How Strong Is the Hydrogen Bond in Hybrid Perovskites?

Katrine L. Svane; Alexander C. Forse; Clare P. Grey; Gregor Kieslich; Anthony K. Cheetham; Aron Walsh; Keith T. Butler

doi:10.1021/acs.jpclett.7b03106

How Strong Is the Hydrogen Bond in Hybrid Perovskites?

Katrine L. Svane, Alexander C. Forse, Clare P. Grey, Gregor Kieslich, Anthony K. Cheetham, Aron Walsh, Keith T. Butler

Department of Materials Science and Engineering

Research output: Contribution to journal › Article › peer-review

160 Citations (Scopus)

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.

Original language	English
Pages (from-to)	6154-6159
Number of pages	6
Journal	Journal of Physical Chemistry Letters
Volume	8
Issue number	24
DOIs	https://doi.org/10.1021/acs.jpclett.7b03106
Publication status	Published - 2017 Dec 21

Bibliographical note

Publisher Copyright:
© 2017 American Chemical Society.

All Science Journal Classification (ASJC) codes

Materials Science(all)
Physical and Theoretical Chemistry

Access to Document

10.1021/acs.jpclett.7b03106

Cite this

@article{d3c30cf8c73b4acfa80b5114107d2001,

title = "How Strong Is the Hydrogen Bond in Hybrid Perovskites?",

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.",

author = "Svane, {Katrine L.} and Forse, {Alexander C.} and Grey, {Clare P.} and Gregor Kieslich and Cheetham, {Anthony K.} and Aron Walsh and Butler, {Keith T.}",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

month = dec,

day = "21",

doi = "10.1021/acs.jpclett.7b03106",

language = "English",

volume = "8",

pages = "6154--6159",

journal = "Journal of Physical Chemistry Letters",

issn = "1948-7185",