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

Research output: Contribution to journalArticle

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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 languageEnglish
Pages (from-to)6154-6159
Number of pages6
JournalJournal of Physical Chemistry Letters
Volume8
Issue number24
DOIs
Publication statusPublished - 2017 Dec 21

Fingerprint

perovskites
formic acid
Hydrogen bonds
Cations
hydrogen bonds
Positive ions
hydrogen
cations
formates
Order disorder transitions
Phase stability
Guanidine
magnetic resonance spectroscopy
Coulomb interactions
Nuclear magnetic resonance spectroscopy
Superconducting transition temperature
halides
Amines
phase transformations
Molecular dynamics

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Physical and Theoretical Chemistry

Cite this

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. https://doi.org/10.1021/acs.jpclett.7b03106
Svane, Katrine L. ; Forse, Alexander C. ; Grey, Clare P. ; Kieslich, Gregor ; Cheetham, Anthony K. ; Walsh, Aron ; Butler, Keith T. / How Strong Is the Hydrogen Bond in Hybrid Perovskites?. In: Journal of Physical Chemistry Letters. 2017 ; Vol. 8, No. 24. pp. 6154-6159.
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Svane, KL, Forse, AC, Grey, CP, Kieslich, G, Cheetham, AK, Walsh, A & Butler, KT 2017, 'How Strong Is the Hydrogen Bond in Hybrid Perovskites?', Journal of Physical Chemistry Letters, vol. 8, no. 24, pp. 6154-6159. https://doi.org/10.1021/acs.jpclett.7b03106

How Strong Is the Hydrogen Bond in Hybrid Perovskites? / Svane, Katrine L.; Forse, Alexander C.; Grey, Clare P.; Kieslich, Gregor; Cheetham, Anthony K.; Walsh, Aron; Butler, Keith T.

In: Journal of Physical Chemistry Letters, Vol. 8, No. 24, 21.12.2017, p. 6154-6159.

Research output: Contribution to journalArticle

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T1 - How Strong Is the Hydrogen Bond in Hybrid Perovskites?

AU - Svane, Katrine L.

AU - Forse, Alexander C.

AU - Grey, Clare P.

AU - Kieslich, Gregor

AU - Cheetham, Anthony K.

AU - Walsh, Aron

AU - Butler, Keith T.

PY - 2017/12/21

Y1 - 2017/12/21

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AB - 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.

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