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Title: How Strong Is the Hydrogen Bond in Hybrid Perovskites?
Authors: Svane, K.L
Forse, A.C
Grey, C.P
Kieslich, G
Cheetham, A.K 
Walsh, A
Butler, K.T
Keywords: Crystalline materials
Magnetic resonance spectroscopy
Molecular dynamics
Nuclear magnetic resonance spectroscopy
Order disorder transitions
Positive ions
First principles
Halide perovskites
Hybrid organic-inorganic
Hydrogen-bonding strength
Metal organic framework
Molecular cations
Solid state nuclear magnetic resonance spectroscopy
Hydrogen bonds
Issue Date: 2017
Publisher: American Chemical Society
Citation: Svane, K.L, Forse, A.C, Grey, C.P, Kieslich, G, Cheetham, A.K, Walsh, A, Butler, K.T (2017). How Strong Is the Hydrogen Bond in Hybrid Perovskites?. Journal of Physical Chemistry Letters 8 (24) : 6154-6159. ScholarBank@NUS Repository.
Rights: Attribution 4.0 International
Abstract: Hybrid organic-inorganic perovskites represent a special class of metal-organic framework where a molecular cation is encased in an anionic cage. The molecule-cage interaction influences phase stability, phase transformations, and the molecular dynamics. We examine the hydrogen bonding in four AmBX3 formate perovskites: [Am]Zn(HCOO)3, with Am+ = hydrazinium (NH2NH3+), guanidinium (C(NH2)3+), dimethylammonium (CH3)2NH2+, and azetidinium (CH2)3NH2+. We develop a scheme to quantify the strength of hydrogen bonding in these systems from first-principles, which separates the electrostatic interactions between the amine (Am+) and the BX3- cage. The hydrogen-bonding strengths of formate perovskites range from 0.36 to 1.40 eV/cation (8-32 kcalmol-1). Complementary solid-state nuclear magnetic resonance spectroscopy confirms that strong hydrogen bonding hinders cation mobility. Application of the procedure to hybrid lead halide perovskites (X = Cl, Br, I, Am+ = CH3NH3+, CH(NH2)2+) shows that these compounds have significantly weaker hydrogen-bonding energies of 0.09 to 0.27 eV/cation (2-6 kcalmol-1), correlating with lower order-disorder transition temperatures. © 2017 American Chemical Society.
Source Title: Journal of Physical Chemistry Letters
ISSN: 1948-7185
DOI: 10.1021/acs.jpclett.7b03106
Rights: Attribution 4.0 International
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