Pyridinium lead tribromide and pyridinium lead triiodide: quasi-one-dimensional perovskites with an optically active aromatic π-system

• Published in: Dalton transactions : an international journal of inorganic chemistry Vol. 47; no. 45; pp. 16313 - 16319
• Main Authors: Selivanov, N I, Murashkina, A A, Kevorkyants, R, Emeline, A V, Bahnemann, D W
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 22.11.2018
• Subjects: Absorption spectra; Conduction bands; Crystal structure; Crystals; Density of states; NMR; Nuclear magnetic resonance; Optical activity; Orbitals; Perovskites; Single crystals; Synthesis; Valence band; X ray photoelectron spectroscopy
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c8dt03041c

Two novel hybrid organic-inorganic perovskites, pyridinium lead tribromide and pyridinium lead triiodide, are prepared. Based on the XRD data, we find that the compounds are quasi-one-dimensional crystals of Pna21 symmetry. DFT calculations demonstrate that the valence band of the new compounds is comprised of the occupied p-orbitals of the halogen anions, while their conduction bands CB and CB + 1 are composed mainly of the unoccupied π-orbitals of the aromatic pyridinium rings. The computed DOS matches well with the recorded XPS spectra. The pyridinium lead tribromide and pyridinium lead triiodide absorption peaks derived from the experimental DRS are located at ∼3.1 eV and ∼2.4 eV, respectively. An agreement between the experimentally and theoretically predicted absorption spectra is found. The synthesized compounds extend the range of quasi-one-dimensional organometallic perovskites suitable for optical and possibly electronic applications.