Crystal structure and strong piezoelectricity of new amino acid based

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Article

Crystal structure and strong piezoelectricity of new amino acid based hybrid crystals: [H-#-(3-Pyridyl)-Ala-OH][ClO] and [H-#-(4-Pyridyl)-Ala-OH][ClO]. 4

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Maciej Wojtas, Vasyl Kinzhybalo, Igor Bdikin, and Andrei L. Kholkin Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01611 • Publication Date (Web): 27 Mar 2019 Downloaded from http://pubs.acs.org on March 28, 2019

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

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Crystal Growth & Design

Crystal structure and strong piezoelectricity of new amino acid based hybrid crystals: [H–β–(3–Pyridyl)–Ala–OH][ClO4] and [H–β–(4–Pyridyl)–Ala–OH][ClO4]. Maciej Wojta´s,∗,† Vasyl Kinzhybalo,‡ Igor Bdikin,¶ and Andrei L. Kholkin§,∥ †Faculty of Chemistry, University of Wroclaw, 14 Joliot–Curie, 50–383 Wroclaw, Poland ‡W. Trzebiatowski Institute of Low Temperature and Structure Research, Polish Academy of Science, PO Box 1410, 50-950 Wroclaw, Poland ¶TEMA-NRD, Mechanical Engineering Department, Aveiro Institute of Nanotechnology (AIN), University of Aveiro, 3810-193 Aveiro, Portugal. §Department of Physics and CICECO - Aveiro Institute of Materials, 3810-193 Aveiro, Portugal. ∥School of Natural Sciences and Mathematics, Ural Federal University, 620000 Ekaterinburg, Russia. E-mail: [email protected] Abstract The

new

amino

acid

based

[H − β − (3 − Pyridyl) − Ala − OH][ClO4 ]

and [H − β − (4 − Pyridyl) − Ala − OH][ClO4 ] crystals were synthesized and their structure and functional piezoelectric properties were investigated in detail. Both analogs crystallize in the polar, piezoelectric P 21 space group. Piezoresponse Force Microscopy (PFM)

measurements

revealed

that

1

shear

ACS Paragon Plus Environment

piezoelectric

coefficient

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of [H − β − (3 − Pyridyl) − Ala − OH][ClO4 ] crystal is more than twice of that in the widely used transducer material lithium niobate, LiNbO3 . The crystal structures of both perchlorate derivatives were determined and the influence of the inter– and intramolecular hydrogen bond network on piezoelectricity of crystals were discussed. The existence of the intramolecular hydrogen bonding was confirmed by means of IR spectroscopy measurements. Thermogravimetric (TGA) technique was applied to study the thermal behavior of title crystals.

Introduction Piezoelectricity was discovered by Curie brothers in 1880 1 and first application of piezoelectric materials was sonar developed during World War I by Paul Langevin and his coworkers. 2,3 These materials (except of the 432 point group) due to the direct piezoelectric effect, when subjected to mechanical stress, generate an electric charge proportional to that stress and due to the converse piezoelectric effect they generate the mechanical stress when an electric field is applied. Nowadays this property is used in many applications, i.a. acoustic transducers, piezomotors or sensors and actuators. 4 One of the important class of piezoelectrics are ferroelectrics. The ferroelectrics are characterized by polar axis which direction can be altered by the application of an external electric field. These materials exhibit piezoelectric constants significantly higher than these found in nature such as some bio–organic materials (e.g. lamellar–bone, collagen). This property makes the ferroelectric organic materials increasingly important because of their potential applications in the areas of microelectronics and micromechanical systems, for instance: field effect transistors and non–volatile memories. 5,6 In comparison to inorganic ferroelectrics/piezoelectrics organic compounds have two main advantages: the price and the ease of controlling the structure trough chemistry. Last years has experienced significant progress in the search of new organic ferroelectrics useful for microelectronics. 4,7,8 It has been shown that highly organized molecular dipole assemblies frequently exhibit piezoelec2


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tricity. It is due to the presence of polar bonds and natural asymmetry, which is a feature of many organic biomaterials, such as proteins, peptides, amino acids and polysaccharides. It appears that one of the most interesting materials for nanoelectronic applications is alanine derivative, L–Phenylalanyl–L–Phenylalanine, which easily self–assembles in the tube–like structures. 9 The structure of this dipeptide as well as in L–Leucyl–L–Leucine, L–Leucyl–L– Phenylalanine and L–Phenylalanyl–L–Leucine was studied in detail by Görbitz 10–12 whereas Gazit’s group 9,13–16 focused on the properties of these dipeptides. Later on, Kholkin et. al 17 demonstrated that peptide nanotubes (PNTs) exhibit strong piezoelectricity with the orientation of polarization along the axis of the tube. Recently we have widen the research of amino acids into the organic–inorganic materials by synthesizing hybrid salts of selected, voluminous amino acid and simple, small inorganic acids (HClO4 , HBF4 etc.) derivatives. 18 It has been shown that tetrafluoroborate derivative of 2–Pyridyl alanine exhibit piezoelectric constants higher than those of lithium niobate. In the current work we present the complementary studies based on X–ray diffraction, thermogravimetry, infrared and Raman spectroscopy and piezoresponse force microscopy (PFM) of two other alanine derivatives: [H–β–(3–Pyridyl)–Ala–OH][ClO4 ] and [H–β–(4–Pyridyl)– Ala–OH][ClO4 ].

