Symmetry Breaking Phase Transition, Second-Order Nonlinear Optical

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Symmetry breaking phase transition, second-order nonlinear optical and dielectric properties of a one-dimensional organic– inorganic hybrid zigzag chain compound [NH3(CH2)5NH3]SbBr5 Han-Yue Zhang, Guang-Quan Mei, and Wei-Qiang Liao Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b01179 • Publication Date (Web): 14 Sep 2016 Downloaded from http://pubs.acs.org on September 20, 2016

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Crystal Growth & Design

Symmetry breaking phase transition, second-order nonlinear optical and dielectric properties of a one-dimensional organic–inorganic hybrid zigzag chain compound [NH3(CH2)5NH3]SbBr5 Han-Yue Zhang,† Guang-Quan Mei,*,§ and Wei-Qiang Liao╪ †

School of Chemistry and Materials Science, Nanjing Normal University, Nanjing,

210023, JiangSu, P. R. China §

Key Laboratory of Jiangxi University for Applied Chemistry and Chemical Biology,

Yichun University, Yichun 336000, China ╪

Ordered Matter Science Research Center, Southeast University, Nanjing 211189, PR

China

ABSTRACT:

A

1,5-pentanediammonium

new

one-dimensional

pentabromoantimonate

organic-inorganic (III)

(1),

material, exhibits

a

centrosymmetric-to-noncentrosymmetric symmetry breaking phase transition at 366.5 K, showing prominent second harmonic generation (SHG) response and dielectric anomalies. The differential scanning calorimetry (DSC) results indicate the phase transition is a second-order one. The variable-temperature structural analyses reveal that the space group changes from Pnma at 393 K in the high-temperature phase to P212121 at 293 K in the low-temperature phase, accompanied by the loss of symmetry

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plane and inversion center. The crystal structure is composed of one-dimensional zigzag chains of corner-sharing SbBr6 octahedra and 1,5-pentanediammonium cations. The origin of the phase transition can be attributed to both the deformation of the zigzag chains and the order-disorder transition of the 1,5-pentanediammonium cations. The compound is SHG-active below the transition temperature, demonstrating its second-order nonlinear optical properties. It is also SHG-inactive above the transition temperature, which further confirms the symmetry breaking phenomenon. These findings will pave a new way to explore organic-inorganic multifunctional phase transition material.

INTRODUCTION Organic−inorganic hybrid materials have long been an attractive topic of research due to their interesting physical properties and novel functionalities, originating from the combination of organic and inorganic components within a single molecular composite.1–6 In recent years, great attention has been focused on their structural phase transitions,5–13 which have potential applications in sensing, environment monitors, signal processing, and data storage, etc.14–17 Structural Phase transitions are always accompanied by symmetry breaking; namely, some symmetry elements can be lost and restored around the transition temperature, which introduces fascinating properties into the system, such as ferroelectricity, switchable dielectric, and nonlinear optical switching.18–26 Therefore, constructing organic−inorganic hybrids with symmetry breaking phase transitions is of great importance from the viewpoint of


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exploring multifunctional materials and novel physical properties. Structurally, organic−inorganic hybrids, which can form a variety of crystal structures from zeroto three-dimensional, are excellent candidates to show structural phase transitions.27–29 The cavities formed by the inorganic parts provide freedom of the molecular motions of the organic cations, which can exhibit order-disorder transition under the external stimuli of temperature, resulting in symmetry breaking and structural phase transitions.27–35 For instance, a series of three-dimensional hybrid metal formate frameworks A[M(HCOO)3]33–39 (where A = organic ammonium cation and B = divalent metal ion) and hybrid double perovskites A2[B’B’’(CN)6]30–32 (with A = organic ammonium cation, B’ = alkali metal ion, and B’’ = trivalent ion) have been found to show interesting symmetry breaking phase transitions, triggered by the order−disorder transition of organic cations. It has also been reported that the order−disorder transition of organic cations in two-dimensional lead-halide layered perovskites can lead to paraelectric-to-ferroelectric symmetry breaking phase transition.40–42

