Two New Nonlinear Optical and Ferroelectric Zn(II) Compounds

---

Subscriber access provided by UNIV OF MISSISSIPPI

Article

Two new nonlinear optical and ferroelectric Zn(II) compounds based on nicotinic acid and tetrazole derivative ligands Dong-Sheng Liu, Yan Sui, Wen-Tong Chen, and Pingyun Feng Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.5b00637 • Publication Date (Web): 25 Jun 2015 Downloaded from http://pubs.acs.org on June 29, 2015

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 free 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 accessible to all readers and 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.

Crystal Growth & Design is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 13

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

Crystal Growth & Design

Two new nonlinear optical and ferroelectric Zn(II) compounds based on nicotinic acid and tetrazole derivative ligands Dong-Sheng Liu*a,b, Yan Sui a, Wen-Tong Chen a, Pingyun Feng* b a

Institute of Applied Chemistry, School of Chemistry & Chemical Engineering, Jinggangshan University,

Ji’an, Jiangxi 343009, P. R. China b

Department of Chemistry, University of California, Riverside, California 92521,USA

*To whom correspondence should be addressed E-mail: [email protected], [email protected]

Two new zinc compounds, [Zn2(mtz)(nic)2(OH)]n·0.5nH2O (1), and [Zn(phtz)(nic)]2n (2), (Hmtz = 5-methyltetrazole, Hphtz = 5-phenyltetrazole, Hnic = nicotinic acid), have been synthesized by a dual-ligand approach under solvothermal conditions. The compounds were characterized by single crystal X-ray diffraction, elemental analysis and infrared spectroscopy, respectively. The X-ray diffraction analysis reveals that both compounds exhibit noncentrosymmetric polar packing arrangement. Compound 1 is a 3D framework constructed from the zigzag chain subunits of [Zn(nic)]+ with 4-connected ‘irl’ topology. Compound 2 possesses 2D 4-connected ‘“sql” topology constructed from the linear chain subunit of [Zn(nic)]+ which are linked together with phtz- ligands. Impressively both of the two compounds display second harmonic generation (SHG) response and ferroelectric behaviors. Furthermore, the photoluminescence of the compounds was also investigated.

Introduction Nonlinear optical (NLO), pyroelectric, piezoelectric, and ferroelectric materials are useful in various areas.1-8 Of particular importance are NLO second harmonic generation (SHG) and ferroelectricity, which are the desired materials in switchable NLO devices, light modulators, information storage and ferroelectric random access memories.9-19 The rational synthesis and design of noncentrosymmetric or polar compounds have attracted much attention in multifunctional materials field.20-26 Traditionally, research of SHG-active and ferroelectricity is mainly focused on pure inorganic compounds such as KH2PO4 (KDP), BaTiO3, and LiNbO3.27,28 Investigation of metal-organic frameworks (MOFs) possessing NLO response and ferroelectric behaviors, which combine the advantages of the inorganic metal ions and organic ligands, still remains in its infancy. It is a great challenge to synthesize MOFs with both ferroelectric and NLO properties because such compounds not only must crystallize in acentric space groups but also should belong to one of the 10 polar point groups.23,29,30 Generally, the most effective and straightforward strategy is to use homochiral organic ligand as building block to assembly these multifunctional MOFs.31-33 The application of the homochiral organic ligand will greatly increase the possibility of constructing MOFs that would crystallize in one of the 10 polar