Experimental Hybrid salts were prepared by reaction of perchloric acid (60%, POCh) with either H–β– (3–Pyridyl)–Ala–OH ((S)-2-Amino-3-(3-pyridyl)propionic acid, Sigma–Aldrich) or H–β–(4– Pyridyl)–Ala–OH ((S)-2-Amino-3-(4-pyridyl)propionic acid, Sigma–Aldrich) in stoichiometric ratio in the water solution. The solutions were then dried at ambient conditions and yielded small, colorless, needle–shaped crystals in both cases. The elemental analysis results agreed well with the proposed formulas: [H-β-(3-Pyridyl)-Ala-OH][ClO4 ] (hereafter abbreviated as [3PyAla][ClO4 ] ): N: 11.51%; C: 36.90%, H: 4.75% and [H-β-(4-Pyridyl)-

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Ala-OH][ClO4 ] (hereafter abbreviated as [4PyAla][ClO4 ] ): N: 11.14%; C: 36.78%, H: 4.12% (theoretical N: 10.50%; C: 36.04%, H: 4.13%). The samples for the AFM measurements were prepared by drying the drop of water solution of [3PyAla][ClO4 ] or [4PyAla][ClO4 ] on the platinum coated silicon substrate. Crystallographic data for compounds [3PyAla][ClO4 ] and [4PyAla][ClO4 ] were collected at 295 and 100 K on a Xcalibur four–circle diffractometer operating in κ–geometry and equipped with a two–dimensional CCD detector and MoKα radiation (λ = 0.71073 ˚ A). The instrument was supported by an Oxford Cryosystems 800 series cryocooler. The determination of the unit cell and data collection was performed with CrysAlis CCD program. 19 The CrysAlis RED software version 1.171.38.46 (Oxford Diffraction) was used for data processing. Analytical numeric absorption correction using a multifaceted crystal model was applied on all data. 20 Direct method structure solution, difference Fourier calculations and full–matrix least squares refinement against F 2 were performed with SHELXT and SHELXL-2014/7 crystallographic software package 21 via the Olex2 interface. 22 All non–hydrogen atoms were located successfully from Fourier maps and were refined with anisotropic temperature factors. The positions of hydrogen atoms of the organic cations were initially located in the difference Fourier maps, and for the final refinement, the hydrogen atoms were placed geometrically. Crystallographic data obtained at room and low temperature did not show the existence of phase transitions between 295 and 100 K, and for the discussion and comparison of the reported compounds the low–temperature refinements were used. Details on the single crystals XRD data collection, reduction and structure parameters for the two compounds are summarized in Table 1. The absolute structure was assigned based on chemical information and confirmed with refined Flack parameters. CCDC 1847725, 1844650, 1847726 and 1844649 contain full crystallographic details for the structure of [3PyAla][ClO4 ] (295 K), [3PyAla][ClO4 ] (100 K), [4PyAla][ClO4 ] (295 K) and [4PyAla][ClO4 ] (100 K), respectively. Thermogravimetric analyses (TGA) and differential thermal analyses (DTA) were performed on a Setaram SETSYS 16/18 instrument in nitrogen atmosphere in the temperature range

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298–900 K and 5 deg·min−1 heating rate for both samples. [3PyAla][ClO4 ] sample mass: 8.440 mg; [4PyAla][ClO4 ] sample mass: 9.478 mg. FT–IR spectra at room temperature (Fluorolube and Nujol mulls, polyethylene windows) were taken using BRUKER 66 spectrometer with the resolution of 2 cm−1 . Raman spectra were collected using a Thermo Scientific Nicolet iS50 Raman module mounted in the sample compartment of a Thermo Scientific Nicolet iS50 FTIR spectrometer. An indium–gallium-arsenide (InGaAs) detector and CaF2 beamsplitter were used to carry out the measurements. Samples were illuminated by a 1.064 µm Nd : YVO4 laser with the power of 250 mW. The interferograms were averaged over 256 scans, Happ–Genzel apodised and Fourier transformed using a zero–filling factor of 2 to yield spectra in the 200–3700 cm−1 range with a resolution of 2 cm−1 . The Scanning Electron Microscopy (SEM) images were prepared using Hitachi S-3400N equipped with detector EDS Thermo Scientific Ultra Dry operating at 5 kV/10 kV. Atomic Force Microscopy (AFM) measurements were carried out using a Veeco AFM Multimode Nanoscope (IV) MMAFM–2, Veeco microscopy. Local piezoelectric properties of the sample were visualized simultaneously by using Atomic Force Microscopy in contact mode and Piezoresponse Force Microscopy methods. The PFM technique is based on the converse piezoelectric effect, which is a linear coupling between the electrical and mechanical properties of a material. To detect the polarization orientation the AFM tip is used as a top electrode, which is moved over the sample surface. For PFM imaging doped (n+) Si cantilevers with the resistivity 0.01–0.02 Ωcm and tip apex radius of less than 10 nm with spring constant 7.4 N/m were used (Nanosensors). AC voltage of 5 V at a frequency of 35 kHz was applied. The measurement frequency was chosen far away from the resonant frequencies of the cantilever sample–holder system to avoid the ambiguity of experimental data. The optical microscope observations were carried out by means of Olympus BX53 polarization microscope.

