TY - JOUR

T1 - The effect of organic cations on the electronic, optical and luminescence properties of 1D piperidinium, pyridinium, and 3-hydroxypyridinium lead trihalides

AU - Selivanov, N.I.

AU - Rozhkova, YuA.

AU - Kevorkyants, R.

AU - Emeline, A.V.

AU - Bahnemann, D.W.

N1 - Funding Information: This work was financially supported by the Russian Foundation for Basic Research (19-03-00836-a) and was performed within the project by Saint-Petersburg State University (Pure ID 51124539) to create the laboratory "Photoactive nanocomposite materials". The authors are grateful to the Resource Center for X-ray diffraction studies, the Resource Center "Nanophotonics", and the Computational Resource Center of Research Park at St-Petersburg State University. Funding Information: This work was financially supported by the Russian Foundation for Basic Research (19-03-00836-a) and was performed within the project by Saint-Petersburg State University (Pure ID 51124539) to create the laboratory “Photoactive nano-composite materials”. The authors are grateful to the Resource Center for X-ray diffraction studies, the Resource Center “Nanophotonics”, and the Computational Resource Center of Research Park at St-Petersburg State University.

PY - 2020/4/14

Y1 - 2020/4/14

N2 - We present a structural and optoelectronic study of 1D piperidinium, pyridinium, and 3-hydroxypyridinium lead trihalides. In contrast to the piperidinium and pyridinium species whose single inorganic chains [PbX 3 1-] n are separated by organic cations, the 3-hydroxypyridinium compound is characterized by double inorganic chains. According to DFT the valence and conduction bands of the piperidinium lead trihalides are composed of occupied p-orbitals of the halogen anions and unoccupied p-orbitals of the Pb 2+ cations. In contrast, the pyridinium species feature low-lying cationic energy levels formed from the cation's π∗-orbitals. Thus, electronic transitions between the cationic energy levels and valence bands require less energy than valence to conduction band transitions in the case of piperidinium lead trihalides. The presence of an OH group in the pyridinium ring leads to a bathochromic shift of the cationic energy levels resulting in a decreased energy of transitions from the cationic energy levels to the valence band. Electronic transitions predicted by DFT are observable in experimental optical absorption and luminescence spectra. This study paves the way for creation of 1D perovskite-like structures with desired optoelectronic properties.

AB - We present a structural and optoelectronic study of 1D piperidinium, pyridinium, and 3-hydroxypyridinium lead trihalides. In contrast to the piperidinium and pyridinium species whose single inorganic chains [PbX 3 1-] n are separated by organic cations, the 3-hydroxypyridinium compound is characterized by double inorganic chains. According to DFT the valence and conduction bands of the piperidinium lead trihalides are composed of occupied p-orbitals of the halogen anions and unoccupied p-orbitals of the Pb 2+ cations. In contrast, the pyridinium species feature low-lying cationic energy levels formed from the cation's π∗-orbitals. Thus, electronic transitions between the cationic energy levels and valence bands require less energy than valence to conduction band transitions in the case of piperidinium lead trihalides. The presence of an OH group in the pyridinium ring leads to a bathochromic shift of the cationic energy levels resulting in a decreased energy of transitions from the cationic energy levels to the valence band. Electronic transitions predicted by DFT are observable in experimental optical absorption and luminescence spectra. This study paves the way for creation of 1D perovskite-like structures with desired optoelectronic properties.

UR - http://www.scopus.com/inward/record.url?scp=85083041867&partnerID=8YFLogxK

U2 - 10.1039/C9DT04543K

DO - 10.1039/C9DT04543K

M3 - Article

VL - 49

SP - 4390

EP - 4403

JO - Dalton transactions

JF - Dalton transactions

SN - 1477-9226

IS - 14

ER -