halide perovskites (LDHPs), the optically active inorganic blocks are separated and surrounded by insulating organic components with intrinsic quantum confinement effects, which readily leads to firmly confined bound excitons in the metal halide species under photo excitation. Simultaneously, the strong electronquantum coupling transiently localizes the excitons along with excited-state structural deformation, which produces selftrapped excitons (STE) with lower excited state energy. [4] Therefore, the bulk LDHPs always display strongly Stokes-shifted broadband light emissions, which are different from the narrow emission bands of 3D halide perovskites. [5] These distinctive luminescent performances endow LDHPs with a series of unique applications complementary to the 3D perovskites in solid-state lighting, X-ray scintillation, remote thermometry, and thermography, especially for white light emitting diodes (WLEDs). [6] Among all the PL qualities, PL quantum yield (PLQY) is one of the most important indicators for optoelectronic applications of hybrid halide perovskites. To achieve higher PLQY and more desirable luminescence performance, substantial optically active centers based on ns 2 electronic configuration of valence shell have been explored including Sn 2+ , Ge 2+ , Pb 2+ , Bi 3+ , and Sb 3+ . [7][8][9] In these fascinating hybrid metal halides, the 5s 2 metal halides readily occupy the maximum of emission efficiency owing to the unique expressed structural distortion level induced by the out shell lone pair. [10] Simultaneously considering the instabilities of Sn 2+ and Ge 2+ halides, toxicity of Pb 2+ , metal as well as low efficiencies of Bi 3+ phases, green 5s 2 Sb 3+ based hybrid metal halides are deemed to be one of most promising ultrabroadband luminescent materials with higher PLQYs and oxidation resistance abilities. [7b,8a,11] Up to now, the PLQYs of 0D hybrid antimony halides based on discrete [SbX 5 ] 2− and [SbX 6 ] 3− units can reach up to near unity due to strong quantum confinement effect. [12] These outstanding PL properties intrigued further in-depth understanding the enhancement or modulating mechanism of PLQY for hybrid antimony halides from molecular design level, which is also greatly desirable for subsequent rational design of new high-performance hybrid halides. Rationally optimizing the photoluminescence performance via accurate structural modulation is one of most important and challenging issues for hybrid halides. Herein, a viable crystal dimensional reduction strategy is proposed to reasonably enhance the photoluminescence quantum yield (PLQY) of hybrid antimony halide. Specifically, a synthetic technique is developed and new 1D [DMPZ]SbCl 5 • H 2 O (DP-SbCl 5 ) is sliced to 0D [DMPZ] 2 SbCl 6 • Cl • (H 2 O) 2 (DP-SbCl 6 ) with crystal dimensional reduction from infinite [SbCl 5 ] 2− chain to discrete [SbCl 6 ] 3− octahedron. Comparing with nonluminescent 1D DP-SbCl 5 , 0D DP-SbCl 6 displays highly efficient broadband yellow light emission with enhanced PLQY up to 75.94%. ...

With mixed transition-metal-complex, alkali-metal, or organic cations as structure-directing agents, a series of novel two-dimensional (2D) layered inorganic-organic hybrid iodoargentates, namely, Kx[TM(2,2-bipy)3]2Ag6I11 (TM = Mn (1), Fe (2), Co (3), Ni (4), Zn (5); x = 0.89-1) and [(Ni(2,2-bipy)3][H-2,2-bipy]Ag3I6 (6), have been solvothermally synthesized and structurally characterized. All the title compounds feature 2D microporous layers composed by [Ag3I7] secondary building units based on AgI4 tetrahedra. Differently, the [Ag3I7] trimers are directly interconnected via corner-sharing to form the 2D [Ag6I11](5-) layer in compounds 1-5, whereas two neighboring [Ag3I7] trimers are initially condensed into a hexameric [Ag6I12] ternary building unit as a new node, which further self-assembles, leading to the 2D [Ag6I10](4-) layer in compound 6. The UV-vis diffuse-reflectance measurements reveal that all the compounds possess proper semiconductor behaviors with tunable band gaps of 1.66-2.75 eV, which lead to highly efficient photocatalytic degradation activities over organic pollutants under visible light irradiation compared to that of N-dotted P25. Interestingly, all the samples feature distinct photodegradative speeds at the same reaction conditions, and compound 1 features the highest photocatalytic activity among the title phases. The luminescence properties, band structures, and thermal stabilities were also studied.

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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.