About cookies on this site Our websites require some cookies to function properly (required). In addition, other cookies may be used with your consent to analyze site usage, improve the user experience and for advertising. For more information, please review your options. By visiting our website, you agree to our processing of information as described in IBM’sprivacy statement. To provide a smooth navigation, your cookie preferences will be shared across the IBM web domains listed here.
Publication
Inorganic Chemistry
Paper
Organic-inorganic perovskites containing trivalent metal halide layers: The templating influence of the organic cation layer
Abstract
Thin sheetlike crystals of the metal-deficient perovskites (H2AEQT)M2/3I4 [M = Bi or Sb; AEQT = 5,5‴-bis-(aminoethyl)-2,2′:5′,2″:5″,2‴- quaterthiophene] were formed from slowly cooled ethylene glycol/2-butanol solutions containing the bismuth(III) or antimony(III) iodide and AEQT·2HI salts. Each structure was refined in a monoclinic (C2/m) subcell, with the lattice parameters a = 39.712(13) Å, b = 5.976(2) Å, c = 6.043(2) Å, β = 92.238(5)°, and Z = 2 for M = Bi and a = 39.439(7) Å, b = 5.952(1) Å, c = 6.031(1) Å, β = 92.245(3)°, and Z = 2 for M = Sb. The trivalent metal cations locally adopt a distorted octahedral coordination, with M-I bond lengths ranging from 3.046(1) to 3.218(3) Å (3.114 Å average) for M = Bi and 3.012(1) to 3.153(2) Å (3.073 Å average) for M = Sb. The new organic-inorganic hybrids are the first members of a metal-deficient perovskite family consisting of (Mn+2/nV(n-2)/nX42- sheets, where V represents a vacancy (generally left out of the formula) and the metal cation valence, n, is greater than 2. The organic layers in the AEQT-based organic-inorganic hybrids feature edge-to-face aromatic interactions among, the rigid, rodlike quaterthiophene moieties, which may help to stabilize the unusual metal-deficient layered structures.