Jakubas

et

al.

found

that

halogenoantimonates(III)

and

halogenobismuthates(III) with the general formula RaMbX3b+a (where R = organic cations, M = Sb(III) or Bi (III), and X = Cl, Br or I) exhibit rich phase transitions related to the reorientation of organic moieties.43–46 Among them, ferroelectric properties have been observed in the chemical stoichiometries R5M2X11, R3M2X9, and RMX4.44–46 Recently, one-dimensional organic-inorganic hybrid metal halide compounds have been extensively studied for their interesting phase transitions, dielectric, and



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ferroelectric properties, associated with the dynamic behaviors of organic cations.47–55 For example, (pyrrolidinium)MnCl3 containing one-dimensional linear chains of face-sharing MnCl6 octahedra displays excellent ferroelectricity with intense red luminescence.51 Remarkable dielectric relaxation was found in thiazolium tribromocadmate(II) with similar infinite linear chains of face-sharing CdBr6 octahedra.53 Encouraged by these pioneering studies, herein, we present a new halogenoantimonates(III)-based one-dimensional organic-inorganic hybrid material [NH3(CH2)5NH3]SbBr5 (1), which consists of zigzag chains of corner-sharing SbBr6 octahedra

separated

by


cations.

It

undergoes

a

centrosymmetric-to-noncentrosymmetric symmetry breaking phase transition at 366.5 K, not only related to the order−disorder transition of 1,5-pentanediammonium cations but also to the deformation of zigzag chains. This compound also exhibits second-order nonlinear optical (NLO) properties, which may be widely used in emerging optoelectronics and photonics technologies.56 Differential scanning calorimetry (DSC) experiments, variable-temperature (VT) structural analyses, and VT second harmonic generation (SHG) and VT dielectric measurements have been performed to study its symmetry breaking phase transition, NLO and dielectric properties. EXPERIMENTAL Synthesis. Yellow single crystals of 1 were obtained by slow evaporation of a hydrobromic acid solution containing equal molar amounts of 1,5-pentanediamine and SbBr3 at room temperature. In the infrared (IR) spectra of 1 (Figure S1, Supporting


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Information), the two bands observed at 3190 and 3137 cm−1 were assigned to the NH3 asymmetric stretching vibrations. The CH2 asymmetric stretching mode can be observed at 2928 cm−1. The powder X-ray diffraction (PXRD) patterns match well with the simulated ones based on the crystal structures of different phases (Figure S2, Supporting Information), confirming the phase purity of the as-grown crystals. Crystallography. Variable-temperature X-ray single-crystal diffraction data at 293 and 393 K were collected on a Rigaku Saturn 924 diffractometer with Mo–Kα radiation (λ = 0.71073 Å). The Crystalclear software package (Rigaku, 2005) was used for data processing including empirical absorption corrections. The structures were solved by direct methods and refined by the full-matrix method based on F2 using the SHELXLTL software package. All non-hydrogen atoms were refined anisotropically using all reflections with I > 2σ (I). The positions of the hydrogen atoms were generated geometrically and refined using a "riding" model with Uiso = 1.2Ueq (C and N). The molecular structures and the packing views were drawn with DIAMOND (Brandenburg and Putz, 2005). Angles and distances between some atoms were carried out using DIAMOND, and other calculations were calculated using SHELXLTL. Crystallographic data and structure refinement at 293 and 393 K are listed in Table 1. Table 1 Crystal data and structure refinements for 1 at 293 and 393 K. Temperature

293 K

393 K

Empirical formula

C5H16N2, SbBr5

C5H16N2, SbBr5

Formula weight

625.46

625.46



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Crystal system

orthorhombic

orthorhombic

Space group

P212121

Pnma

a/Å

7.9639(16)

14.04(2)

b/Å

13.942(3)

8.044(12)

c/Å

14.065(3)

13.97(3)

β/deg

90.00

90.00

Volume (Å3), Z

1561.7(5), 4

1578(5), 4

Density (g cm−3)

