Ln)I 5 ] n [Ln = 3,5‐bis(1‐ethylpyridinium‐4‐yl)‐1,2,4‐triazol‐4‐ide] but longer than that in [isopropylviologen][CuI 3 ] (2.526(1) Å, isopropylviologen = N , N ′‐diisopropyl‐4,4′‐bipyridinium) and [Tab‐Tab][CuI 3 ] [2.530(1) Å, Tab‐Tab = 4‐(trimethylammonio)phenyldisulfide] . The average of Cu–I bond lengths of Cu(5)I 3 and Cu(10)I 3 was 2.531 Å, obviously shorter than the Cu–I distances in the CuI 4 tetrahedra in compound 2 .…”

Section: Resultsmentioning

confidence: 49%

“…The central copper(I) cation may exhibit two‐, three‐, four‐, or sixfold coordination forming rhombohedral Cu 2 I 2 units, linear [CuBr 2 ] – entities, ladder‐like [Cu 2 Br 3 ] – [6] edge‐shared or bi‐bridged Cu 2 Br 6 4– , Cu 2 X 6 4– dimers (X = Cl, Br, I), triangular [Cu 3 Br] or CuNX 2 units, tetrahedral Cu 2 X 2 /CuX 4 /Cu 2 X 6 /Cu 4 I 4 clusters, and distorted tetrahedral CuBr 4 2– [13] or octahedral CuX 6 coordination complexes . The great number of Cu coordination environment realized with halogen atoms (X) gives rise to a plethora of coordination polymers such as 1D (CuX) ∞ chains, 0D Cu 8 I 8 “double‐chains”, (CuX) ∞ columnar frameworks, (CuBr) ∞ , (CuI) ∞ layer, or 2D cuprous iodide layer Cu 4 I 5 – …”

Section: Introductionmentioning

confidence: 99%

Microwave‐assisted Synthesis, Crystal Structures, and Thermal Stability of C₁₁H₁₀N₂Cu₂Br₃ and C₂₂H₂₀N₄Cu₈I₁₀

Deng

Rao

et al. 2018

Zeitschrift anorg allge chemie

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Complexes of C11H10N2Cu2Br3 (1) and C22H20N4Cu8I10 (2) [C22H20N4 = 1,1"‐(1,2‐ethanediyl)‐bis‐4,4′‐bipyridinium] were synthesized via the microwave‐assisted solvo‐thermal reactions of C22H20N4Br2, CuSO4·5H2O, and NaX (X = Br, I) and characterized by XRD, FTIR, and thermogravimetric analysis. The crystal structures were determined by single‐crystal X‐ray diffraction analyses. C11H10N2Cu2Br3 crystallized in the monoclinic space group C2/c (no. 15) with lattice parameters a = 24.658(3) Å, b = 6.71(9) Å, c = 17.368(9) Å, β = 98.274(1)°, V = 2847.7(1) Å3, whereas C22H20N4Cu8I10 crystallized in the monoclinic space group P21/n (no. 14) with lattice parameters a = 7.392(2) Å, b = 20.809(7) Å, c = 25.412(7) Å, β = 92.06(8) °, V = 3906.6(8) Å3. Complex 1 showed a 2D layered structure composed of [Cu4Br6]– chains connected via 1,1"‐(1,2‐ethanediyl)‐bis‐4,4′‐bipyridinium ligands. Complex 2 possessed a 3D framework, in which puckered [Cu8I10]2– layers were linked by organic ligands. The thermogravimetric analysis indicated that both two complexes were stable up to 230 °C and 170 °C, respectively.

