TY - JOUR

T1 - Metal halide perovskites with photoactive organoboron cations: DFT case study

AU - Кеворкянц, Руслан Эдуардович

AU - Shtarev, D.S.

PY - 2026/3/1

Y1 - 2026/3/1

N2 - Crystal structures and optoelectronic properties of hypothetical quasi low-dimensional lead halide perovskites (C2N2BH4)2PbX4 and C5N2BH15PbX4 (X = Cl, Br, I) with aromatic five-membered diazaborole and linear boratahexenediamine cations are studied using density functional theory (DFT) as implemented in Vienna Ab initio Simulation Package (VASP). The compounds are dynamically stable, as confirmed by their harmonic phonon spectra. According to the calculations, the perovskites are semiconductors with electronic bandgaps computed using Heyd-Scuseria-Ernzerhof 06 (HSE06) density functional and taking into account spin-orbit coupling (SOC) effects in the ranges [1.64-2.02] eV ((C2N2BH4)2PbX4) and [1.64-1.87] eV (C5N2BH15PbX4). Unlike most hybrid organic-inorganic perovskites (HOIPs) whose organic cations bear merely a structural role and do not participate in valence band (VB) to conduction band (CB) electronic transitions, the proposed perovskites feature VBs comprised mainly from the organoboron cations contributions. It is demonstrated that the organoboron cations and halogen anions act as Lewis acids and Lewis bases, respectively, and form donor-acceptor bonds. This work broadens our knowledge of the physics and chemistry of HOIPs, which is fundamental to modern photovoltaics and optoelectronics.

AB - Crystal structures and optoelectronic properties of hypothetical quasi low-dimensional lead halide perovskites (C2N2BH4)2PbX4 and C5N2BH15PbX4 (X = Cl, Br, I) with aromatic five-membered diazaborole and linear boratahexenediamine cations are studied using density functional theory (DFT) as implemented in Vienna Ab initio Simulation Package (VASP). The compounds are dynamically stable, as confirmed by their harmonic phonon spectra. According to the calculations, the perovskites are semiconductors with electronic bandgaps computed using Heyd-Scuseria-Ernzerhof 06 (HSE06) density functional and taking into account spin-orbit coupling (SOC) effects in the ranges [1.64-2.02] eV ((C2N2BH4)2PbX4) and [1.64-1.87] eV (C5N2BH15PbX4). Unlike most hybrid organic-inorganic perovskites (HOIPs) whose organic cations bear merely a structural role and do not participate in valence band (VB) to conduction band (CB) electronic transitions, the proposed perovskites feature VBs comprised mainly from the organoboron cations contributions. It is demonstrated that the organoboron cations and halogen anions act as Lewis acids and Lewis bases, respectively, and form donor-acceptor bonds. This work broadens our knowledge of the physics and chemistry of HOIPs, which is fundamental to modern photovoltaics and optoelectronics.

KW - DFT

KW - Donor-acceptor bond

KW - HOIP

KW - Optoelectronic properties

KW - Organoboron

UR - https://www.mendeley.com/catalogue/f73dc542-fc52-32e9-a5db-e1c2ea6ace70/

U2 - 10.1016/j.jpcs.2025.113393

DO - 10.1016/j.jpcs.2025.113393

M3 - Article

VL - 210

JO - Journal of Physics and Chemistry of Solids

JF - Journal of Physics and Chemistry of Solids

SN - 0022-3697

M1 - 113393

ER -