ACS Paragon Plus Environment

Crystal Growth & Design

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

point groups essential for NLO-active or ferroelectric behavior.34 But the synthesis and separation of the homochiral organic ligand is always complex and costly. Moreover, the NLO-active or ferroelectric material may not always be obtained when the homochiral ligands are applied. Recently, some research groups have prepared a few MOFs with NLO-active or ferroelectric behaviors by using asymmetric bridging ligands replacing the homochiral ligands.35-51 It confirmed that NLO-active or ferroelectric MOFs can be efficiently generated by the introduction of an asymmetric bridging ligand under the solvothermal reactions conditions. The key factor is that the use of asymmetrical ligands will ensures the absence of inversion centers on the bridging ligands. When both the metal center and the bridging ligand lack center of symmetries, it will greatly guarantee the acentricity of the network. In literature, it is a general strategy to assemble noncenteric MOFs by using single asymmetric bridging ligand and get some 2D coordination networks.49 But mixing an asymmetric bridging ligand with a symmetric bridging ligand to assemble noncenteric MOFs was rarely presented up to now.26 Encouraged by these works, we envisioned that asymmetric bridging ligand could provide convenient access to MOF crystals with SHG response and ferroelectricity and also could lead more diverse frameworks. Nicotinic acid, as a good asymmetric bridging ligand with pyridyl-nitrogen and carboxyl-oxygen donor atoms, has been widely used to constructing MOFs. When the bent configuration of this ligand link tetrahedrally connected metal centers, the metal centers will have at most C2v symmetry and thus will not possess a center of symmetry. This will be likely to create noncenteric polymeric compounds. Moreover, the tetrazole-based ligand also has strong coordination ability with metal because of the aromaticity and multiple N-donor atoms and has been utilized as multifunctional organic linkers for the generating coordination polymers.52-56 With the presence of two different negative charged ligands in the synthesis, materials with interesting structures and properties are expected.57 With this dual-ligand synthetic strategy and as a part of our ongoing research on the construction of ferroelectric complexes,58-60 two new noncenteric MOFs, [Zn2(mtz)(nic)2(OH)]n·0.5nH2O (1), and [Zn(phtz)(nic)]n (2) have been successfully synthesized under solvothermal conditions. The materials are constructed by tetrahedrally connected Zn2+ centers, asymmetric bridging ligands and tetrazole-based ligands. The ferroelectric behaviors, NLO-active, thermal stabilities and photoluminescence properties of the two compounds have been investigated.

Experimental Reagents and physical measurements All reagents and solvents employed were commercially available and used without further purification. Infrared spectra were recorded in the range 4000-400 cm-1 on a Perkin-Elmer FT-IR spectrum 2000 spectrometer by using KBr pellets for 1. Infrared spectra were recorded in the range

ACS Paragon Plus Environment

Page 2 of 13

Page 3 of 13

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

Crystal Growth & Design

4000-550 cm-1 on a Nicolet 6700 FT-IR spectrometer for 2. Elemental analysis was determined with a Perkin-Elmer model 240C instrument. Thermal analysis was performed on a Delta Series TGA7 instrument in N2 atmosphere with heating rate of 10℃/min from 30 to 700 ℃. Powder X-ray diffraction (PXRD) data were obtained by using Rigaku D/MAX 2500V/PC diffractometer with Cu Ka (λ = 1.54056Å) radiation. A step size of 0.05º and counting time of 1.2s/step were applied in a 2θ range of 5.0-60.0 degree. The electric hysteresis loops were recorded on a Ferroelectric Tester Multiferroic made by Radiant Technologies, Inc. Powder SHG measurements were carried out by the Kurtz-Perry method. The measurements were performed by using a Q-switched Nd:YAG laser at 1064 nm with an input pulse of 350 mV.

