Two-Dimensional and Emission-Tunable: An Unusual Perovskite Constructed from Lindqvist-Type [Pb6Br19]7– Nanoclusters

Li, Xin‐Xiong; Ha, Thu; Águila, Andrés Granados del; Huang, Yinjuan; Chen, Wangqiao; Li, Yongxin; Ganguly, Rakesh; Morris, Samuel A.; Xiong, Qihua; Li, Dongsheng; Zhang, Qichun

doi:10.1021/acs.inorgchem.8b02535

Cited by 23 publications

(24 citation statements)

References 33 publications

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“…The GSB rises at sub-picosecond timescale due to the fast band-edge population 52 and then goes through a slow decay process, lasting in the hundreds of ps, which is associated with the excitonexciton annihilation given the high fluence used in the measurement. 39 The TA features are markedly similar to those of previous studies under lower excitation power densities, confirming that the excitons remain the main excited-state species here (i.e. below the Mott transition).…”

Section: Acs Paragon Plus Environmentsupporting

confidence: 86%

“…It is worth noting that the intensity of the PL peaks drops as the size of the A-site cation increases (Figure b). The PLQY (ϕ) is defined by the equation , where k r and k n are the rate constants of the radiative and nonradiative decay, respectively. − Because of the similar dielectric environments of the compounds, the exciton binding energy and the radiative decay rate are generally expected to be similar. The observed decrease of the PL intensity, however, suggests a higher nonradiative decay rate in the larger A-site cation compounds, which is also confirmed by the time-resolved PL (TRPL) measurement (Figure c).…”

Section: Results and Discussionmentioning

confidence: 89%

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Negative Pressure Engineering with Large Cage Cations in 2D Halide Perovskites Causes Lattice Softening

et al. 2020

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Organic-inorganic hybrid halide perovskites are promising semiconductors with tailorable optical and electronic properties. The choice of A-site cation to support a three-dimensional (3D) perovskite structure AMX 3 (where M is a metal, and X is a halide) is limited by the geometric Goldschmidt tolerance factor. However, this geometric constraint can be relaxed in twodimensional (2D) perovskites, providing us an opportunity to understand how various the A-site cations modulate the structural properties and thereby the optoelectronic properties. Here, we report the synthesis and structures of single-crystals (BA) 2 (A)Pb 2 I 7 where BA = butylammonium, and A = methylammonium (MA), formamidinium (FA), dimethylammonium (DMA) or guanidinium (GA), a series of A-site cation varied in size. Single-crystal X-ray diffraction reveals that the MA, FA, and GA structures crystallize in the same Cmcm space group, while the DMA imposes the Ccmb space group. We observe that as the A-site cation becomes larger, the Pb−I bond continuously elongates, expanding the volume of the perovskite cage, equivalent to exerting "negative pressure" on the perovskite structures. Optical studies and DFT calculations show the Pb−I bond length elongation reduces overlap of the Pb s-and I p-orbitals and increases the optical bandgap, while Pb−I−Pb angles play a secondary role. Raman spectra show lattice softening with

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Section: Acs Paragon Plus Environmentsupporting

confidence: 86%

Section: Results and Discussionmentioning

confidence: 89%

Negative Pressure Engineering with Large Cage Cations in 2D Halide Perovskites Causes Lattice Softening

et al. 2020

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“…[22][23][24][25][26] 2D perovskites can be obtained by chemically slicing the 3D perovskite lattice through different planes, giving (100)-, (110)-and (111)-oriented perovskites. [27][28][29][30] Since the report of 2D perovskites as white-light emitters by Karunadasa and coworkers in 2014, [22][23] several other 2D perovskites [25][26][31][32][33][34][35][36] and even some lower-dimensional metal halide hybrids [37][38][39] have been demonstrated to exhibit white-light emission at room temperature. The broad emission is associated with lattice distortion to generate self-trapped excitons (STE), facilitated by the phonon-assisted emissive relaxation of the strongly bound exciton resulting from quantum confinement.…”