2.660

2.633

F(000)

1144.0

1144.0

Reflections collected/unique

10877/3564

11206/1938

Rint

0.0625

0.0959

Parameters refined

121

88

Goodness-of-fit on F2

1.052

1.089

R1/wR2 [ I > 2σ(I)]

0.0440/0.0714

0.0761/0.1718

Physical measurements. IR spectra were recorded at ambient temperature using a Shimadzu model IR-60 spectrometer with KBr pellets. PXRD was measured on a Rigaku D/MAX 2000 PC X-ray diffraction Instrument at selected temperatures. Differential scanning calorimetry was carried out on a Perkin–Elmer Diamond DSC instrument by heating and cooling the polycrystalline samples (12.2 mg) in the temperature range 345–385 K with a heating rate of 5 K/min under nitrogen at atmospheric pressure in aluminum crucibles. Variable-temperature second harmonic generation (SHG) experiments were executed by Kurtz-Perry powder SHG test using


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an unexpanded laser beam with low divergence (pulsed Nd:YAG at a wavelength of 1064 nm, 5 ns pulse duration, 1.6 MW peak power, 10 Hz repetition rate). The instrument model is Ins 1210058, INSTEC Instruments, while the laser is Vibrant 355 II, OPOTEK. The pressed-powder pellet sandwiched between two parallel copper electrodes was used for dielectric constant measurements. Complex dielectric permittivity ε (ε = ε′ – iε″) was measured on a Tonghui TH2828A instrument in the temperature range between 310 and 400 K and over the frequency range of 10 KHz to 1 MHz with an applied electric field of 1 V. RESULTS AND DISCUSSION Phase Transition of 1. It is well known that DSC is an effective thermodynamic way to detect the existence of a reversible temperature-triggered phase transition. The phase transition behavior of 1 was first confirmed by the DSC measurements. The DSC curves show a pair of heat anomalies at 366.5 K on heating and 363.8 K upon cooling, indicating that a reversible structural phase transition occurs at Tc = 366.5 K (Figure 1). The combined narrow thermal hysteresis of 2.7 K and the broad shape of the anomalies demonstrate that this phase transition is of second-order type. For convenience, the phase above Tc is labeled as the high-temperature phase (HTP) and the phase below Tc as the low-temperature phase (LTP).



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Figure 1. DSC curves of 1. Variable-temperature Structures of 1. The structural phase transition was further investigated by determining the variable-temperature crystal structures of 1 (Table 1). At 393 K in the HTP, 1 crystallizes in the orthorhombic crystal system with a centrosymmetric space group Pnma and the point group D2h. At 293 K in the LTP, the crystal structure of 1 was still refined in the orthorhombic crystal system but with a non-centrosymmetric space group P212121 and the point group D2. Therefore, this phase transition is a symmetry breaking one. Namely, a symmetry breaking phenomenon occurs during the transition from HTP to LTP. The symmetric operation change presented in Figure 2 clearly shows that the 2-fold screw axis remains unchanged while the mirror plane perpendicular to the b axis and the inversion center disappear in the LTP. Symmetric elements decrease by half from eight (E, C2, C2’, C2’’, i, σh, σV, σ’V) in the HTP to four (E, C2, σV, σ’V) in the LTP, which is in good accordance with Landau phase transition theory, probably indicating a second-order phase transition. In addition, the space group P212121 in the LTP is a subgroup of Pnma in the HTP, which has maximal non-isomorphic subgroups, including Pna21,


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Pmn21, Pmc21, P212121, P21/c, and P21/m, being consistent with the Curie symmetry principle.