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Crystal Growth & Design 1 2 3 Table 1: Crystal data, experimental details and structure refinement results for 4 [3PyAla][ClO4 ] and [4PyAla][ClO4 ] crystals at 100 K and 295 K. 5 6 7 [3PyAla][ClO4 ] [4PyAla][ClO4 ] 8 9 Crystal data 10 formula, Mr C8H11ClN2O6, 266.64 Chemical 11 Temperature (K) 100 295 100 295 12 Crystal system, space group Monoclinic, P 2 1 13 a, b, c (˚ A) 5.141(2),9.146(3), 5.181(2),9.206(3), 5.141(2),9.176(3), 5.168(2),9.264(3), 14 10.756(3) 10.862(3) 10.791(3) 10.915(3) 15 ◦ β ( ) 96.21(3) 95.95(3) 96.06(3) 95.78(3) 16 3 ˚ V ( A ) 502.8(3) 515.3(3) 506.2(3) 519.9(3) 17 Z 2 18 F(000) 276 19 −1 µ (mm ) 0.40 0.39 0.40 0.39 20 Crystal size (mm) 0.38 × 0.22 × 0.09 0.38 × 0.22 × 0.09 0.64 × 0.33 × 0.04 0.65 × 0.32 × 0.05 21 22 Data collection 23 T , T 0.889,0.969 0.912,0.974 0.829,0.985 0.835,0.982 min max 24 No. of measured, independent 11064,2485,2345 11261,2572,2327 10788,2495,2340 34364,2682,2530 25 and observed [I> 2σ(I)] reflections 26 Rint 0.029 0.026 0.040 0.035 27 ◦ Θ ,Θ ( ) 29.5,2.9 29.4,2.9 29.6,2.9 29.6,3.8 max min 28 29 Refinement 30 2 2 2 R[F > 2σ(F )], wR(F ), S 0.029,0.067,1.08 0.032,0.070,1.08 0.032,0.076,1.07 0.027,0.070,1.05 31 No. of reflections 2485 2572 2495 2682 32 No. of parameters 155 155 155 155 33 No. of restraints 1 1 1 1 34 −3 ˚ ∆ρ , ∆ρ (e· A ) 0.23,-0.48 0.20,-0.33 0.26,-0.37 0.20,-0.24 max min 35 Absolute structure Flack x determined using 36 985 968 987 1129 37 23 quotients [(I+)-(I-)]/[(I+)+(I-)] 38 0.00(2) -0.01(2) -0.03(3) -0.040(18) 39 Absolute structure parameter 40 41 42 43 44 Both compounds [3PyAla][ClO4 ] and [4PyAla][ClO4 ] crystallize in the monoclinic polar P 21 45 46 space group with the asymmetric unit that consist of one protonated 3-(3-pyridyl)alanine 47 48 (or 3-(4-pyridyl)alanine) counterion and one perchlorate anion as illustrated in Fig. 1. All 49 50 the molecules lay in general positions. The ClO4 – anions are slightly distorted out from 51 52 a regular tetrahedral geometry. The Cl—O bond lengths in the perchlorate group range 53 54 from 1.4349(19) to 1.4509(18) ˚ A for [3PyAla][ClO4 ] and from 1.429(2) to 1.447(2) ˚ A for 55 56 57 58 6 59 ACS Paragon Plus Environment 60

Crystal structure

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Figure 1: Molecular structure of [3PyAla][ClO4 ] (a) and [4PyAla][ClO4 ] (b) at 100 K, along with the crystallographic numbering scheme and hydrogen–bonding interactions (marked as dashed lines). Displacement ellipsoids were drawn with the 50% probability level. [4PyAla][ClO4 ] . The corresponding O—Cl—O angles are within 108.97(11)–110.31(11)◦ for the former and 108.68(12)–110.24(14)◦ range for the latter compound, respectively. It is worth of note that another amino acid–inorganic acid hybrid salt [2PyAla][ClO4 ] may be characterized by very similar values of these angles whereas the Cl—O bonds are slightly shorter. 18 The geometrical parameters (bond lengths and angles) for two organic molecules in the crystals are very similar and are in good agreement with those reported for the related compounds, such as [2PyAla][ClO4 ] and [2PyAla][BF4 ]

18

, corroborating the protonation of

both the amine and pyridine nitrogen atoms. One of C—H groups of the pyridinium ring forms an intramolecular C—H. . . O hydrogen bond with O atom of the carboxyl group as a result of tilting of the latter group towards the pyridinium ring (Fig. 1a and b). This bonding is reflected by similar torsion angles for the bonds C3—C2—C1—O2: -56.79(2) and -56.09(2)◦ in [3PyAla][ClO4 ] and [4PyAla][ClO4 ] compounds, respectively. The analysis of the crystal structure of title closely related perchlorates revealed that there are four strong intermolecular hydrogen bonds: between the hydrogen atoms bonded to the N atoms of the pyridinium and ammonium groups and two oxygen atoms of the perchlorate anions and two oxygen atoms of the carboxyl group (see Table 2 and Fig. 2). In both compounds the N1—H1A. . . O2 bonds connect neighboring cations into chains propagating along the a–axis direction, and the N1—H1C. . . O1 hydrogen bonds produce the second chain parallel to the b–axis. The N1—H1B. . . O11 and N11—H11. . . O14 hydrogen bonds in [3PyAla][ClO4 ] (and the N1—H1B. . . O11 and N11—H11. . . O13 hydrogen bonds in 7



[4PyAla][ClO4 ] ) arrange the cations into the third chain sequence which is extended along the [101] crystallographic direction. As a result, these chains are connected with each other by the perchlorate anions being nodes in the resulting 3D network. As shown in Fig. 2a–b, organic ions within the ab plane are linked into two–dimensional layer by means of two types of hydrogen–bonds X—H. . . O (where X = N and C) interactions (labeled as ’The hydrogen bonds between cations’ in Table 2). The perchlorate anion in both compounds accepts nine hydrogen bonds: five N—H. . . O type and four C—H. . . O type (Fig. 2c–d). As it was

Figure 2: The hydrogen-bonded arrangements of organic counterions in a) [3PyAla][ClO4 ] and b) [4PyAla][ClO4 ] compounds connected by N—H. . . O (cyan dashed lines) and C—H. . . O (yellow dashed lines) hydrogen bonds. (c) and (d) illustrate the organic cations in the environment of perchlorate anions for [3PyAla][ClO4 ] and [4PyAla][ClO4 ] , respectively. The strongest hydrogen bonds are marked with bold dashed lines Hydrogen atoms not involved in hydrogen bonding are omitted for clarity. Symmetry codes: (iii) 1 − x, 0.5 + y, 1 − z; (v) 1 − x, −0.5 + y, 1 − z; (vi) −1 + x, y, z; (vii) −1 + x, y, 1 + z.