Synthesis Synthesis of [Zn2(mtz)(nic)2(OH)]n·0.5nH2O (1) A mixture of ZnSO4·7H2O (0.575 g, 2 mmol), Hmtz (0.168 g, 2 mmol), Hnic (0.122g, 1.0mmol), NaOH (0.040g, 1.0mmol), ethanol (2mL) and water (8mL) was stirred for 30 min in air, then sealed in a 23 mL Teflon autoclave and heated at 130℃ for 3 days. After the sample was cooled to room temperature at a rate of 10℃/h, colorless block crystals were obtained in ca. 38% yield based on Zn. IR (KBr, cm−1): 3450 (m), 2919 (w), 2850 (w), 2343 (w), 1599 (m), 1556 (m), 1488 (s), 1384 (vs), 1249 (m), 1182 (m), 1094 (m), 699 (s), 491 (m) (figure S1) Elemental analysis (%) calcd for C28H26N12O11Zn4: (Mr = 968.09) C, 34.93; H, 2.72; N, 17.47; found: C, 34.08; H, 2.48; N, 17.62. Synthesis of [Zn(phtz)(nic)]2n (2) Similarly, complex 2 was prepared in the same manner as that for 1 but with Hphtz (0.292 g, 2 mmol) to replace Hmtz. Colorless block crystals were obtained in ca. 32% yield based on Zn. IR (cm−1): 3060m, 1610m, 1530m, 1460 (s), 1390s, 1320m, 1290w, 1200w, 1200m, 1180s, 1020s, 931m, 854w, 783s, 731s, 687s, 600m. (figure S1) Elemental analysis (%) calcd for C26H18N10O4Zn2: (Mr = 665.24) C, 46.94; H, 2.73; N, 21.05; found: C, 46.73; H, 2.52; N, 21.32. X-ray crystallography Suitable single crystals of two complexes were mounted on glass fibers for X-ray measurement. Reflection data were collected at room temperature on a Rigaku Saturn 724 CCD diffractometer with graphite monochromatized Mo Kα radiation( λ=0.71073 Å). Crystal structures were solved by the direct method. All calculations were performed using the SHELX-97 program.61 All non-hydrogen atoms were refined by full-matrix least-squares techniques on F2 with anisotropic thermal parameters. Hydrogen atoms associated with C atoms in the compounds 1 and 2 were fixed at calculated positions and refined by using a riding mode. The hydroxyl hydrogen atoms and H atoms of water molecules for 1 were found from difference maps and refined with O-H distance restraint 0.82(1) Å. Crystal data and

ACS Paragon Plus Environment

Crystal Growth & Design

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 4 of 13

details of the data collection and the structure refinements are given in Table 1. Selected bond lengths and bond angles of the compounds are listed in Table S1. Table 1 Crystal data and structure refinement for compounds 1 and 2. Compound Empirical formula Formula weight Temperature Crystal system Space group a, Å b, Å c, Å α, (deg) β, (deg) γ, (deg) V, Å3 Z Dcal, g/cm3 µ(Mo Kα),mm-1 F(000) 2Ө (deg) Reflections collected Reflections observed (>2δ) Data Completeness Data / restraints / parameters GOF on F2 R1, wR2 [I>2δ(I)] R1, wR2 [all data] Absolute structure parameter Max peak, hole/(e·Å3) a

b

R1=∑||Fo| - |Fc||/∑|Fo|.

1 C28H26N12O11Zn4 968.09 298(2) K Orthorhombic Ccc2 9.912(2) 12.884(3) 14.024(3 90 90 90 1790.9(6) 2 1.795 2.722 972 3.16 - 26.38 6241 1796 0.993 1815 / 4 / 138 1.091 0.0275, 0.0754 0.0278, 0.0758 0.038(18) 0.452, -0.447

2 C26H18N10O4Zn2 665.24 298(2) K Monoclinic Pc 14.441(3) 10.325(2) 8.959(2) 90 96.25(3) 90 1328.0(5) 2 1.664 1.861 672 3.23 - 26.37 10083 4833 0.988 5185 / 2 / 380 1.095 0.0399, 0.0806 0.0444, 0.0952 0.010(15) 0.411, -0.413

wR2=[∑w(Fo2 - Fc2)2/∑w(Fo2)2]1/2.

