The influence of copper on the optical band gap of heterometallic iodido antimonates and bismuthates

Möbs, Jakob; Luy, Jan‐Niclas; Shlyaykher, Alena; Tonner, Ralf; Heine, Johanna

doi:10.1039/d1dt02828f

Cited by 13 publications

(10 citation statements)

References 79 publications

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“…In CuBiI , these units are further connected through corner-sharing into chains, a motif that has not been previously observed in main group halogenido metalate chemistry before. However, a number of compounds with anions of the same composition have been reported, including the condensed molecular anion [Bi 3 I 11 ] 2– , the larger molecular anion [Bi 6 I 22 ] 4– , of which five different isomers are known, − and two different types of chain-like [Bi 3 I 11 ] 2– anions, , where a wider chain motif is formed entirely through edge-sharing of {BiI 6 } octahedra. A combination of face- and corner-sharing connections, as seen in CuBiI has been observed in [M(tpy) 2 ][Bi 2 I 8 ] (M = Fe, Cu; tpy = 2,2′:6′2″-terpyridine).…”

Section: Resultsmentioning

confidence: 99%

Enhanced Circular Dichroism and Polarized Emission in an Achiral, Low Band Gap Bismuth Iodide Perovskite Derivative

Möbs,

Klement,

Stuhrmann

et al. 2023

J. Am. Chem. Soc.

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Lead halide perovskites and related main-group halogenido metalates offer unique semiconductor properties and diverse applications in photovoltaics, solid-state lighting, and photocatalysis. Recent advances in incorporating chiral organic cations have led to the emergence of chiral metal-halide semiconductors with intriguing properties, such as chiroptical activity and chirality-induced spin selectivity, enabling the generation and detection of circularly polarized light and spin-polarized electrons for applications in spintronics and quantum information. However, understanding the structural origin of chiroptical activity remains challenging due to macroscopic factors and experimental limitations. In this work, we present an achiral perovskite derivative [Cu2(pyz)3(MeCN)2][Bi3I11] (CuBiI; pyz = pyrazine; MeCN = acetonitrile), which exhibits remarkable circular dichroism (CD) attributed to the material’s noncentrosymmetric nature. CuBiI features a unique structure as a poly-threaded iodido bismuthate, with [Bi3I11]2– chains threaded through a cationic two-dimensional coordination polymer. The material possesses a low, direct optical band gap of 1.70 eV. Notably, single crystals display both linear and circular optical activity with a large anisotropy factor of up to 0.16. Surprisingly, despite the absence of chiral building blocks, CuBiI exhibits a significant degree of circularly polarized photoluminescence, reaching 4.9%. This value is comparable to the results achieved by incorporating chiral organic molecules into perovskites, typically ranging from 3–10% at zero magnetic field. Our findings provide insights into the macroscopic origin of CD and offer design guidelines for the development of materials with high chiroptical activity.

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Section: Resultsmentioning

confidence: 99%

Enhanced Circular Dichroism and Polarized Emission in an Achiral, Low Band Gap Bismuth Iodide Perovskite Derivative

Möbs,

Klement,

Stuhrmann

et al. 2023

J. Am. Chem. Soc.

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“…Examples include [MV][BiI 5 ] (where MV 2+ = methyl viologen), which contains one-dimensional chains of corner-sharing [BiI 6 ] 3− octahedra and exhibits a band gap of 1.48 eV [34], and [C 3 H 5 N 2 S][BiI 4 ], which has a band gap of 1.78 eV and contains one-dimensional chains of edgesharing octahedra [52]. Incorporation of additional metals to form ternary iodobismuthates, such as [HPy] 2 [Py][CuBi 3 I 12 ] (where Py = pyridine) which has a band gap of 1.59 eV [53], may provide an alternative approach to achieve significant reductions in the band gap [54].…”

Section: Thermal Stability and Uv-vis Diffuse Reflectancementioning

confidence: 99%

Synthesis and Characterisation of Iodobismuthates Containing N-substituted 1,4-Diazabicyclo[2.2.2]octane

2022

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Two new hybrid iodobismuthates, [C8H17N2][C10H22N2][BiI6] (1) and [C6H12N2]0.5[C10H22N2]3.5[Bi2I10][Bi2I9] (2), have been prepared by solvothermal synthesis in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) and ethanol. Both compounds have been characterized by single-crystal and powder X-ray diffraction, infrared and UV–Vis spectroscopies and thermogravimetric analysis. Structure determination reveals that the crystal structure of 1 contains mononuclear [BiI6]3− anions, whilst 2 contains an unusual combination of dinuclear anions, [Bi2I9]3− and [Bi2I10]4−, consisting of two edge- and two face-sharing [BiI6]3− octahedra, respectively. Mono- and diethylated derivatives of DABCO, which are formed in situ under solvothermal conditions, act as countercations and are located between the discrete anions. The optical band gaps of 1 and 2, which are 2.29(1) and 2.03(2) eV respectively, are consistent with the red color of these compounds, and are comparable to the band gaps measured for other iodobismuthates containing discrete anions. Graphical Abstract Two new iodobismuthates, [C8H17N2][C10H22N2][BiI6] (1) and [C6H12N2]0.5[C10H22N2]3.5[Bi2I10][Bi2I9] (2), have been synthesized under solvothermal conditions, and their crystal structures determined by single-crystal X-ray diffraction.

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“…According to this strategy, heterometallic copper- and silver-containing iodobismuthates with zero-dimensional [ 19 , 20 , 21 , 22 , 23 , 24 ], one-dimensional [ 20 , 25 , 26 , 27 , 28 ] ( Figure S1 ) or two-dimensional [ 29 , 30 ] anionic motifs have been characterized previously. However, the overall number of known heterometallic iodometallates remains lower than that of homometallic ones, but this trend can change, as recent works clearly demonstrate [ 27 , 31 , 32 , 33 , 34 ].…”

Section: Introductionmentioning

confidence: 99%

Copper- and Silver-Containing Heterometallic Iodobismuthates: Features of Thermochromic Behavior

Shentseva

Usoltsev

Korobeynikov

et al. 2023

IJMS

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Nine heterometallic iodobismuthates with the general formula Cat2{[Bi2M2I10}] (M = Cu(I), Ag(I), Cat = organic cation) were synthesized. According to X-ray diffraction data, their crystal structures consisted of {Bi2I10} units interconnected with Cu(I) or Ag(I) atoms through I-bridging ligands, forming one-dimensional polymers. The compounds are thermally stable up to 200 °C. Optical band gaps (Eg), estimated at room temperature via diffuse reflectance measurements, range from 1.81 to 2.03 eV. Thermally induced changes in optical behavior (thermochromism) for compounds 1–9 were recorded, and general correlations were established. The thermal dependence of Eg appears to be close to linear for all studied compounds.

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The influence of copper on the optical band gap of heterometallic iodido antimonates and bismuthates

Abstract: The electronic situation at the copper atom controls the optical properties in a series of multinary iodido antimonates and bismuthates.

Cited by 13 publications

References 79 publications

Enhanced Circular Dichroism and Polarized Emission in an Achiral, Low Band Gap Bismuth Iodide Perovskite Derivative

Enhanced Circular Dichroism and Polarized Emission in an Achiral, Low Band Gap Bismuth Iodide Perovskite Derivative

Synthesis and Characterisation of Iodobismuthates Containing N-substituted 1,4-Diazabicyclo[2.2.2]octane

Copper- and Silver-Containing Heterometallic Iodobismuthates: Features of Thermochromic Behavior

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