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“…Several halocuprates(I) with this anionic structural feature are described in the literature. The use of DABCO and its protonated forms in halocuprate(I) syntheses has yielded a Cu 4 I 6 2-cluster with an in-situ mono-methylated DABCO molecule 25 , and a 3D inorganic framework structure 26 . The same complex anion containing trans edgesharing tetrahedra was obtained with twofold protonated diamines such as ethylene diamine or piperazine as cations.…”

Section: Introductionmentioning

confidence: 99%

Halocuprate(i) zigzag chain structures with N-methylated DABCO cations – bright metal-centered luminescence and thermally activated color shifts

et al. 2015

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Two compounds 1,4-dimethyl-1,4-diazoniabicyclo[2.2.2]octane catena-tetra-μ-halo-dicuprate(I) with DABCOMe2 Cu2X4 (1: X = Br, 2: X = I) were synthesized by hydrothermal reaction of copper(I) halides with the corresponding 1,4-diazoniabicyclo[2.2.2]octane (DABCO) dihydrohalides in an acetonitrile/methanol mixture. Both compounds crystallize monoclinically, 1 with a = 9.169(4) Å, b = 10.916(6) Å, c = 15.349(6) Å, β = 93.93(2)°, V = 1533(1) Å(3), Z = 4, space group P2(1)/n (no. 14) and 2 with a = 15.826(9) Å, b = 9.476(5) Å, c = 22.90(2) Å, β = 90.56(5)°, V = 3434(5) Å(3), Z = 8, space group P2(1) (no. 4), respectively (lattice constants refined from powder diffraction data measured at 293 K). The cations in both compounds are formed by in situ N-methylation of DABCOH2(2+) cations by methanol in a S(N)2 reaction. Both compounds contain an anionic copper(I) halide chain structure consisting of trans edge-sharing CuX4 tetrahedra. The chains are strongly kinked at every 2(nd) junction thus forming a zigzag structure. The shortest halide-halide distances are observed between the halide ions of adjacent tetrahedra which are approaching each other due to the kinking. This structure type shows a specific luminescence behavior. Under optical excitation, the compounds exhibit yellow (1) and green (2) emission with photoluminescence quantum yields of Φ(PL) = 52 and 4%, respectively, at ambient temperature. According to DFT and TDDFT calculations, the emission is assigned to be a phosphorescence essentially involving a metal centered transition between the HOMO consisting mainly of copper 3d and halide p orbitals and the LUMO consisting mainly of copper 4s and 4p orbitals. The temperature dependence of the emission spectra, decay times, and quantum yields has been investigated in detail, especially for 1. From the resulting trends it can be concluded that the emission for T≤ 100 K stems from energetically lower lying copper halide segments. Such segments represent the structural motif of the halocuprate(I) chains. With increasing temperature energetically higher lying segments are populated which also emit, but open the pathway for thermally activated energy transfer to quenching defects.

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Synthesis and photoluminescent properties of two 2D and 3D iodocuprates modified by a protonated ligand

Cited by 33 publications

References 64 publications

Low-Dimensional Hybrid Cuprous Halides Directed by Transition Metal Complex: Syntheses, Crystal Structures, and Photocatalytic Properties

Low-Dimensional Hybrid Cuprous Halides Directed by Transition Metal Complex: Syntheses, Crystal Structures, and Photocatalytic Properties

Microwave‐assisted Synthesis, Crystal Structures, and Thermal Stability of C₁₁H₁₀N₂Cu₂Br₃ and C₂₂H₂₀N₄Cu₈I₁₀

Halocuprate(i) zigzag chain structures with N-methylated DABCO cations – bright metal-centered luminescence and thermally activated color shifts

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Synthesis and photoluminescent properties of two 2D and 3D iodocuprates modified by a protonated ligand

Cited by 33 publications

References 64 publications

Low-Dimensional Hybrid Cuprous Halides Directed by Transition Metal Complex: Syntheses, Crystal Structures, and Photocatalytic Properties

Low-Dimensional Hybrid Cuprous Halides Directed by Transition Metal Complex: Syntheses, Crystal Structures, and Photocatalytic Properties

Microwave‐assisted Synthesis, Crystal Structures, and Thermal Stability of C11H10N2Cu2Br3 and C22H20N4Cu8I10

Halocuprate(i) zigzag chain structures with N-methylated DABCO cations – bright metal-centered luminescence and thermally activated color shifts

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Microwave‐assisted Synthesis, Crystal Structures, and Thermal Stability of C₁₁H₁₀N₂Cu₂Br₃ and C₂₂H₂₀N₄Cu₈I₁₀