Figure 2. Symmetry breaking in 1 during its phase transition from the HTP (Pnma) to the LTP (P212121). In the HTP, the asymmetric unit consists of one Sb atom, four Br atoms, and one 1,5-pentanediammonium cation (Figure 3a). The Sb1 atom, lying in a special position of mirror plane, is octahedrally coordinated by two bridging and four terminal Br ligands. The two trans-positioned terminal Br atoms (Br3 and Br4) and the bridging Br1 atom are also located in special positions of a mirror plane and a center of inversion, respectively, while the cis-positioned terminal Br2 atom occupies a general position. Thus, the octahedron has four distinct pairs of Sb–Br bond distances ranging from 2.637(3) to 3.001(3) Å, showing significant distortion (Table S1). The bonds involving bridging Br atoms are the longest, while those involving terminal lying opposite bridging Br atoms are the shortest (Figure 4a). The other two trans-positioned terminal Sb–Br bonds have intermediate lengths. The lone electron



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pair of center Sb(III) atom may be deformed from its initial symmetry due to the formation of Sb–Br–Sb bonds,57 which results in the elongation of the bridging bonds while shortening of the opposite terminal ones. The cis-Br–Sb–Br angles between 84.15(12)° and 95.12(11)° deviating strongly from the ideal octahedral value of 90° also display the distortion of the SbBr6 octahedron (Table S1). These bond distances and angles are comparable with those observed in other structurally similar bromoantimonates(III).58 The elementary building blocks of SbBr6 octahedra share two cis corners with two other neighbours to form an infinite [SbBr5]n2− polyanionic zigzag chain running along the b axis (Figure 4a). The free space between the chains is occupied by the 1,5-pentanediammonium cations, of which the C1, C2, and C5 atoms lie on a special position of mirror plane parallel to the ac plane (Figure 3a and 5a). The cation is orientationally disordered over two equivalent positions related by this mirror plane with the N1, C3, C4, and N2 atoms distributed equally over the mirror plane. The cations connect adjacent anionic chains by weak N–H···Br hydrogen bonds (Figure 5a), with average N···Br distances of 3.705 Å for N1 donor and 3.545 Å for N2 donor (Table S2).

Figure 3. Molecular structures of 1 shown at different temperatures. (a) High-temperature

phase

(393

K):

the



cation

is

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orientationally disordered over two equivalent positions related by a mirror plane. (b) The low-temperature phase (293 K): the 1,5-pentanediammonium cation becomes ordered. Hydrogen atoms were omitted for clarity.

Figure 4. Comparison between the zigzag chains at (a and b) 393 K and (c and d) 293 K.

Figure 5. Packing diagrams of 1 at (a) 393 and (b) 293 K. The dashed lines stand for



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N–H···Br interactions. Carbon-bound H atoms were omitted for clarity. In the LTP, the SbBr6 octahedron contains five independent Br atoms, and all of its atoms occupy general positions (Figure 3b). The special positions of the mirror plane and the inversion center vanish, in good agreement with the above analysis of the symmetric operation change. The octahedron also displays strong distortion with six distinct pairs of Sb–Br bond distances in the range of 2.622(3) to 3.024(4) Å, similar to those in the HTP (Table S1). The cis-Br-Sb-Br angles (84.51(2)°–95.31(5)°) also shows no obvious changes (Table S1). However, the Sb–Br–Sb angle decreases dramatically from 180.0° in the HTP to 165.1° in the LTP, indicating the deformation of anionic chains during the phase transition (Figure 4a and c). Such deformation can be obviously seen along the chain direction (Figure 4b and d). The site symmetry of the 1,5-pentanediammonium cations also changes with all of the atoms lying in general positions. The cation becomes ordered, and the N1, C3, C4, and N2 atoms are refined with a single site. (Figure 3b). The cation has a single orientation with the C–N bonds aligning along the a axis. The average donor–acceptor distances for donor N1 and donor N2 are 3.520 and 3.503 Å, respectively, indicating stronger N–H···Br hydrogen-bonding interactions in the LTP (Table S2). Therefore, it is clear that the most distinct differences between these two phases are the deformation of the zigzag chains and the disorder-order transition of the 1,5-pentanediammonium cations, accompanied by the loss of symmetry plane and inversion center, which are the main driving forces of this symmetry breaking phase transition.


