Near Zero Area Compressibility in a Perovskite-Like Metal–Organic

Jul 6, 2018 - For the first time, a near ZAC single material is explicitly reported. This study opens up an exciting research field on pressure-resist...
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Near Zero Area Compressibility in a PerovskiteLike Metal-Organic Frameworks [C(NH)][Cd(HCOO)] 2

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Qingxin Zeng, Kai Wang, and Bo Zou ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b08599 • Publication Date (Web): 06 Jul 2018 Downloaded from http://pubs.acs.org on July 7, 2018

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Near Zero Area Compressibility in a Perovskite-Like Metal-Organic Frameworks [C(NH2)3][Cd(HCOO)3] Qingxin Zeng, Kai Wang,* and Bo Zou State Key Laboratory of Superhard Materials, College of Physics, Jilin University, Changchun 130012, China KEYWORDS: high-pressure, zero area compressibility, anomalous mechanics, density functional theory calculations

ABSTRACT: Materials with zero area compressibility (ZAC) can keep their crystal uncompressed in two specific directions upon uniformly compression. High-pressure angledispersive X-ray powder diffraction (ADXRD) experiments reveal a ZAC phenomenon in the ab-plane in crystal of a formate-based perovskite, [C(NH2)3][Cd(HCOO)3]. The ZAC behavior is ascribed to the unique rhombohedral [Cd(HCOO)3]- frameworks and confirmed by density functional theory (DFT) calculations. For the first time, a near ZAC single material is explicitly report. This study opens up an exciting research field on pressure-resistant materials. We anticipate more ZAC materials to be discovered in the following explorations under the inspiration of this work.

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Most materials contract in all crystal directions with increasing pressure, whilst a limited number of bizarre ones expand along one (two) specific direction when compressed uniformly, the so called negative linear (area) compressibility (NLC,1-6 NAC7-9). Even rarer is zero linear/area compressibility (ZLC/ZAC), with which property the materials neither expands nor contracts in one/two specific direction over a certain pressure range.10 The excellent property endows ZLC/ZAC materials with potential applications such as in sonar, hydrophones, and telecommunication optical fibers that can keep their dimensions unchanged under high-pressure conditions such as the deep-sea environments.11-12 ZLC/ZAC nanocomposites could be achieved by combining the NLC/NAC materials with materials with positive linear compressibility (PLC).13-14 However, the fabrications of ZLC/ZAC composites are heavily hampered by the narrow pressure range in which the NLC/NAC behavior exists. For example, the c-axis of Ag3[Co(CN)6]-I crystals has the most extreme NLC effect, but its length undergoes a sudden decrease at 0.19 GPa with a phase transition.3 It is therefore preferable to engineer ZLC/ZAC behavior at the atomic level within a single material. The structurally related family of organic–inorganic hybrid perovskites with general formula ABX3 have attracted extraordinary attention in physics, chemistry, and materials science recently. The highly tolerant substitutions of the A, B and X sites ions have given rise to a large family with various geometric structures at the molecular level,15-16 which therefore offer a great deal of remarkable functional properties, such as negative linear compressibility, negative thermal expansion, multiferroic behavior, magnetism, hydrogen storage, photophysical and electronic properties.4,17-23 Previous reports indicate that compressibility and thermal expansion are highly related to crystal structure topology.2,24 ZLC/ZAC is hence expected in this intriguing family for its diversity of crystal structures. Herein, we study the pressure-induced structural

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evolutions in a formate-based perovskite, [C(NH2)3][Cd(HCOO)3] ([C(NH2)3]+ = guanidinium), by performing high-pressure angle-dispersive X-ray powder diffraction (ADXRD) experiments and density functional theory (DFT) calculations. And a near ZAC behavior is found in this material. Under ambient conditions, [C(NH2)3][Cd(HCOO)3] crystallizes in the trigonal structure with space group 3.17 There are 6 molecules in one unit cell. All of the cadmium atoms in the unit cell are equivalent and located at the origin (Wyckoff position 6b). Each metal ion connects to six nearest neighboring metal ions through six bridges of formate ligand in anti–anti mode to form the anionic NaCl-type [Cd(HCOO)3]- frameworks, with the [C(NH2)3]+ template in the center of the rhombohedral cavity of the frameworks as shown in Figure 1. The rhombohedral [Cd(HCOO)3]- frameworks are related to the famous “wine-rack” topology, which is the most common structural feature associated with anomalous mechanical responses, such as NLC and NTE.2,25-26 The distinction is that wine-rack topology is a 2D structure with one of its diagonals paralleled to the NLC direction while [Cd(HCOO)3]- frameworks is a 3D structures. Therefore, [Cd(HCOO)3]- frameworks have more complicated geometric relationships with the unit cell parameters than the 2D wine-rack topology.

