ABSTRACT
Two-dimensional (2D) organic-inorganic hybrid copper halide perovskites have drawn tremendous attention as promising multifunctional materials. Herein, by incorporating ortho-, meta-, and para-chlorine substitutions in the benzylamine structure, we first report the influence of positional isomerism on the crystal structures of chlorobenzylammonium copper(II) chloride perovskites A2CuCl4. 2D polar ferromagnets (3-ClbaH)2CuCl4 and (4-ClbaH)2CuCl4 (ClbaH+ = chlorobenzylammonium) are successfully obtained. They both adopt a polar monoclinic space group Cc at room temperature, displaying significant differences in crystal structures. In contrast, (2-ClbaH)2CuCl4 adopts a centrosymmetric space group P 21/ c at room temperature. This associated structural evolution successfully enhances the physical properties of the two polar compounds with high thermal stability, discernible second harmonic generation (SHG) signals, ferromagnetism, and narrow optical band gaps. These findings demonstrate that the introduction of chlorine atoms into the interlayer organic species is a powerful tool to tune crystal symmetries and physical properties, and this inspires further exploration of designing high-performance multifunctional copper-based materials.
ABSTRACT
We present the influence of positional isomerism on the crystal structure of fluorobenzylammonium copper(II) chloride perovskites A2CuCl4 by incorporating ortho-, meta-, and para-fluorine substitution in the benzylamine structure. Two-dimensional (2D) polar ferromagnet (3-FbaH)2CuCl4 (3-FbaH+ = 3-fluorobenzylammonium) is successfully obtained, which crystallizes in a polar orthorhombic space group Pca21 at room temperature. In contrast, both (2-FbaH)2CuCl4 (2-FbaH+ = 2-fluorobenzylammonium) and (4-FbaH)2CuCl4 (4-FbaH+ = 4-fluorobenzylammonium) crystallize in centrosymmetric space groups P21/c and Pnma at room temperature, respectively, displaying significant differences in crystal structures. These differences indicate that the position of the fluorine atom is a driver for the polar behavior in (3-FbaH)2CuCl4. Preliminary magnetic measurements confirm that these three perovskites possess dominant ferromagnetic interactions within the inorganic [CuCl4]∞ layers. Therefore, (3-FbaH)2CuCl4 is a polar ferromagnet, with potential as a type I multiferroic. This work is expected to promote further development of high-performance 2D copper(II) halide perovskite multiferroic materials.
ABSTRACT
We present a comprehensive review of the structural chemistry of hybrid lead halides of stoichiometry APbX 4, A 2PbX4 or A A'PbX 4, where A and A' are organic ammonium cations and X = Cl, Br or I. These compounds may be considered as layered perovskites, containing isolated, infinite layers of corner-sharing PbX 4 octahedra separated by the organic species. First, over 250 crystal structures were extracted from the CCDC and classified in terms of unit-cell metrics and crystal symmetry. Symmetry mode analysis was then used to identify the nature of key structural distortions of the [PbX 4]∞ layers. Two generic types of distortion are prevalent in this family: tilting of the octahedral units and shifts of the inorganic layers relative to each other. Although the octahedral tilting modes are well known in the crystallography of purely inorganic perovskites, the additional layer-shift modes are shown to enormously enrich the structural options available in layered hybrid perovskites. Some examples and trends are discussed in more detail in order to show how the nature of the interlayer organic species can influence the overall structural architecture; although the main aim of the paper is to encourage workers in the field to make use of the systematic crystallographic methods used here to further understand and rationalize their own compounds, and perhaps to be able to design-in particular structural features in future work.
ABSTRACT
A new hybrid lead(ii) halide perovskite, (TzH)2PbCl4, ([TzH+] = 1,2,4-triazolium), adopts a (001)-oriented layered perovskite structure, which can be considered as derived from the n = 1 Ruddlesden-Popper (RP) type. Variable temperature single crystal X-ray diffraction reveals a structural phase transition in the region 125 K < T < 173 K between a high temperature, high symmetry polymorph, space group Cmcm, and a low temperature, low symmetry chiral polymorph, space group P212121, which has a tripled unit cell volume. UV-Vis spectra suggest a band gap of 3.30 eV for (TzH)2PbCl4. A second polymorph of the bromide analogue, (TzH)2PbBr4-II, is also reported, and structural relationships between all three variants are discussed.
