Abstract
Dense formate frameworks with a perovskite-like architecture exhibit multiferroic behavior and tunable mechanical properties. In such materials, interactions between the protonated amine and the metal-formate cavity have a large impact on the mechanical properties. We use complementary single-crystal X-ray diffraction and 1H solid state nuclear magnetic resonance spectroscopy to investigate amine-cavity interactions in [NH3NH2]Zn(HCOO)3. The results suggest that these interactions can be described as salt bridges similar to those in proteins and artificially synthesized helical polymers, where ionic interactions and hydrogen bonds are present at the same time. Nanoindentation and high-pressure single-crystal X-ray diffraction were used to study the mechanical properties of [NH3NH2]Zn(HCOO)3, yielding elastic moduli of E001 = 26.5 GPa and E110 = 24.6 GPa and a bulk modulus of K = 19 GPa. The mechanical properties suggest that, despite the relatively low packing density of [NH3NH2]Zn(HCOO)3, the amine-cavity interactions strengthen the framework significantly in comparison with related materials.
| Original language | English |
|---|---|
| Pages (from-to) | 312-317 |
| Number of pages | 6 |
| Journal | Chemistry of Materials |
| Volume | 28 |
| Issue number | 1 |
| DOIs | |
| Publication status | Published - 2016 Jan 12 |
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All Science Journal Classification (ASJC) codes
- Chemistry(all)
- Chemical Engineering(all)
- Materials Chemistry
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Role of Amine-Cavity Interactions in Determining the Structure and Mechanical Properties of the Ferroelectric Hybrid Perovskite [NH3NH2]Zn(HCOO)3. / Kieslich, Gregor; Forse, Alexander C.; Sun, Shijing; Butler, Keith T.; Kumagai, Shohei; Wu, Yue; Warren, Mark R.; Walsh, Aron; Grey, Clare P.; Cheetham, Anthony K.
In: Chemistry of Materials, Vol. 28, No. 1, 12.01.2016, p. 312-317.Research output: Contribution to journal › Article
TY - JOUR
T1 - Role of Amine-Cavity Interactions in Determining the Structure and Mechanical Properties of the Ferroelectric Hybrid Perovskite [NH3NH2]Zn(HCOO)3
AU - Kieslich, Gregor
AU - Forse, Alexander C.
AU - Sun, Shijing
AU - Butler, Keith T.
AU - Kumagai, Shohei
AU - Wu, Yue
AU - Warren, Mark R.
AU - Walsh, Aron
AU - Grey, Clare P.
AU - Cheetham, Anthony K.
PY - 2016/1/12
Y1 - 2016/1/12
N2 - Dense formate frameworks with a perovskite-like architecture exhibit multiferroic behavior and tunable mechanical properties. In such materials, interactions between the protonated amine and the metal-formate cavity have a large impact on the mechanical properties. We use complementary single-crystal X-ray diffraction and 1H solid state nuclear magnetic resonance spectroscopy to investigate amine-cavity interactions in [NH3NH2]Zn(HCOO)3. The results suggest that these interactions can be described as salt bridges similar to those in proteins and artificially synthesized helical polymers, where ionic interactions and hydrogen bonds are present at the same time. Nanoindentation and high-pressure single-crystal X-ray diffraction were used to study the mechanical properties of [NH3NH2]Zn(HCOO)3, yielding elastic moduli of E001 = 26.5 GPa and E110 = 24.6 GPa and a bulk modulus of K = 19 GPa. The mechanical properties suggest that, despite the relatively low packing density of [NH3NH2]Zn(HCOO)3, the amine-cavity interactions strengthen the framework significantly in comparison with related materials.
AB - Dense formate frameworks with a perovskite-like architecture exhibit multiferroic behavior and tunable mechanical properties. In such materials, interactions between the protonated amine and the metal-formate cavity have a large impact on the mechanical properties. We use complementary single-crystal X-ray diffraction and 1H solid state nuclear magnetic resonance spectroscopy to investigate amine-cavity interactions in [NH3NH2]Zn(HCOO)3. The results suggest that these interactions can be described as salt bridges similar to those in proteins and artificially synthesized helical polymers, where ionic interactions and hydrogen bonds are present at the same time. Nanoindentation and high-pressure single-crystal X-ray diffraction were used to study the mechanical properties of [NH3NH2]Zn(HCOO)3, yielding elastic moduli of E001 = 26.5 GPa and E110 = 24.6 GPa and a bulk modulus of K = 19 GPa. The mechanical properties suggest that, despite the relatively low packing density of [NH3NH2]Zn(HCOO)3, the amine-cavity interactions strengthen the framework significantly in comparison with related materials.
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U2 - 10.1021/acs.chemmater.5b04143
DO - 10.1021/acs.chemmater.5b04143
M3 - Article
VL - 28
SP - 312
EP - 317
JO - Chemistry of Materials
JF - Chemistry of Materials
SN - 0897-4756
IS - 1
ER -