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Table 2: Selected hydrogen-bond parameters of [3PyAla][ClO4 ] and [4PyAla][ClO4 ] at 295 K. [3PyAla][ClO4 ] D—H. . . A N1—H1A. . . O2ii† N1—H1B. . . O11 N1—H1C. . . O1iii† N11—H11. . . O14iv C2—H2. . . O1i C2—H2. . . O2i C14—H14. . . O2 C2—H2. . . O12 N1—H1B. . . O12ii N11—H11. . . O13iii C12—H12. . . O11iii C15—H15. . . O11v C16—H16. . . O13iv C16—H16. . . O14v

[4PyAla][ClO4 ]

D—H H. . . A D. . . A D—H. . . A D—H. . . A The strongest hydrogen bonds 0.91 1.91 2.792(3) 163.0 N1—H1A. . . O2ii† 0.91 2.25 3.122(3) 160.3 N1—H1B. . . O11 0.91 1.87 2.737(3) 158.6 N1—H1C. . . O1iii† 0.88 2.19 2.946(3) 143.7 N11—H11. . . O13iv The hydrogen bonds between cations 1.00 2.60 3.322(3) 128.8 C2—H2. . . O1i 1.00 2.46 3.168(3) 127.3 C2—H2. . . O2i 0.95 2.59 3.342(3) 136.1 C15—H15. . . O2 Other hydrogen bonds 1.00 2.58 3.265(3) 126.0 C2—H2. . . O12 0.91 2.40 2.898(3) 114.8 N1—H1B. . . O12ii 0.88 2.44 3.096(3) 132.1 N11—H11. . . O14v 0.95 2.51 3.413(3) 159.4 C13—H13. . . O11iii 0.95 2.51 3.282(3) 138.3 C12—H12. . . O13iii 0.95 2.39 3.291(3) 158.2 C12—H12. . . O14iv 0.95 2.72 3.378(3) 127.2 C16—H16. . . O11v

D—H H. . . A D. . . A D—H. . . A 0.91 0.91 0.91 0.88

1.92 2.25 1.85 2.18

2.803(3) 3.117(3) 2.732(3) 2.984(3)

162.9 159.5 161.5 152.0

1.00 1.00 0.95

2.58 2.49 2.60

3.314(3) 3.201(3) 3.349(4)

130.0 127.8 136.3

1.00 0.91 0.88 0.95 0.95 0.95 0.95

2.56 2.37 2.43 2.47 2.64 2.32 2.60

3.263(3) 2.877(3) 3.005(3) 3.381(4) 3.375(4) 3.184(4) 3.367(4)

127.5 114.8 123.6 161.2 134.5 151.4 138.1

Symmetry codes: (i) −x, y + 1/2, −z + 1; (ii) x + 1, y, z; (iii) −x + 1, y + 1/2, −z + 1; (iv) x + 1, y, z − 1; (v) −x + 1, y − 1/2, −z + 1. †: the hydrogen bonds between cations as well

discussed earlier, the geometric features of organic and inorganic subunits of both analyzed crystals are very alike, so the packing of the crystals (illustrated by Fig. 3) is almost identical. The largest structural difference occurs in the arrangement of perchlorate anions with respect to counterions which is caused by the different location of N atom in pyridinium ring. This, in turn, affects the location of the N—H. . . O and C—H. . . O hydrogen bonds in [3PyAla][ClO4 ] and [4PyAla][ClO4 ] . The Hirshfeld surface analysis and 2D fingerprint plots were generated using the CrystalExplorer software 24 and employed in order to check the contributions of the weak intermolecular interactions present in these structures. While aromatic π − π stacking interactions are absent in both structures, weak C—O. . . π and Cl—O. . . π interactions were found present (see Fig. S1 in Supplemental Materials). In both compounds O2 atom is involved in an intermolecular C—O. . . π interaction with the π system of the pyridyl ring. The distances

9



between ring centroid and interacting O2 atom equal 3.3913(13) ˚ A in [3PyAla][ClO4 ] and 3.3994(13) ˚ A in [4PyAla][ClO4 ] . In the case of intermolecular Cl—O. . . π interaction observed for [3PyAla][ClO4 ] , the O14 atom of the perchlorate anion interacts with the pyridyl ring of an adjacent molecule (3.1588(12) ˚ A), while in [4PyAla][ClO4 ] this distance amounts 3.4063 ˚ A. However, in [4PyAla][ClO4 ] , beside the Cl—O14. . . π interaction the atom O13 is also involved in the weak Cl—O13. . . π interaction (3.7363(13) ˚ A) what additionally stabilizes the packing of the crystals.

Figure 3: The packing diagrams of a) [3PyAla][ClO4 ] and b) [4PyAla][ClO4 ] viewed along [100] showing the N—H. . . O (cyan dashed lines) and C—H. . . O (yellow dashed lines) hydrogen bonds.

IR and Raman measurements Figures 4(a) and (b) show the IR and Raman spectra of [3PyAla][ClO4 ] and [4PyAla][ClO4 ] , respectively. IR spectra were recorded in fluorolube and nujol oil at ambient conditions. Both IR spectra recorded in nujol are characterized by broad, intense absorption forming 10


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a continuum resembling a Hadˇzi’s trio, 25 therefore the IR spectra can be well fit with 3 components. In the case of [3PyAla][ClO4 ] the peak maxima are at 2850 cm−1 , 1460 cm−1 and 1100 cm−1 whereas the respective peak maxima of [4PyAla][ClO4 ] lie at 2900 cm−1 , 1500 cm−1 and 1100 cm−1 . In both cases the observed images fit the asymmetric potential with double minimum for hydrogen motion. This potential may be described with the formula: 26

V (r, R) = a2 (R)r2 + a3 (R)r3 + a4 (R)r4 ,

where r stands for the coordinate of the proton movement, R is the coordinate of the hydrogen bridge vibration and a2 , a3 and a4 are parameters dependent on R. The origin of the Hadˇzi’s trio is the coupling of the hydrogen bridge vibrations, which are damped by interactions with the lattice phonons 27 with the anharmonic stretching vibrations of the proton of the hydrogen bond. It is worth of note that the Hadˇzi’s trio is observed despite the intramolecular O. . . H—C bonds may be considered as rather weak interactions. Table 3 presents the bands frequencies and their assignments. The assignments of 28–30 were used as guides.

