The double perovskites Cs 2 AgBiBr 6 and Cs 2 AgBiCl 6 have been synthesized from both solid state and solution routes. X-ray diffraction measurements show that both compounds adopt the cubic double perovskite structure, space group Fm3̅ m, with lattice parameters of 11.2711(1) Å (X = Br) and 10.7774(2) Å (X = Cl). Diffuse reflectance measurements reveal band gaps of 2.19 eV (X = Br) and 2.77 eV (X = Cl) that are slightly smaller than the band gaps of the analogous lead halide perovskites, 2.26 eV for CH 3 NH 3 PbBr 3 and 3.00 eV for CH 3 NH 3 PbCl 3 . Band structure calculations indicate that the interaction between the Ag 4d-orbitals and the 3p/4porbitals of the halide ion modifies the valence band leading to an indirect band gap. Both compounds are stable when exposed to air, but Cs 2 AgBiBr 6 degrades over a period of weeks when exposed to both ambient air and light. These results show that halide double perovskite semiconductors are potentially an environmentally friendly alternative to the lead halide perovskite semiconductors.

The structures of the lead halide perovskites CsPbCl3 and CsPbBr3 have been determined from X-ray powder diffraction data to be orthorhombic with Pnma space group symmetry. Their structures are distorted from the cubic structure of their hybrid analogs, CH3NH3PbX3 (X = Cl, Br), by tilts of the octahedra (Glazer tilt system a – b + a –). Substitution of the smaller Rb+ for Cs+ increases the octahedral tilting distortion and eventually destabilizes the perovskite structure altogether. To understand this behavior, bond valence parameters appropriate for use in chloride and bromide perovskites have been determined for Cs+, Rb+, and Pb2+. As the tolerance factor decreases, the band gap increases, by 0.15 eV in Cs1–x Rb x PbCl3 and 0.20 eV in Cs1–x Rb x PbBr3, upon going from x = 0 to x = 0.6. The band gap shows a linear dependence on tolerance factor, particularly for the Cs1–x Rb x PbBr3 system. Comparison with the cubic perovskites CH3NH3PbCl3 and CH3NH3PbBr3 shows that the band gaps of the methylammonium perovskites are anomalously large for APbX3 perovskites with a cubic structure. This comparison suggests that the local symmetry of CH3NH3PbCl3 and CH3NH3PbBr3 deviate significantly from the cubic symmetry of the average structure.

The halide double perovskite solid solution Cs2AgBiBr6−xClx has been investigated and found to exhibit a band gap that increases from 2.2 eV to 2.8 eV as the Cl− content increases, with an upward deviation from Vegard's law when x > 5.

Herein we report the synthesis, structure, and band gaps of four layered halide double perovskites, i.e., BA2Cu0.5In0.5Cl4, BA2Ag0.5In0.5Cl4, BA2Ag0.5Sb0.5Cl4, and BA2Ag0.5Sb0.5Br4 [BA = butylammonium = CH3(CH2)3NH3 +], each of which has the n = 1 Ruddlesden–Popper structure. In addition, the crystal structure of BA2Ag0.5Bi0.5Br4 is revisited and that of BA2PbCl4 is reported for the first time. Only BA2Ag0.5Sb0.5Cl4 has the tetragonal I4/mmm symmetry of the undistorted Ruddlesden–Popper structure. The other five compounds have orthorhombic structures due to tilts of the octahedra and orientational ordering of the butylammonium groups. As the lateral dimensions of the inorganic layer decrease, the c/a ratio increases due to decreased interdigitation of the alkyl ends of the butylammonium cations. This structural feature may help to explain the increased stability of the bromide phases with respect to the chloride phases. There are features in the diffraction patterns of BA2Ag0.5Bi0.5Br4 and BA2Cu0.5In0.5Cl4 that suggest ordering of octahedral cations within the layers, but in those compounds there appears to be a high concentration of stacking faults between layers that limits long-range, three-dimensional ordering of cations. In the other cases the scattering powers of the cations (Ag/Sb and Ag/In) are too similar to say anything definitive about cation ordering. The band gaps of these compounds range from 2.65 to 4.27 eV, with the bromide compositions possessing smaller band gaps than the chlorides. The band gaps of layered BA2M0.5M′0.5X4 compositions studied here are roughly 0.5–0.8 eV larger than analogous Cs2MM′X6 cubic double perovskites due to a combination of dimensional reduction (3D → 2D), distortions of the octahedral environment around the M/M′ ions, and octahedral tilting distortions.

