TY - JOUR
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.
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/12/21
Y1 - 2017/12/21
N2 - 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.
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.
UR - http://www.scopus.com/inward/record.url?scp=85039151539&partnerID=8YFLogxK
U2 - 10.1021/acs.jpclett.7b03106
DO - 10.1021/acs.jpclett.7b03106
M3 - Article
C2 - 29216715
AN - SCOPUS:85039151539
SN - 1948-7185
VL - 8
SP - 6154
EP - 6159
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 24
ER -