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Raman nujol fluorolube

(a)

fluorolube

3500 3000 2500 2000 1500 1000 (b)

500

nujol fluorolube

3500 3000 2500 2000 1500 1000

Transmittance [arb. units]

nujol Raman intensity [arb. units]

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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500

-1

wavenumber [cm ]

Figure 4: Infrared (nujol and fluorolube oil) and Raman spectra of [3PyAla][ClO4 ] (a) and [4PyAla][ClO4 ] (b). The dashed lines show Hadˇzi’s trio and its sum for respective compounds.

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Table 3: Vibrational frequencies of [3PyAla][ClO4 ] and [4PyAla][ClO4 ] recorded in ambient conditions.

Raman

[3PyAla][ClO4 ]

FT–IR

[4PyAla][ClO4 ] Raman FT–IR Wavenumbers [cm−1 ] 3562mf ,3558m 3280sh,3280shf ,3266s, 3264vsf 3173sh,3173shf ,3159m, 3158mf 3096m,3079w,3057sh 3095m,3094sf

3479m 3189w,3189wf ,3176w, 3176wf 3110m 3138w, 3138wf , 3126vw, 3126vwf 3110wf ,3110w 3093w,3051m 3094m, 3094mf ,3073m, 3073mf 3000w,2987w,2971m 2990mf , 2988sh 2983sh,2961m 2960vsn ,2922vsn ,2862vsf , 2934m 2824vsn 2917mf ,2873w 2705w, 2705wf 3274w

2567vwf ,2564vw 2483vw,2483vwf 2108vw,2108vwf

1634m 1597m,1592sh 1507vw

1420m,1414sh 1368w 1352w 1322m

1999w,1999wf ,1948vw, 1948vwf ,1889vw,1894vwf 1647vs,1647vsf , 1624vs, 1640m 1624vsf 1584vs,1584vsf ,1568sh, 1611w 1568shf 1545s,1545vsf 1507s,1507vsf 1505vw,1490w 1473m,1473mf ,1465mn , 1445vwf 1419m,1419sf ,1412m, 1412mf 1380shf ,1377mn , 1365mf ,1364w,1355w, 1335mf ,1351s,1351sf 1324sf ,1323s,1309m, 1308mf 1286m,1258w,1246w 1226w,1206vw,1191w

1289w 1248m,1227m, 1208vw,1194w 1135w,1127w 1102vw,1079vw 1052w,1041w 1027vs 971w,933vs,920m

1128vs 1106vs,1075vs

910w,898w

906m,896m,865m

865vw,856vw,844vw 827w 784sh,780s 713vw 684vw 634m,626s,600vw, 580vw

825m,802vw 842vw,817vw 778s 718m 682vs 637w,626vs,602w

1051w,1041w 998w,968m,930w

1450w 1420vw,1404vw

523s,487m,464w, 434w

sym. NH2 stretch. asym. NH3 stretch. and C—H aromatic

2855mf ,2854vsn 2715w,2703vwf ,2652vw, 2652vwf 2563vw,2560vwf NH stretch. in NH3 2474vwf ,2471w 2347vw,2347vwf stretch.CNH bend. 2118vw,2108vwf , 2022w,2019wf 1869vw,1869f 1648vs,1648vsf ,1637vs, 1637vsf 1605vs,1605sf ,1586vs, 1586vsf ,1586vsf 1540sh,1537shf 1516s,1513vsf ,1508s, 1507vsf 1465sn ,1454sn ,1448mf

NH3 puckering C=C and C=N conjugated CH2 bend

1419m,1419mf ,1405m, 1404sf 1377mn 1361m,1360mf

CH3 bend NH3 puckering

NH2 bend. C=N conjugated

CN stretch

1280m,1258w 1222w,1211m,1201m 1124vs 1095vs,1078vs

NH bend H3 —N1 —C2 —C3 bend

862vw,

1040s,1022m 1009m,990w,986w,933w, asym NC2 stretch 924w 898w,887w,864m, sym NC2 stretch 849w,833w 828m,806w

788sh,780m 736w,732vw,715vw 663vw,655vw,651m 626m,621sh

784s,778s 730m,723w 675w,650w 627vs,599w

553m 497sh,488w,468m, 528m,499w,485vw, 464sh 428vw 453vw,451w 343vw 13 316vw,306vw ACS Paragon Plus Environment 272vw,237vw,214m, 204m n –bands of nujol oil;f –bands observed in fluorolube oil vs–very strong;s–strong;m–medium;w–weak;vw–very weak;sh–shoulder 518w,484m,464s, 458m 443w,433vw 395vw,383vw 310vw 250m,212m

asym. NH2 stretch.

2985wf 2959vsn ,2957wf ,2924vsn

1364m,1355sh 1343sh,1343shf ,1336m, 1333mf 1330m,1320sh 1315sh,1304m 1281w,1263w,1252vw 1221m,1212w, 1199m,1160vw 1131vw 1099vw,1087vw 1066w 1064w,1048vw,1009s 971w,954vw,931s, 923vs 910vw,900vw

Assignments

NH2 rocking HNC bend. OCOH + NH2 bend OH bend


Thermal behavior Figure 5 presents the results of thermogravimetric (TGA) measurements of the [3PyAla][ClO4 ] (a) and [4PyAla][ClO4 ] (b) samples. Both crystals are thermally stable up to c.a. 476 K ([3PyAla][ClO4 ] ) and 448 K ([4PyAla][ClO4 ] ). At these temperatures the decomposition of the salts starts and up to 900 K both crystals loose about 80% of the initial mass. In the case of [4PyAla][ClO4 ] there is visible additional small weight loss below 448 K. It is, however, less than 1% of the initial mass thus may be related with the presence of water in the sample. Beside this the thermal behavior of both studied crystals is very similar and demonstrates the same exoenergetic thermal anomalies manifested as two peaks what is common for perchlorate derivatives. 31,32 During this process both samples loose about 25% of the initial mass what perfectly agrees with the pyrolytic process of ClO4 – −−→ Cl – + 2 O2 proposed by Markowitz et al. 32

