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

Abstract

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.

Quaternary Phosphorus‐Induced Iodocuprate(I)‐Based Hybrids: Water Stabilities, Tunable Luminescence and Photocurrent Responses

“…The Cu–I distances follows the following approximate order: d(Cu–µ 4 ‐I) > d(Cu–µ 3 ‐I) > d(Cu–µ 2 ‐I). This trend can also be observed in other iodocuprate hybrids , . Cu(1)I 4 , Cu(2)I 4 , Cu(3)I 4 , Cu(2) #1 I4 and Cu(3) #2 I4 (#1 x , – y + 1/2, z ‐1/2; #2 x , – y + 1/2, z + 1/2) tetrahedra are self‐condensed by edge‐sharing to generate a Cu 5 I 11 unit (Figure a).…”

A 3D Iodoplumbate Semiconducting Open Framework with Visible‐light‐induced Photocatalytic Performance

“…Inorganic‐organic halometallate hybrids have received great interest due to their distinctive properties inherited from inorganic and organic components as well as the potential properties resulting from their interactions . Reasonable design and fabrication halometallates based on the flexible molecular engineering and energy band engineering results in a new trend in solid state chemistry, leading to many multi‐functional materials with potential applications in various areas such as semiconductors, luminescence, ferroelectric, thermochromism, photochromism, etc . Actually, most of these depend on the nature of templates or structural directing agents (SDAs).…”

Tripyridine‐Derivative‐Derived Semiconducting Iodo‐Argentate/Cuprate Hybrids with Excellent Visible‐Light‐Induced Photocatalytic Performance

“…These materials, as well as the reported [(Me) 3 (4‐TPT)] 2 [Cu 12 I 18 ], [Pb 5 Cu 2 I 16 ][(Me) 2 (4‐TPT)] 2 , [Pb 3 Cu 6 I 14 ] [(Me) 3 (4‐TPT)] 2 and [Me 3 (4‐TPT)][Cu 5 I 8 ], possess narrow band gaps of 1.02–2.19 eV. The values are comparable to those of organic ammoniums or metal complex templated halide hybrids, which feature small band gaps and exhibit attractive optoelectronic properties. Therefore, we are delighted to discover that introducing N ‐alkylation TPT‐derivatives as SDAs in halides may be an effective synthetic strategy for regulating electronic band structures, which can decrease the band gap and accordingly increase visible‐light absorption.…”

“…For the efficient use of solar energy, the exploration of photocatalysts that is sensitive to visible‐light is of great significance. Metal halide‐based hybrids have attracted considerable attention due to their distinctive photoelectric properties . Particularly, the good performance in semiconducting properties make halides ideal candidates as efficient photocatalysts.…”

“…Lei and Yue et al. systematically investigated halogenides in the presence of transition metal‐complexes, which display efficient photocatalytic properties . Zhang, Fu, and co‐workers.…”