How Strong Is the Hydrogen Bond in Hybrid Perovskites?

被引：204

作者：

Svane, Katrine L. ^{[1
]}

Forse, Alexander C. ^{[2
,7
,8
,9
]}

Grey, Clare P. ^{[2
]}

Kieslich, Gregor ^{[3
]}

Cheetham, Anthony K. ^{[4
]}

Walsh, Aron ^{[5
,6
]}

Butle, Keith T. ^{[1
]}

机构：

[1] Univ Bath, Dept Chem, Bath BA2 7AY, Avon, England

[2] Univ Cambridge, Dept Chem, Cambridge CB2 1EW, England

[3] Tech Univ Munich, Dept Chem, Lichtenbergstr 4, D-85748 Garching, Germany

[4] Univ Cambridge, Dept Mat Sci & Met, Cambridge CB3 0FS, England

[5] Imperial Coll London, Dept Mat, Exhibit Rd, London SW7 2AZ, England

[6] Yonsei Univ, Dept Mat Sci & Engn, Seoul 03722, South Korea

[7] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA

[8] Univ Calif Berkeley, Dept Chem & Biomol Engn, Berkeley, CA 94720 USA

[9] Univ Calif Berkeley, Berkeley Energy & Climate Inst, Berkeley, CA 94720 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2017年 / 8卷 / 24期

基金：

英国工程与自然科学研究理事会; 英国科学技术设施理事会;

关键词：

METAL-ORGANIC FRAMEWORKS; MOLECULAR-DYNAMICS; PHASE-TRANSITION; DIELECTRIC ANOMALIES; NMR CRYSTALLOGRAPHY; THERMAL-EXPANSION; DISORDER; TEMPERATURE; BEHAVIOR; MOTION;

D O I：

10.1021/acs.jpclett.7b03106

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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)(2)NH2+, and azetidinium (CH2)(3)NH2+. 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.

引用

页码：6154 / 6159

页数：6

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