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Figure 1. The structure of [C(NH2)3][Cd(HCOO)3]. (a) The structure of rhombohedral cavity of the anionic NaCl-type [Cd(HCOO)3]- frameworks and the center [C(NH2)3]+ template. (b) The 3D structure of the cavity-template units in 2 × 2 × 2 size in [C(NH2)3][Cd(HCOO)3] crystal viewed from the a direction. The Hydrogen atoms are omitted for clarity. (c) Selected diffraction patterns of [C(NH2)3][Cd(HCOO)3] at elevated pressures from 1atm to 2.90 GPa. (d) Experimental (spheres) and computational (circles) evolutions of the changes of lattice parameters as a function of pressure. In situ high pressure ADXRD measurements were carried out utilizing diamond anvil cells at room temperature to investigate the pressure-induced structural variations of [C(NH2)3][Cd(HCOO)3] over the pressure range of 1atm to 2.90 GPa. Figure 1Error! Reference source not found.c depicts the representative ADXRD patterns at elevated pressures. Taking no

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account of the normal shifts of diffraction peak positions, it is evident that the original ADXRD patterns were maintained without appearance of new diffraction peaks over the whole process of compressing, indicating that the original crystal structure space group 3 was kept over the pressure range from ambient to 2.90 GPa without any phase-transitions. All the Bragg peaks should shift toward high diffraction angle region as a result of d-spacing shortening under compression, while it is worth of stressing that the (2-10) Bragg peak position kept nearly unmoved under compression, which indicates that the d-spacing of (2-10) plane neither expanded nor contracted under compression up to 2.90 GPa. The pressure-induced evolution of the relative lattice parameters extracted from Pawley refinements is shown in Figure 1d. The high hardness of the a- and b-axis could be apparently deduced from the hardly shrinking of the length of lattice parameters a and b (only by about 1.0% up to 2.90 GPa). On the contrary, the caxis underwent a dramatic decreasing in length by about 9.2% at 2.90 GPa. The linear compressibility of the unit cell axes was calculated utilizing the online program PASCal and presented in Table S1 (Supporting Information, SI).27 Over the pressure range of 1atm to 2.90 GPa, the a- and b-axis exhibited a very small linear compressibility (3.33 TPa-1), while the linear compressibility of c-axis was relatively larger (32.9 TPa-1), showing an intriguing distinct mechanical anisotropy. Particularly, the ab-plane showed a near zero area compressibility over the pressure range of ambient to 0.53 GPa (this pressure range is typical for many practical applications28), during which the compressibility of the a-axis (and b-axis) was just 0.94 TPa-1 (Table S1, SI). Such a value of compressibility is far less than typical values for crystalline materials (5–20 TPa-1).29 The rhombohedral [Cd(HCOO)3]- frameworks were investigated to analyze the mechanical anisotropy in [C(NH2)3][Cd(HCOO)3] crystals. Figure 2a depicts the model of the rhombohedra

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unit in the unit-cell lattice. The body diagonal paralleled to the c-axis is a 3-fold axis of the rhombohedra unit and is half the length of lattice parameter c. The tetrahedral top apex of the rhombohedra unit in Figure 2a is emphasized in Figure 2b. The Cd atom is located at Wyckoff position b with coordinate of (0, 0, 0), the lattice parameters are therefore related to the rhombohedra with a one-to-one mapping relationships:

    2 ∙ sin 

(1)

  232  1 (2) where r is the length of the rhombohedral framework strut of Cd-formate-Cd linker; and θ is one of the three equivalent intra-framework angles (Cd···Cd···Cd) that located at the apex region as shown in Figure 2b.

