Multinuclear solid-state NMR investigation of structurally diverse low-dimensional hybrid metal halide perovskites

• Published in: Journal of materials chemistry. A, Materials for energy and sustainability Vol. 12; no. 35; pp. 23461 - 23474
• Main Authors: Hooper, Thomas J. N., Febriansyah, Benny, Krishnamoorthy, Thirumal, Wong, Walter P. D., Xue, Kai, Ager, Joel W., Mathews, Nripan
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 10.09.2024
• Subjects: Bromine isotopes; Cations; Dynamic structural analysis; Halides; Lead; Lead isotopes; Magnetic properties; Metal halides; Molecular dynamics; NMR; NMR spectroscopy; Nuclear magnetic resonance; Optoelectronics; Perovskites; Solid state; Spectroscopy; Spin-lattice relaxation; Tin; Tin isotopes
• ISSN: 2050-7488; 2050-7496
• DOI: 10.1039/D4TA02833C

Owing to their synthetic versatility and optoelectronic tunability, low-dimensional hybrid metal halide perovskites (MHPs) provide a key avenue for the design of future optoelectronic materials. Nuclear magnetic resonance (NMR) spectroscopy has emerged as a powerful tool for structural characterisation and molecular dynamics elucidation in MHPs, which are known to control the materials' optoelectronic properties. In this work, we utilise solid state NMR to study structurally diverse hybrid MHPs containing 2D, 1D and 0D inorganic motifs that are templated by a series of xylylenediammonium cations and compare their characteristics with those of archetype 3D perovskites. The highly resolved scalar coupling pattern ( J 1 ( 207 Pb– 79/81 Br) = 1.98 kHz) in the 207 Pb NMR spectrum of 0D meta -xylylenediammonium lead bromide (( m XDA) 2 PbBr 6 ), reveals that 207 Pb NMR of methylammonium lead bromide (MAPbBr 3 ) and formadinium lead bromide (FAPbBr 3 ) is sensitive to local Br positional disorder, associated with the fast reorientation of the MA/FA cations. Variable temperature 1 H spin–lattice relaxation quantifies the correlation time of the reorientation of the MA/FA cations at picosecond timescales, in contrast to the slower motion of the bulky cations in the low-dimensional perovskites. Additionally, the study of meta -xylylenediammonium tin halides (( m XDA) 2 Sn X 6 ) provides the first direct detection of tin-halide scalar coupling patterns ( J 1 ( 119 Sn– 79/81 Br) = 1.51 kHz; J 1 ( 119 Sn– 35/37 Cl) = 260 Hz).