Section: Introductionmentioning

confidence: 99%

Small Cyclic Diammonium Cation Templated (110)-Oriented 2D Halide (X = I, Br, Cl) Perovskites with White-Light Emission

et al. 2019

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Two-dimensional (2D) halide perovskites exhibit excellent potential for optoelectronics because of their outstanding physical properties and structural diversity. White-light emission is one property of 2D perovskites that originates from self-trapped excitons (STE) in the highly distorted structures. The so-called (110)-oriented 2D perovskites are generally distorted and believed to be good candidates for white-light emitting devices. Here, we report (110)-oriented 2D perovskites, C4N2H12PbX4 (X = I, Br, Cl), templated by the small cyclic diammonium cation, 3aminopyrrolidine (3APr). Structural characterization by single-crystal X-ray diffraction reveals that the distortion of the inorganic part of the structures is influenced by the stereochemical conformation of the cation between the perovskite layers. The experimental bandgaps follow the trend I < Br < Cl (2.56 eV, 3.29 eV, 3.85 eV, respectively). DFT calculations reveal a weak but significant electronic band dispersion along the stacking axis, suggesting a non-negligible interlayer electronic coupling caused by the short proximity of adjacent inorganic layers. The high level of distortion results in the emergence of white-light emission, rarely seen in iodide perovskites, as well as the bromide and chloride isostructural analogues, which provides perfect platform to compare the broad emission mechanism for all three halides. The bromide and chloride perovskites show longer lifetimes and higher color rendering index (CRI) (83 and 85), relevant to solid-state lighting. Temperature-dependent PL measurements confirm that the broad emission comes from different STE mechanism for different halides, with the peak broadening persisting even at low temperature for the chloride compound.

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“…Metal halides have attracted great interest in the domains of semiconductors, catalysis,p hotochromism and nonlinear optics owing to not only their fascinating structural characteristics but the promising physico-chemical properties. [1][2][3][4][5][6][7][8][9][10][11][12] Amongt hem, argentum halide family, especiallyt he iodoargentates, have been widely synthesized and reported. [13][14][15][16][17][18][19][20] By virtue of the various coordination geometries of Ag I as well as the flexible linkageo fi odide ions, iodoargentatess how diverse specieso fa rchitectures with zero-dimensional (0D) clusters, 1D chains, 2D layersa nd even 3D intricate networks.I ng eneral, the iodoargentates usually display anionic skeletons, wherein cationico rganic molecules or metal-organic complexes are occupied the space of frameworks as counterions and structuredirectinga gents (SDAs) or templates.…”

Section: Introductionmentioning

confidence: 99%

“…Metal halides have attracted great interest in the domains of semiconductors, catalysis, photochromism and nonlinear optics owing to not only their fascinating structural characteristics but the promising physico‐chemical properties . Among them, argentum halide family, especially the iodoargentates, have been widely synthesized and reported .…”

Section: Introductionmentioning

confidence: 99%

A Series of Iodoargentates Directed by Solvated Metal Cations Featuring Uptake and Photocatalytic Degradation of Organic Dye Pollutants

Wei

Wang

Pan

et al. 2019

Chemistry An Asian Journal

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By using solvated metal cations as structure-directing agents, three new iodoargentates, namely,[ Fe(DMSO) 6 ] [Ag 6 I 9 ]·DMSO (1), [Fe(H 2 O) 6 ][Ag 15 I 18 ]( 2)a nd [Cd(DMSO) 6 ] [Ag 8 I 10 ]( 3)( DMSO = dimethyl sulfoxide) have been solvothermally prepared and structurallyc haracterized. The structures of compounds 1 and 2 can be described as 1D chains constructed from the linkageo f[ Ag 6 I 9 ]a nd [Ag 5 I 11 ]b uilding units, respectively.F or compound 3,t he [Ag 10 I 22 ]b uilding blocks are directly interconnected to form a2 D[ Ag 8 I 10 ]l ayer,which are furtheri nterconnected via intermolecularf orces to generate a3 Ds upramolecular framework with 1D large channels occupied by [Cd(DMSO) 6 ] 2 + cations.I nterestingly, compounds 1-3 exhibit an ion-exchange behavior for the adsorption of as pecific dye (methylene blue, MB). Moreover, photocatalytic experimentsi ndicate that these iodoargentates can be considered as promisingp hotocatalysts for the degradation of organic dyep ollutants.[a] Dr.

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Two-Dimensional and Emission-Tunable: An Unusual Perovskite Constructed from Lindqvist-Type [Pb₆Br₁₉]^7– Nanoclusters

Cited by 23 publications

References 33 publications

Negative Pressure Engineering with Large Cage Cations in 2D Halide Perovskites Causes Lattice Softening

Negative Pressure Engineering with Large Cage Cations in 2D Halide Perovskites Causes Lattice Softening

Small Cyclic Diammonium Cation Templated (110)-Oriented 2D Halide (X = I, Br, Cl) Perovskites with White-Light Emission

A Series of Iodoargentates Directed by Solvated Metal Cations Featuring Uptake and Photocatalytic Degradation of Organic Dye Pollutants

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