A Zr metal–organic framework (MOF) 1-CoCl3 has been synthesized by solvothermal reaction of ZrCl4 with a carboxylic acid-functionalized CoIII-PNNNP pincer complex H4(L-CoCl3) ([L-CoCl3]4– = [(2,6-(NHPAr2)2C6H3)­CoCl3]4–, Ar = p-C6H4CO2 –). The structure of 1-CoCl3 has been determined by X-ray powder diffraction and exhibits a csq topology that differs from previously reported ftw-net Zr MOFs assembled from related PdII- and PtII-PNNNP pincer complexes. The Co-PNNNP pincer species readily demetallate upon reduction of CoIII to CoII, allowing for transmetalation with late second and third row transition metals in both the homogeneous complex and 1-CoCl3 . Reaction of 1-CoCl3 with [Rh­(nbd)­Cl]2 (nbd = 2,5-nobornadiene) results in complete Rh/Co metal exchange at the supported diphosphine pincer complexes to generate 1-RhCl, which has been inaccessible by direct solvothermal synthesis. Treating 1-CoCl3 with PtCl2(SMe2)2 in the presence of the mild reductant NEt3 resulted in nearly complete Co substitution by Pt. In addition, a mixed metal pincer MOF, 1-PtRh, was generated by sequential substitution of Co with Pt followed by Rh.

We report the successful electrochemical intercalation of F-ions into a densely packed perovskite oxide from a liquid electrolyte at room temperature. Using galvanostatic oxidation and electrochemical impedance spectroscopy coupled with operando X-ray diffraction, we show that roughly 0.5 equivalents of F-ions can be inserted onto the vacant A-site of the perovskite ReO3. Density functional theory calculations indicate that the intercalated phase is thermodynamically unfavorable compared to other less densely packed polymorphs of ReO3F. Pairing X-ray spectroscopy, neutron total scattering measurements, and magic-angle spinning 19F NMR confirms a rapid decomposition of the product on removal from the cell but nevertheless, these results clearly demonstrate that small anions like fluoride can be intercalated into solids as readily as alkali cations at room temperature, which opens new opportunities to electrochemically fluorinate many new materials. File list (2)download file view on ChemRxiv FxReO3.pdf (12.07 MiB) download file view on ChemRxiv supporting_information.pdf (5.70 MiB)

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We report on the reversible, electrochemical (de)fluorination of CsMnFeF 6 at room temperature using a liquid electrolyte. CsMnFeF 6 was synthesized via three methods (hydrothermal, ceramic, and mechanochemical), each of which yields products in a defect pyrochlore structure with varying particle sizes and phase purities. After three galvanostatic cycles, approximately one fluoride ion can be reversibly (de)inserted into mechanochemical CsMnFeF 6 for multiple cycles. Ex situ X-ray absorption spectroscopy confirmed that both Mn 2+ and Fe 3+ are redox active. The cell impedance decreases after one cycle, suggesting that the formation of fluoride vacancies in early cycles generates mixed-valent Fe and enhances the material's conductivity. Ex situ synchrotron diffraction revealed subtle expansion and contraction of the CsMnFeF 6 cubic lattice on insertion and removal, respectively, during the first two cycles. New reflections intensify in the ex situ diffraction patterns from cycle 3, corresponding to a topotactic transformation of CsMnFeF 6 from the pyrochlore structure into an orthorhombic polytype that continues cycling fluoride ions reversibly.