Role of Amine-Cavity Interactions in Determining the Structure and Mechanical Properties of the Ferroelectric Hybrid Perovskite [NH3NH2]Zn(HCOO)3

Gregor Kieslich; Alexander C. Forse; Shijing Sun; Keith T. Butler; Shohei Kumagai; Yue Wu; Mark R. Warren; Aron Walsh; Clare P. Grey; Anthony K. Cheetham

doi:10.1021/acs.chemmater.5b04143

Role of Amine-Cavity Interactions in Determining the Structure and Mechanical Properties of the Ferroelectric Hybrid Perovskite [NH₃NH₂]Zn(HCOO)₃

Gregor Kieslich, Alexander C. Forse, Shijing Sun, Keith T. Butler, Shohei Kumagai, Yue Wu, Mark R. Warren, Aron Walsh, Clare P. Grey, Anthony K. Cheetham

Department of Materials Science and Engineering

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

42 Citations (Scopus)

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	https://doi.org/10.1021/acs.chemmater.5b04143
Publication status	Published - 2016 Jan 12

All Science Journal Classification (ASJC) codes

Chemistry(all)
Chemical Engineering(all)
Materials Chemistry

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Kieslich, G., Forse, A. C., Sun, S., Butler, K. T., Kumagai, S., Wu, Y., Warren, M. R., Walsh, A., Grey, C. P., & Cheetham, A. K. (2016). Role of Amine-Cavity Interactions in Determining the Structure and Mechanical Properties of the Ferroelectric Hybrid Perovskite [NH₃NH₂]Zn(HCOO)₃. Chemistry of Materials, 28(1), 312-317. https://doi.org/10.1021/acs.chemmater.5b04143

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. / Role of Amine-Cavity Interactions in Determining the Structure and Mechanical Properties of the Ferroelectric Hybrid Perovskite [NH₃NH₂]Zn(HCOO)₃. In: Chemistry of Materials. 2016 ; Vol. 28, No. 1. pp. 312-317.

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title = "Role of Amine-Cavity Interactions in Determining the Structure and Mechanical Properties of the Ferroelectric Hybrid Perovskite [NH3NH2]Zn(HCOO)3",

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.",

author = "Gregor Kieslich and Forse, {Alexander C.} and Shijing Sun and Butler, {Keith T.} and Shohei Kumagai and Yue Wu and Warren, {Mark R.} and Aron Walsh and Grey, {Clare P.} and Cheetham, {Anthony K.}",

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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 › peer-review

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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.

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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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