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Figure 6. Temperature-dependent variation of the SHG effect measured in the powdered state of 1 clearly showing that below Tc, the SHG effect is active, while above Tc, the SHG effect is zero. SHG Characterizations of 1. The symmetry breaking in the phase transition was then confirmed by the SHG effect, which is very sensitive to the breaking of inversion symmetry because only non-centrosymmetric materials are SHG-active.7,59 The SHG response of 1 as a function of temperature in the heating process is plotted in Figure 6. Above Tc, the SHG intensity is basically zero, suggesting that the HTP is centrosymmetric. Below Tc, the SHG intensity has a finite value, indicating that the inversion symmetry disappears and the centrosymmetric phase changes to a noncentrosymmetric one in the LTP. This is consistent with the symmetry breaking transition from a centrosymmetric structure (Pnma) to a noncentrosymmetric one (P212121). The SHG-active state in the LTP also shows the second order optical nonlinearity of 1. The continuous variation of the SHG intensity in the vicinity of the Tc reveals a second-order phase transition, in fairly good agreement with the DSC results. The SHG curves recorded on cooling correspond well with those obtained upon heating (Figure S3, Supporting Information), showing a reversible characteristic.



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Figure 7. Real part (ε′) of the dielectric permittivity of 1 as a function of temperature at 1 MHz upon heating and cooling. Inset: temperature-dependent of the ε′ of 1 at 10 kHz, 100 kHz, and 1 MHz on heating. Dielectric properties of 1. The temperature dependence of the dielectric permittivity, especially within a relatively high frequency regime, is very valuable for studying structural phase transition.5–13 The real part (ε′) of the dielectric permittivity of 1 were investigated in the temperature range from 310 to 400 K with frequencies of 10, 100, and 1 MHz. As shown in Figure 7, the ε′ value at 1 MHz increases progressively from 14.3 at 310 K to the maximal value of 22.5 at around Tc upon heating, and then it shows a slight decrease on further heating. The dielectric anomaly at around Tc confirms the phase transition. A clear dielectric anomaly at 363.8 K is also observed in the cooling process. The hysteresis of the two dielectric anomalies is about 2.7 K, in good accordance with the DSC results. The temperature position of the dielectric anomaly shows no obvious shift with frequency decreasing, implying no dielectric relaxation process is witnessed around the phase transition temperature. Unlike the remarkable dielectric relaxation behaviors associated with the molecular


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motion of thiazolium cation found in thiazolium tribromocadmate(II),53 the dipolar motion of the 1,5-pentanediammonium cation in 1 may be relatively fast.32 CONCLUSION In summary, we have presented a new one-dimensional organic–inorganic hybrid nonlinear optical material, which exhibits a centrosymmetric-to-noncentrosymmetric symmetry breaking phase transition at 366.5 K, confirmed by the combined DSC, VT structural analyses, VT-SHG, and VT dielectric measurements. The symmetry plane and the inversion center disappear during the phase transition. Both the deformation of the zigzag chains and the order-disorder transition of the 1,5-pentanediammonium cations play essential roles in the mechanism of this phase transition. It is believed that this finding throws light on the design of new organic–inorganic hybrid nonlinear optical phase transition material. Supporting information. IR spectrum, powder X-ray diffraction patterns, the temperature-dependence of the second harmonic generation effect on cooling, bond distances and angles, and hydrogen-bond geometry of the crystal structures. CCDC 1495687 at 293 K, and 1495688 at 393 K. This information is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION

Corresponding Author *E-mail: [email protected] ACKNOWLEDGMENT



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For Table of Contents Use Only Symmetry breaking phase transition, second-order nonlinear optical and dielectric properties of a one-dimensional organic–inorganic hybrid zigzag chain compound [NH3(CH2)5NH3]SbBr5 Han-Yue Zhang, Guang-Quan Mei and Wei-Qiang Liao Table of Contents graphic and synopsis

The organic–inorganic hybrid zigzag chain compound exhibits a symmetry breaking phase transition at 366.5 K, coupled with striking second harmonic generation (SHG) response and dielectric anomalies.


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Symmetry Breaking Phase Transition, Second-Order Nonlinear Optical

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