0

heat flow

(a)

weight loss

-20

exo

-60

-80

476 K

0

(b) endo

-20

weight loss [%]

-40 heat flow [arb. units]

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 14 of 30

-40

-60 448 K

300

400

500

600

-80

700

800

900

Temperature [K]

Figure 5: TGA scans of [3PyAla][ClO4 ] and [4PyAla][ClO4 ] . The scans were performed in flowing nitrogen with a ramp rate of 5 deg·min−1 ([3PyAla][ClO4 ] sample mass: 8.440 mg; [4PyAla][ClO4 ] sample mass: 9.478 mg). The vertical dashed line shows the begin of the weight loss of the sample. 14


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PFM measurements Figure 6(a) presents the optical microscope (magnification 200×) image of the [3PyAla][ClO4 ] sample. One can see the elongated, either needle or plate shaped crystals. Inset shows the SEM image, arrows illustrate the crystal orientation. The AFM images (Figure 6(b), (c) and (d)) were acquired in a contact mode and the topography, out–of–plane (OOP) and in–plane (IP) piezoresponse signals were recorded simultaneously. The AFM topography image is consistent with the picture taken by optical microscope. As grown polycrystal consists of small microcrystals (islands) as well as well separated needle shaped crystals. On the OOP piezoresponse image the islands exhibit either positive or negative signal (corresponding to opposite polarization directions), whereas the needle shaped crystals’ signal is slightly positive. Though the IP signal is several times higher than the OOP one the in–plane image is less contrast than the former one. Notwithstanding one can observe the positive and negative signals. It is worth of note that there is no strict correlation between the OOP and IP signals indicating different polarization directions in the grown crystals .

15



Figure 6: (a)The optical microscopy image of [3PyAla][ClO4 ] taken with magnification 200× together with SEM image (mag. 470×), (b) topography, (c) topography with piezoresponse OOP and (d) topography with piezoresponse IP of [3PyAla][ClO4 ] sample. (e) The optical microscopy image of [4PyAla][ClO4 ] taken with magnification 40× together with SEM image (mag. 1400×), (f) topography, (g) piezoresponse OOP and (h) piezoresponse IP of [4PyAla][ClO4 ] sample (f). The stripes on (g) and (h) are due to different voltages applied to the sample. (i) Profile graph along lines marked on (f), (g) and (h). The dotted line intersecting the graph stands for the piezoresponse 0 value. 16


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Figure 6(e) shows the image of [4PyAla][ClO4 ] sample taken by optical microscope. The inset is the SEM image along with crystallographic axis of the sample. Similarly to [3PyAla][ClO4 ] the crystals are either needle or plate shaped ones. Pictures (f), (g) and (h) present the images of topography of one selected crystal, its OOP and IP piezoresponse components, respectively. The stripes visible on the PFM images are due to the different magnitudes of driving voltage applied as will be explained below. Fig. 6(i) shows the cross– section of topography and piezoresponse signals of the sample taken along the lines marked in the corresponding AFM and PFM images. The piezoresponse is strongly correlated with the topography of the sample but the change of the IP signal from negative to positive suggests that even the individual needle shaped crystals are composed of grown together small crystals with the different orientation of polarization. This effect of concretion seems to be confirmed by the shape of OOP signal which is generally speaking strongly negative (ca. -2 arbitrary units) however on the edge of the crystal no signal is observed. It should be emphasized that the IP signal is several times higher than the OOP one as it was in the case of [3PyAla][ClO4 ] crystals. It is worth of note that the concretion of crystals was present also in H–β–(2–Pyridyl)–Ala–OH 33 and [2PyAla][ClO4 ] . 18 Most probably the way of preparation the sample on the substrate (see Experimental section) may lead to the growth of the non–uniform microcrystals. In order to prove the piezoelectric character of [3PyAla][ClO4 ] and [4PyAla][ClO4 ] the piezoresponse vs. AC electric field (driving voltage) measurements were carried out. However, it should be borne in mind that due to the inhomogeneous E–field distribution 34 the PFM allows to estimate only the effective piezoresponse. To get the idea what are the values of the effective piezoelectric modulus in our samples’ piezoresponse was compared with that of the commercially available LiNbO3 (LNO) sample (periodically poled lithium niobate, cut normal to the polar axis, NT-MDT). In this way it was possible to quantify the magnitude of piezoeffect in materials avoiding rigorous calculations. 35 The following diagram shows the piezoelectric modulus matrix for the point group 2 with

17



Page 18 of 30

standard axes orientation, 36 where a light dote stands for a modulus that is zero. 



· · d14 · d16  ·   d  21 d22 d23 · d25 ·  · · · d34 · d36

    

The longitudinal deformation of [3PyAla][ClO4 ] and [4PyAla][ClO4 ] may be due to driving voltage applied parallel to the b axis. Beside this the shear deformation of samples exposed to the electric field of the same direction (parallel to the b axis) is dependent only on the d25 component. Thus it was possible to detect IP signal due to that shear component of the piezotensor, corresponding to the polarization parallel to the a axis. The piezoresponse signal was acquired while the sample was scanned. The driving voltage was increased every ca. 30 lines and both OOP and IP signals were recorded simultaneously. Fig. 7(a) shows the dependence of the piezoresponse on scanned area (the driving voltage applied is shown on the graph). The piezoresponse obtained at each AC electric field was averaged and its dependence vs. driving voltage is presented on Fig. 7(b). Taking d33 LNO as equal to 17 pm/V (see Wong 37 ) the d22 which stands for a longitudinal component and d25 which stands for a shear component of the piezotensor yielded from OOP and IP signals, respectively, were calculated. The most striking feature is the fact that piezoresponse of IP signal of [3PyAla][ClO4 ] is twice as much as that of LNO sample. It should be adverted that the recorded piezoresponse is very stable and both titled crystals can be driven under high excitation level since neither nonlinearity nor irreversibility even at AC voltage of 15 V were observed. It is worth of note that the common feature of crystals under investigation is the higher IP response than OOP one. Moreover the piezoelectric coefficients, d25 and d22 , of [3PyAla][ClO4 ] are higher than d25 and d22 of [4PyAla][ClO4 ] , respectively.