Figure 2. (a) The model of the rhombohedra unit of [Cd(HCOO)3]- frameworks in the unit cell lattice, its tetrahedral top apex is magnified in (b). (c) The scheme of the near ZAC along the ab-

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plane and the PLC along the c-axis. Only part of Cd atoms are shown and the formate ligands are simplified to be blue sticks for clarity. Without a phase transition, the relationships therefore also applies to crystal structures at high pressure. The values of r and θ derived from lattice parameters at each pressure using eq (1) and (2) are shown in Figure 3. It is easily seen that the length of r decreased as a result of bond shortening while the intra-framework θ increased due to rhombohedral framework hinging over the compression process. According to eq (1), the decrease in r and the increase in θ have the opposite effect on the variation of length in lattice parameters a and b. The decrease in r contributes to the contraction of a, on the contrary, the increase in θ counteracts the contraction. The competitive relationship between r and θ gives rise to the high steadiness of the a- and baxis, which contracted by only 0.04% up to 0.53 GPa, indicating a near zero area compressibility along the ab-plane. As for the c-axis, both the decrease in r and the increase in θ could result to the contraction of the c-axis according to eq (2). As a result of the combined action of r and θ, the c-axis was shortened remarkably under compression with a large linear compressibility. Therefore, the near ZAC behavior along the ab-plane and the PLC behavior along the c-axis are ascribed to the tetrahedron mechanism schematically described in Figure 2c. Intriguingly, the high stiffness (ab-plane) and softness (c-axis) naturally coexist in this single material.

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Figure 3. Experimental variations of framework parameters r and θ as a function of pressure (red spheres for r; blue spheres for θ). In order to better investigate the variations of framework under compression, DFT calculations were performed from ambient to 3 GPa with a step size of 0.1 GPa. The change rate of the calculated lattice parameters are depicted in Figure 1d. Up to 2.90 GPa, the computational shrinkages of the a- and c-axis are 0.6% and 10.0% compared to 1.0% and 9.2% for experimental data, respectively. The subtle distinction reflects a high consistency of the computational and experimental results. The near ZAC behavior along the ab-plane and PLC behavior along the c-axis are also observed in the computational data. To reveal the pressureinduced variations of framework lattice r and θ, some key bond lengths and angles were monitored over the computational compression process, see in Figure 4. The C-O bond lengths and O-C-O angles undergo very subtle changes from 0 to 3 GPa, indicating the high rigidity of sp2 hybridized formate ligand. Therefore, the decrease in r is mainly caused by the decreases of Cd-O bond lengths and Cd-O-C angles, as shown in Figure 4b and 4c. Meanwhile, the increase

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in O-Cd-O angles accounts for the increase in framework angles θ under compression (Figure 4c).

Figure 4. (a) X-ray structure of [C(NH2)3][Cd(HCOO)3], The Hydrogen atoms are omitted for clarity. (b) Computational evolution of bond length (Cd-O as squares; C-O as circles) as a function of pressure. (c) Computational evolution of angle (O-C-O as red circles; Cd-O-C as red squares; O-Cd-O as blue triangles) as a function of pressure. In conclusion, a perovskite-like metal-organic frameworks [C(NH2)3][Cd(HCOO)3] was found to exhibit near zero area compressibility along its ab-plane by high-pressure angle-dispersive X-ray powder diffraction experiments and furtherly confirmed by density functional theory calculations. The abnormal mechanical response is ascribed to the unique rhombohedral frameworks of [C(NH2)3][Cd(HCOO)3] crystal structure. To our knowledge, this is the first explicit report on a single material with the intrinsic property of near ZAC. Compared to ZAC composites fabricated from NLC/NAC components, the single materials with ZAC are easier to obtain and meanwhile are free of constraints of the NLC/NAC components on negative compressibility values and pressure ranges. This study opens up an exciting new research field,

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the effects of external pressure on zero compressibility, which is of crucial importance for application of zero compressibility materials in the future. We anticipate more materials with smaller or ever absolutely zero compressibility to be discovered in the following explorations under the inspiration of this work. ASSOCIATED CONTENT Supporting Information. The following files are available free of charge. Sample preparation, high-pressure ADXRD measurements, DFT calculations, Pawley refinement, volume change rate, compressibility. (PDF) AUTHOR INFORMATION Corresponding Author *E-mail: [email protected]. ORCID Kai Wang: 0000-0003-4721-6717 Bo Zou: 0000-0002-3215-1255 Notes The authors declare no competing financial interest. ACKNOWLEDGMENT This work is supported by the National Science Foundation of China (NSFC) (Nos. 21673100, 21725304, 11774120, 91227202), the Chang Jiang Scholars Program of China (No. T2016051),

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Changbai Mountain Scholars Program (No. 2013007), and program for innovative research team (in science and technology) in university of Jilin Province. The work concerning in situ ADXRD measurements was performed at the 4W2 High Pressure Station in Beijing Synchrotron Radiation Facility. REFERENCES (1)

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