Chemically diverse and multifunctional hybrid organic–inorganic perovskites

Li, Wei; Wang, Zheming; Deschler, Felix; Gao, Song; Friend, Richard H.; Cheetham, Anthony K.

doi:10.1038/natrevmats.2016.99

Cited by 1,027 publications

(830 citation statements)

References 198 publications

(200 reference statements)

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“…[81,164,175] HP(AX) structures employ many of the ligands we discussed for HP(A) and HP(X) compounds. [81,164,175] HP(AX) structures employ many of the ligands we discussed for HP(A) and HP(X) compounds.…”

Section: Organic A-and X-sites: Hp(ax)mentioning

confidence: 99%

Mix and Match: Organic and Inorganic Ions in the Perovskite Lattice

Gebhardt

Rappe

2018

Advanced Materials

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X-site anions are possible, with only two general requirements that must be fulfilled: i) charge neutrality in the ABX 3 unit (typically, X is a divalent or monovalent anion, hence A and B cations with oxidation states between +1 and +5 can be combined) and ii) the ionic radii of the chosen composition must allow the above coordination, or different phases become more stable. Both of these simple design rules have a certain flexibility.The electronic argument i) can be stretched by allowing the combination of multiple ABX 3 units to form an overall charge neutral unit. For example, this is the case when considering A 2 BB′X 6 or AA′B 2 X 6 systems. Such double perovskite systems are known with B and B′ (A and A′) being the same elemental species (disproportion in oxidation state, e.g., Cs 2 Au + Au 3+ I 6 ) [20] or different ones (e.g., SrBaTi 2 O 6 [21] and SrPbTi 2 O 6 [22] for A-site disproportion or K 2 NbTaO 6 [23] and Bi 2 FeCrO 6 [24] for the B-site). Of course, this concept can also be used to combine three ABX 3 units (e.g., (CaTiO 3 ) n (SrTiO 3 ) l (BaTiO 3 ) m [25-27]) and much more complex stoichiometries with mixed ratios (e.g., (Pb 2 InNbO 6 ) 3/4 (Ba 2 InBiO 6 ) 1/4 [28] or [CaMn 3 3+ ][Mn 3 3+ Mn 4+ ] O 12 ] [29] ). Furthermore, although the bonding character in oxide perovskites is often mainly ionic, some compositions have an increased level of covalency (e.g., halides, sulfides, Bi-and Pbbased oxide perovskites). Thus, the electronic shell configuration and other effects like the steric demands of a metal lonepair will influence the structure and stability of ABX 3 perovskite compounds.In addition, the geometric argument ii) allows for some flexibility. For a perfectly cubic perovskite, the (effective) ionic radii r must fulfill the relation of Goldschmidt's tolerance factor 2( ) 1 A X B X t r r r r = + + = . [30,31] However, perovskites can exist also with t being not ideal, usually in a range of about 0.75 < t < 1.05. [8] Whenever t ≠ 1, the crystal distorts from an ideal cubic lattice, usually in form of off-center displacements, octahedral rotations, or a combination of both. The classification of Glazer [32,33] can be used to describe such distortions from a perfectly cubic perovskite. [34] It is further possible that ABX 3 compounds are stable whose t does not fall into the interval that is required for the perovskite crystal structure. In these cases that are no longer stabilized by deformations and tilting, one observes other phases where the connectivity of BX 6Materials science evolves to a state where the composition and structure of a crystal can be controlled almost at will. Given that a composition meets basic requirements of stoichiometry, steric demands, and charge neutrality, researchers are now able to investigate a wide range of compounds theoretically and, under various experimental conditions, select the constituting fragments of a crystal. One intriguing playground for such materials design is the perovskite structure. While a game of mixing and matching ions has been pla...

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Section: Organic A-and X-sites: Hp(ax)mentioning

confidence: 99%

Mix and Match: Organic and Inorganic Ions in the Perovskite Lattice

Gebhardt

Rappe

2018

Advanced Materials

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“…[7] These materials can be prepared as nanoparticles and thin films,a nd their properties can be tuned by varying both the composition and the morphology. [9][10][11] Like the analogous perovskites,t hese materials tend to display multiple phases.T he active distortion modes are often characterised by rigid rotations of the metal-coordination octahedra, avoiding the energy penalty that would come from distorting them. More generally still, these materials are part of the broader family of metal-organic perovskite analogues,i nw hich possible linkers include the formate, azide,t hiocyanate,a nd dicyanamide anions.…”

mentioning

confidence: 99%

Crossover between Tilt Families and Zero Area Thermal Expansion in Hybrid Prussian Blue Analogues

Phillips

Fortes

2017

Angew Chem Int Ed

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Materials in the family of Prussian blue analogues (C H N ) K[M(CN) ], where C H N is the imidazolium ion and M=Fe, Co, undergo two phase transitions with temperature; at low temperatures the imidazolium cations have an ordered configuration (C2/c), while in the intermediate- and high-temperature phases (both previously reported as R3‾m ) they are dynamically disordered. We show from high-resolution powder neutron diffraction data that the high-temperature phase has zero area thermal expansion in the ab-plane. Supported by Landau theory and single-crystal X-ray diffraction data, we re-evaluate the space group symmetry of the intermediate-temperature phase to R3‾ . This reveals that the low-to-intermediate temperature transition is due to competition between two different tilt patterns of the [M(CN) ] ions. Controlling the relative stabilities of these tilt patterns offers a potential means to tune the exploitable electric behaviour that arises from motion of the imidazolium guest.

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“…Zeolitic metal-azolate frameworks (MAFs), a subclass of porous MOFs, have been attracting particular attention due to their potential application [1] superior to traditional zeolites in many fields, such as gas storage/separation [2][3][4], catalysis [5], sensing, and drug delivery [6,7]. In practical application, the zeolitic MAFs would experience several rounds of mechanical manufacturing processes.…”

Section: Introductionmentioning

confidence: 99%

Enhanced Framework Rigidity of a Zeolitic Metal-Azolate via Ligand Substitution

et al. 2017

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Abstract:The elastic properties of a zeolitic metal-azolate framework, Zn(mtz) 2 (MAF-7, mtz − = 3-methyl-1,2,4-triazolate), have been examined from the view point of the first principles calculations and experiments. Our results demonstrate that the three independent elastic constants of MAF-7 are about 5.0-73.3% higher than those of ZIF-8, though they are isomorphic. The electron-donating effect of the nitrogen atom at the 2-position in mtz-ring dominantly accounts for such a prominent difference. The detailed analysis of the full elastic tensors reveals that the volume moduli, shear moduli, and Poisson's ratios of MAF-7 are about 3.4% to 20.1%, 3.2% to 20.6%, and −30.3% to 12.3% higher than those of ZIF-8. The underlying structural reasons were discussed to explain the anisotropic difference of those properties. Moreover, the conclusion deduced from first-principle calculations was also been verified by nanoindentation and high-pressure synchrotron X-ray diffraction measurements.

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Chemically diverse and multifunctional hybrid organic–inorganic perovskites

Cited by 1,027 publications

References 198 publications

Mix and Match: Organic and Inorganic Ions in the Perovskite Lattice

Mix and Match: Organic and Inorganic Ions in the Perovskite Lattice

Crossover between Tilt Families and Zero Area Thermal Expansion in Hybrid Prussian Blue Analogues

Enhanced Framework Rigidity of a Zeolitic Metal-Azolate via Ligand Substitution

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