18


Page 19 of 30

LNO

IP

(a)

OOP

[3PyAla][ClO ] IP

OOP

(b)

4

[4PyAla][ClO ] IP

6

6

4

[3PyAla][ClO ] OOP

38.6

0.3 pm/V

20.0

0.3 pm/V

17.7

0.9 pm/V

5.8

0.9 pm/V

4

[4PyAla][ClO ] OOP 4

4

2

Piezoresponse [arb. units]

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


4

2

0

0 15 | 0 | 2.5 | 5

0 2 4 6 8 10 12 14 16

| 7.5 | 10 | 12.5|15

Driving voltage [V]

Driving voltage [V]

Figure 7: (a) The IP and OOP piezoresponse of [3PyAla][ClO4 ] vs. driving voltage. (b) The driving voltage dependence of piezoresponse of LNO, [3PyAla][ClO4 ] and [4PyAla][ClO4 ] .

Discussion Both studied crystals exhibit strong piezoelectric properties. The in–plane piezoresponse of [3PyAla][ClO4 ] seems to be the most striking finding of these studies – the effective coefficient d25 is twice as much as the d33 of LNO. It is interesting to compare the studied crystals [3PyAla][ClO4 ] and [4PyAla][ClO4 ] with [2PyAla][ClO4 ] (i.e. the perchlorate derivative of 2–pyridyl alanine crystal, ref. 18 Table4 illustrates selected properties of these crystals (symmetry, piezoelectric properties). It is clearly seen that there are significant differences between investigated crystals. The 3– pyridyl and 4–pyridyl alanine derivatives crystallize in polar monoclinic P 21 space group whereas 2–pyridyl one in nonpolar orthorhombic P 21 21 21 . Equally large dissimilarities concern the magnitude of piezoelectric coefficients which are much smaller in the case of

19



Page 20 of 30

Table 4: Selected properties of [3PyAla][ClO4 ] , [4PyAla][ClO4 ] and [2PyAla][ClO4 ] space group

polarity

longitudinal component

shear component

P 21 P 21 P 21 21 21

yes yes no

18 6 ≈0

39 20 3

Crystal [3PyAla][ClO4 ] [4PyAla][ClO4 ] [2PyAla][ClO4 ]

number of strongest H–bonds intramolecular intermolecular 1 1 1

4 4 7

[2PyAla][ClO4 ] (although the studies of piezoresponse were carried out by means of different AFM systems the experimental setup was comparable in each case and the piezoelectric effect was referred to the LNO). It seems that the origin of such a state of affairs, beside the dependence of piezoelectric tensor on symmetry of crystal – see ref., 18 is the strength of the hydrogen bonds. The N—H. . . O hydrogen bonds of [2PyAla][ClO4 ] seem to be stronger than these observed in titled crystals what can be demonstrated by their parameters. The distances of donor–acceptor are similar in both cases but the angles donor– H–acceptor are substantially more linear (therefore stronger e.g. ref 38 ) in the structure of [2PyAla][ClO4 ] than in [3PyAla][ClO4 ] and [4PyAla][ClO4 ] . Moreover, oxygen from perchlorate ions in [2PyAla][ClO4 ] acts as an acceptor in 7 different hydrogen bonds whereas in titled crystals just in 4. Thus the supramolecular structure of 2–pyridyl derivative seems to be more rigid than the structure of 3– and 4–pyridyl analogs. This can lead to the conclusion that the rigidity of the crystal structure negatively affects i.e. diminishes the magnitudes of piezoelectric coefficients. It is worthy of note that the H–bonds comparison above was performed for structures determined at room temperature. It is worth of note that though some hydrogen bonds in [3PyAla][ClO4 ] and [4PyAla][ClO4 ] may be considered as so called ’forced hydrogen bonds’ (see ref. 39 ) the perchlorate anion is ordered at 100 K as well as 298 K. Therefore one can conclude that [ClO4 ] – is well fixed in the crystal lattice. The rigidity of the structures of crystals under investigations may be additionally strengthened by the Cl—O. . . π interactions with the π system of the pyridyl ring. In the case of [3PyAla][ClO4 ] one deals with 1 Cl—O. . . π interactions but in the [4PyAla][ClO4 ] 2 such interactions are present. On the one hand the geometrical parameters of these interactions, 20


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see for example figure S1a, show that they are very subtle, but, on the other hand, they are “charge assisted”. 40,41 It means that, however the distance O–π exceeds the sum of the van der Waals radii of carbon and oxygen one should note that the π system belongs to the positively charged pirydyl ring and the oxygen to perchlorate anion what makes such an interaction unskippable. Thus the additional interaction may increase the stability of packing of crystal and thereby the rigidity of [4PyAla][ClO4 ] structure, which in turn causes the magnitude of piezoresponse of [3PyAla][ClO4 ] higher than that of [4PyAla][ClO4 ] . Another interesting issue is why the [3PyAla][ClO4 ] (or [4PyAla][ClO4 ] ) and [2PyAla][ClO4 ] crystallize in two different crystallographic systems despite the relatively little difference in structure. One can suggest that the dominant role is played by hydrogen bonds network but the crystal structure depends on many other factors as well, for example conformation and charge state of cation or composition and dynamical state of anion. 42,43 It has been shown that L–arginine and L–histidine may undergo 9 different transition pathways and formation mechanism on the basis of structure analysis of more than 80 salts of these amino–acids. 44 For instance the salts of L-arginine crystallize either in orthorhombic system (space group P 21 21 21 ) – (L–ArgH)ClO4 45 or monoclinic system (P 21 ) – (L–ArgH2 )(NO3 )2 46 or triclinic (P 1) – (L–ArgH2 )(ClO4 )2 . 47 The case above resembles that observed by us in pyridyl alanine derivatives: space group of [2PyAla][ClO4 ] crystal is orthorhombic P 21 21 21 , space group of [3PyAla][ClO4 ] and [4PyAla][ClO4 ] is monoclinic P 21 and space group of [2PyAla][BF4 ]

18

is triclinic P 1. It seems that the crucial factor in the case of investigated by us crystals is the hydrogen bond network but in general there is no simple correlation between between the structure (symmetry) and hydrogen bonds – see for example Görbitz 10 or Surekha et al. 48 It seems reasonable to broaden these research into new derivatives of amino acids. This allows to create almost unlimited number of new salts with potentially high piezoelectric properties. 47 Beside this such materials exhibit nonlinear optical (NLO) properties 48–50 due to the presence of the chiral carbon atom of amino acid (the only exception is αglycine).

