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Transformation of Perovskite BaBiO 3 into Layered BaBiO 2.5 Crystals Featuring Unusual Chemical Bonding and Luminescence
Author(s) -
Li Hong,
Zhao Qing,
Liu BoMei,
Zhang JunYing,
Li ZhiYong,
Guo ShaoQiang,
Ma JuPing,
Kuroiwa Yoshihiro,
Moriyoshi Chikako,
Zheng LiRong,
Sun HongTao
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201801257
Subject(s) - luminescence , perovskite (structure) , ionic bonding , crystallography , chemical bond , materials science , stoichiometry , covalent bond , crystal structure , rietveld refinement , chemistry , nanotechnology , ion , optoelectronics , organic chemistry
Engineering oxygen coordination environments of cations in oxides has received intense interest thanks to the opportunities for the discovery of novel oxides with unusual properties. Herein, the synthesis of stoichiometric layered BaBiO 2.5 by a nontopotactic phase transformation of perovskite BaBiO 3 is presented. By analyzing the synchrotron X‐ray diffraction data by the maximum‐entropy method/Rietveld technique, it was found that Bi is involved in an unusual chemical bonding situation with four oxygen atoms featuring one ionic bond and three covalent bonds, which results in an asymmetric coordination geometry. Photophysical characterization revealed that this peculiar structure shows near‐infrared luminescence differing from that of conventional Bi‐containing compounds. Experimental and theoretical results led to the proposal of an excitonic nature of the luminescence. This work highlights that synthesizing materials with uncommon Bi−O bonding and Bi coordination geometry provides a pathway to the discovery of systems with new functionalities. This could inspire interest in the exploration of a range of materials containing heavier p‐block elements with prospects for finding systems with unusual properties.