ABSTRACT
Two 'hollow' B-site deficient perovskites, (TzH)11(H3PO2)Sn6I23 and (TzH)3Sn2I7 (TzH+ = 1,2,4-triazolium, H3PO2 = hypohosphorous acid), have been prepared. (TzH)11(H3PO2)Sn6I23 is the first example of a 2D layered structure of this type. Leaving the same reaction mixture for an extended time also affords the 3D derivative (TzH)3Sn2I7.
ABSTRACT
We present three new hybrid layered lead(II) bromide perovskites of generic composition A2PbBr4 or AA'PbBr4 that exhibit three distinct structure types. [TzH]2PbBr4 ([TzH+] = 1,2,4-triazolium) adopts a (001)-oriented layer structure and [AaH]2PbBr4, ([AaH+] = acetamidinium) adopts a (110)-oriented type, whereas [ImH][TzH]PbBr4, ([ImH+] = imidazolium) adopts a rare (110)-oriented structure with enhanced corrugation (i.e., 3 × 3 type). The crystal structures of each are discussed in terms of the differing nature of the templating molecular species. Photoluminescent spectra for each are reported and the behaviors discussed in relation to the different structure of each composition.
ABSTRACT
Two unique hybrid tin iodides, with generic compositions A0.5A'0.5SnI3 and A1.5A'0.5SnI4 have been prepared. Each shows ordering of the two organic moieties (A and A') on distinct crystallographic sites, leading to novel 3D and 2D structure types, respectively.
ABSTRACT
The hybrid perovskites (ImH)(GuH)PbBr4 and (TzH)(GuH)PbBr4 (ImH+ = imidazolium, GuH+ = guanidinium, TzH+ = 1,2,4-triazolium) both adopt (110)-oriented layer structures. However, the GuH+ cation adopts differing crystallographic sites in the two structures (intra-layer versus inter-layer); this is discussed in terms of the sizes of the organic cations and their hydrogen-bonding preferences.
ABSTRACT
Since the observation that the properties of ferroic domain walls (DWs) can differ significantly from the bulk materials in which they are formed, it has been realized that domain wall engineering offers exciting new opportunities for nanoelectronics and nanodevice architectures. Here, a novel improper ferroelectric, CsNbW2 O9 , with the hexagonal tungsten bronze structure, is reported. Powder neutron diffraction and symmetry mode analysis indicate that the improper transition (TC = 1100 K) involves unit cell tripling, reminiscent of the hexagonal rare earth manganites. However, in contrast to the manganites, the symmetry breaking in CsNbW2 O9 is electronically driven (i.e., purely displacive) via the second-order Jahn-Teller effect in contrast to the geometrically driven tilt mechanism of the manganites. Nevertheless CsNbW2 O9 displays the same kinds of domain microstructure as those found in the manganites, such as the characteristic six-domain "cloverleaf" vertices and DW sections with polar discontinuities. The discovery of a completely new material system, with domain patterns already known to generate interesting functionality in the manganites, is important for the emerging field of DW nanoelectronics.
ABSTRACT
The ambient-temperature structures (orthorhombic, space group Cmc21) of the polar hexagonal tungsten bronzes RbNbW2O9 and KNbW2O9 have been determined by high-resolution powder neutron diffraction. Displacement of the A-site cation along the polar c axis with concomitant octahedral tilting occurs to optimize the A cation bonding environment, hence reducing the coordination from 18 to 16. This effect is more evident in KNbW2O9 due to decreased A cation size. The octahedral tilting in both compositions results in a doubling of the c axis that has not previously been reported, highlighting the importance of neutron diffraction as a complementary technique for structural determination of such systems.
ABSTRACT
The perovskite Li0.2Na0.8NbO3 is shown, by powder neutron diffraction, to display a unique sequence of phase transitions at elevated temperature. The ambient temperature polar phase (rhombohedral, space group R3c) transforms via a first-order transition to a polar tetragonal phase (space group P42mc) in the region 150-300°C; these two phases correspond to Glazer tilt systems a-a-a- and a+a+c-, respectively. At 500°C a ferroelectric-paraelectric transition takes place from P42mc to P42/nmc, retaining the a+a+c- tilt. Transformation to a single-tilt system, a0a0c+ (space group P4/mbm), occurs at 750°C, with the final transition to the aristotype cubic phase at 850°C. The P42mc and P42/nmc phases have each been seen only once and twice each, respectively, in perovskite crystallography, in each case in compositions prepared at high pressure.