21



Moreover, investigation of single crystals enable us to look for correlation between crystal structure and functional piezoelectric properties. It is worth noting that incorporation into the structure heterocyclic rings enrich the hydrogen bond network what may lead to the emergence of ferroelectricity. 51 It should be also emphasized that amino acids based materials are by far more safe for environment than those lead based like Pb[ZrTi]O3 . The studies of hybrid, organic–inorganic crystals presented in this work perfectly fit in with this subject.

Acknowledgements The work was supported by Faculty of Chemistry, University of Wroclaw, program The Leading National Research Center (KNOW) for the years 2014–2018. This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, POCI-01-0145FEDER-007679 (FCT Ref. UID /CTM /50011/2013), financed by national funds through the FCT/MEC and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement. I.B. acknowledges FCT for its financial support (grant IF/00582/2015). M.W. would like to thank Prof. Roman Szostak for carrying out the measurements of the Raman spectroscopy.

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Supplementary material Maciej Wojta´s, Vasyl Kinzhybalo, Igor Bdikin and Andrei L. Kholkin Crystal structure and strong piezoelectricity of new amino acid based hybrid crystals: [H– β–(3–Pyridyl)–Ala–OH][ClO4 ] and [H–β–(4–Pyridyl)–Ala–OH][ClO4 ]

Figure S1: The diagram of C—O. . . π and Cl—O. . . π interaction (a and d), the Hirshfeld surface (b and e) and 2D fingerprint plot (c and f) for [4PyAla][ClO4 ] and for [3PyAla][ClO4 ] , respectively.

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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 A) for [3PyAla][ClO4 ] and [4PyAla][ClO4 ] at Table S1: Selected bond lengths (˚ 19 20 21 [3PyAla][ClO4 ] [4PyAla][ClO4 ] 22 23 C2—N1 1.498(3) Cl1—O11 1.4444(18) C2—N1 Cl1—O11 1.4441(16) 24 Cl1—O12 1.4349(19) C2—C3 1.529(3) Cl1—O12 1.429(2) C2—C3 25 Cl1—O13 1.4489(18) C15—C16 1.376(4) Cl1—O13 1.447(2) C16—N11 26 Cl1—O14 1.4509(18) C3—C13 1.513(3) Cl1—O14 1.445(2) C3—C14 27 C1—O1 1.258(3) N11—C12 1.353(3) C1—O1 1.25(3) C12—C13 28 C1—O2 1.256(3) N11—C16 1.338(3) C1—O2 1.26(3) C12—N11 29 C1—C2 1.528(3) C12—C13 1.384(3) C1—C2 1.531(4) C13—C14 30 C13—C14 1.396(4) C14—C15 1.388(3) C14—C15 1.408(4) C15—C16 31 O11—Cl1—O13 109.24(11) N1—C2—C3 110.82(18) O11—Cl1—O13 109.67(12) N1—C2—C3 32 O11—Cl1—O14 108.97(11) C13—C3—C2 115.2(2) O11—Cl1—O14 108.68(12) C3—C2—C1 33 O12—Cl1—O11 109.71(11) C16—N11—C12 123.4(2) O12—Cl1—O11 109.85(12) C16—C15—C14 34 O12—Cl1—O13 110.31(11) N11—C12—C13 119.8(2) O12—Cl1—O13 110.24(14) N11—C16—C15 35 O12—Cl1—O14 109.52(12) C12—C13—C3 118.9(2) O12—Cl1—O14 109.51(14) C12—N11—C16 36 O13—Cl1—O14 109.06(11) C12—C13—C14 117.7(2) O14—Cl1—O13 108.86(12) C14—C3—C2 37 O1—C1—C2 117.2(2) C14—C13—C3 123.4(2) O1—C1—O2 127.1(3) N11—C12—C13 38 O2—C1—O1 126.8(2) C15—C14—C13 120.5(2) O1—C1—C2 117.2(2) C12—C13—C14 39 O2—C1—C2 116(2) C16—C15—C14 119.8(2) O2—C1—C2 115.7(2) C13—C14—C3 40 C1—C2—C3 113.01(19) N11—C16—C15 118.7(2) N1—C2—C1 109.8(2) C15—C14—C3 41 N1—C2—C1 110.01(18) C13—C14—C15 117.9(2) 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 29 59 ACS Paragon Plus Environment 60

100 K.

1.497(3) 1.527(3) 1.343(4) 1.508(3) 1.374(4) 1.334(4) 1.389(4) 1.376(4) 110.7(2) 113.7(2) 119.5(3) 120.1(3) 122(3) 115.7(2) 120.2(3) 120.2(3) 119.9(2) 122.2(2)


For Table of Contents Use Only, Crystal structure and strong piezoelectricity of new amino acid based hybrid crystals: [H–β–(3–Pyridyl)–Ala–OH][ClO4 ] and [H–β–(4–Pyridyl)–Ala–OH][ClO4 ] , Maciej Wojta´s, Vasyl Kinzhybalo, Igor Bdikin and Andrei L. Kholkin

Piezo In-Plane (IP) signal of [3PyAla][ClO4] higher than piezoresponse of Lithium niobate (LNO)

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Crystal structure and strong piezoelectricity of new amino acid based

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