Ionothermal synthesis, structure and optical properties of three new organic–inorganic hybrid imidazolium bromoplumbate complexes

Niu, Jingping; Zhai, Quan‐Guo; Luo, Junhua; Li, Shu-Ni; Jiang, Yucheng; Hu, Mancheng

doi:10.1016/j.inoche.2011.01.045

Cited by 14 publications

(7 citation statements)

References 46 publications

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“…The 1D “perovskitoids” (which refers to exclusively face-sharing ABX 3 compounds) (hep)PbBr 3 and (hex)PbBr 3 belong to the common CsNiBr 3 structure type, with face-sharing polymeric [PbBr 3 ] − chains (Figure ). − Usually, a bulky cationic template, which is capable of separating the inorganic sections far apart, will lead to the formation of such low-dimensional structure type. , The (hep)PbBr 3 and (hex)PbBr 3 crystallize in noncentrosymmetric monoclinic space groups Cc and P 2 1 , respectively. In Figure a,b, the infinite [PbBr 3 ] − chains in the structure extend along the c -axis for (hep)PbBr 3 ( a -axis for (hex)PbBr 3 ), and the individual chains are crystallographically nonequivalent, which lower the symmetry.…”

Section: Resultsmentioning

confidence: 99%

Structural Diversity in White-Light-Emitting Hybrid Lead Bromide Perovskites

et al. 2018

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Hybrid organic-inorganic halide perovskites are under intense investigations because of their astounding physical properties and promises for optoelectronics. Lead bromide and chloride perovskites exhibit intrinsic white-light emission believed to arise from self-trapped excitons (STEs). Here, we report a series of new structurally diverse hybrid lead bromide perovskites that have broad-band emission at room temperature. They feature Pb/Br structures which vary from 1D face-sharing structures to 3D corner- and edge-sharing structures. Through single-crystal X-ray diffraction and low-frequency Raman spectroscopy, we have identified the local distortion level of the octahedral environments of Pb within the structures. The band gaps of these compounds range from 2.92 to 3.50 eV, following the trend of "corner-sharing < edge-sharing < face-sharing". Density functional theory calculations suggest that the electronic structure is highly dependent on the connectivity mode of the PbBr octahedra, where the edge- and corner-sharing 1D structure of (2,6-dmpz)PbBr exhibits more disperse bands and smaller band gap (2.49 eV) than the face-sharing 1D structure of (hep)PbBr (3.10 eV). Using photoemission spectroscopy, we measured the energies of the valence band of these compounds and found them to remain almost constant, while the energy of conduction bands varies. Temperature-dependent PL measurements reveal that the 2D and 3D compounds have narrower PL emission at low temperature (∼5 K), whereas the 1D compounds have both free exciton emission and STE emission. The 1D compound (2,6-dmpz)PbBr has the highest photoluminescence quantum yield of 12%, owing to its unique structure that allows efficient charge carrier relaxation and light emission.

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Section: Resultsmentioning

confidence: 99%

Structural Diversity in White-Light-Emitting Hybrid Lead Bromide Perovskites

et al. 2018

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“…Hybrid organic–inorganic halide perovskites with the chemical formula AMX 3 (A = CH 3 NH 3 + , HC (NH 2 ) 2+ , or Cs + ; M = Pb 2+ , Ge 2+ , Sn 2+ ; X = I – , Br – , Cl – ) have attracted extensive attention in the last ten years because of their enormous potential in the field of optoelectronics. − However, the commercialization of AMX 3 perovskites suffers from an instability problem caused by external factors such as humidity, light illumination, and heating treatment. − The application of low-dimensional perovskites is an emerging method to overcome the poor stability of these materials. The three-dimensional structure is changed into a lower dimensional structure by replacing A-site atoms with larger cations. − The reduction in the structural dimension enables more organic cations to enter the perovskite lattice, resulting in more interesting changes in the performance of the material and, to a greater extent, precise design of the perovskites can be achieved. − Larger organic cations generally possess hydrophobicity and low volatility, which result in low dimensional perovskite materials with higher chemical stability. − Low-dimensional perovskites have aroused wide public concern over recent years due to their superior stability. − They are recognized as a promising candidate in optoelectronic devices such as photovoltaics , and light-emitting diodes (LEDs). , …”

Section: Introductionmentioning

confidence: 99%

Low-Dimensional Hybrid Lead Iodide Perovskites Single Crystals via Bifunctional Amino Acid Cross-Linkage: Structural Diversity and Properties Controllability

Xie

Wang

et al. 2021

ACS Appl. Mater. Interfaces

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Three-dimensional perovskite AMX3 has great potential in photoelectric applications, but the poor stability is a major problem that restricts its practical application. The emergence of lower dimensional perovskite solves this problem. Here, we have synthesized a group of novel low-dimensional perovskites with diverse structures. Different amino acids were incorporated in the perovskite cage. The formulas of the compounds are (A′) m PbI m+2 (A′ = COOH(CH2) n NH2, n = 1, 3, 5, 7, 9). These families of materials demonstrate structure-related stability, tunable bandgap, and different photoluminescence. Single-crystal X-ray diffraction indicated that the five materials employ different structure types varying from edge-sharing structures to face- and corner-sharing Pb/I structures by adjusting the number of C atoms in organic cations, and the level of [PbI6]4– octahedral distortion was also identified. The film prepared using these materials with longer carbon chains (n = 5, 7, 9) showed better stability, and they did not decompose within one year at 75% RH, 40 °C. The bifunctional organic ions containing carboxyl groups as spacer cations will form additional hydrogen bonding between perovskite layers, resulting in higher stability of the material. The band gaps of these materials vary from 2.19 to 2.6 eV depending on the octahedral connection mode and [PbI6]4– octahedral distortion level, density functional theory calculations (DFT) are consistent with our experimental trends and suggest that the face-sharing structure has the maximum band gap due to its flatter electron band structure. Bright green fluorescence was observed in (COOH(CH2)7NH3)2PbI4 and (COOH(CH2)9NH3)2PbI4 when excited by 365 nm UV light. A thorough comprehension of the structure–property relationships is of great significance for further practical applications of perovskites.

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“…Previous studies have shown that haloplumbate hybrids, with a wide range of interesting optical, semiconducting, and other physical properties, are technically important [7][8][9], and their haloplumbate anions exhibit a wide variety of coordination numbers and stereochemistries due to the flexibility of the Pb(II) coordination polyhedron and the templating effect of the cations [10]. Recent development has revealed that introduction of transition metal (TM) complex cations into inorganic systems can produce inorganicorganic hybrids with unique topological structures and interesting physical properties [11,12].…”

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confidence: 99%