Results and Discussion Crystal structure of [Zn2(mtz)(nic)2(OH)]n·0.5nH2O (1) Compound 1 crystallizes in the noncentrosymmetric space group Ccc2, which belongs to the polar point group C2v. The asymmetrical unit of 1 contains one Zn atom, one nicotinic ligand, half a mtzligand, half a hydroxide group and half a free water molecule. As shown in Figure 1a, the Zn(II) ion is coordinated with two nitrogen atoms from a nic- ligand (N1) and mtz- ligand (N2), two oxygen atoms from the hydroxide group(O3) and the other nic ligand(O1ii), respectively, to form a slightly distorted ZnN2O2 tetrahedron with the cis-bond angles ranging from 103.3(1) -106.5(1)°. All the Zn-N and Zn-O bond lengths are in the normal range and comparable to those of the Zn(II)- tetrazole and the Zn(II)-nicotinate compounds.62-65 In this structure, the Zn atoms are bridged into a zigzag chain by µ2-nic– (N,O) ligand along the c-axis direction, then Zn atoms of the two adjacent chains are connected together by hydroxide groups with an interval of one Zn atom and form a 2D cation layer [Zn2(nic)2(OH)]+ (figure 1b) along the ac plane. Adjacent layers are linked together through the µ2-metz– ligands and the residual coordination sites of

ACS Paragon Plus Environment

Page 5 of 13

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

Crystal Growth & Design

Zn2+ ions, and result in a 3D framework (Figure 1c). Considering Zn2+ ions as 4-connected nodes, the connections representing nic-, metz- and hydroxide group, respectively, compound 1 can also be simplified as a 4-connected ‘irl’ topological network with the Schläfli symbol of (42·63·8) (Figure 1d).

Figure 1a) Coordination environment of Zn2+ center in compound 1 with the thermal ellipsoids drawn at the 30% probability level. All H atoms of C atoms were omitted for clarity (Symmetry codes: (i) -x, -y, z; (ii) -x, y, -0.5+z); 1b) View of 2D cation layer [Zn2(nic)2(OH)]+ along the ac plane; 1c) View of the 3D packing diagram. Hydrogen atoms are omitted for clarity except the H atoms of the free water and hydroxide groups; 1d) View of the 4-connected ‘irl’ topological net of 1 with the Schläfli symbol of (42·63·8), (cyan: Zn nodes).

Crystal structure of [Zn(phtz)(nic)]2n (2) Complex 2 crystallizes in an acentric space group Pc which belongs to the polar point group (Cs), and the asymmetric unit contains two crystallographically independent Zn(II) centers, two phtz ligands and two inc ligands. The Zn(II) atoms, nic and phtz ligands are all sited in the general position. Zn1 and Zn2 atoms are four-coordinated and adopt tetrahedral geometry (figure 2a). Each of the Zn(II) atom is surrounded by three N atoms and one O atom, in which the N atoms come from two independent phtz ligands and one nic ligand, and the O atom comes from the other nic ligand. The Zn-N bond distances range from 1.996(9) to 2.036(7) Å. The Zn1-O1and Zn2-O3 bond distances are 1.920(5) and 1.938(3) Å, respectively, which are all in the normal range. 63-67 The cis-angles at central Zn1 and Zn2 ions fall in the range of 98.8(2)-115.2(2)° and 100.7(2)-118.3(2)°, which indicates that the tetrahedral geometry around Zn atom is slightly distorted.

ACS Paragon Plus Environment

Crystal Growth & Design

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

In this structure, the Zn1 and Zn2 atoms are bridged into a linear chain by µ2-nic- (N,O) ligands along the a axis direction. The dihedral angles between the adjacent carboxyl groups of nic ligands of the linear chain are 84.30°. Adjacent linear chains are linked into 2D layer through the bridging phtzligands and the residual coordination sites of Zn2+ ions along the ac plane with the dihedral angles about 94° between the adjacent pleats (figure 2b). The 2D layers stack up through the intermolecular forces leading to 3D supramolecular framework formation (figure 2d). Topologically, the 2D network can be viewed as an ‘sql’ topology with the Schläfli symbol68 of 44.62 when the four coordination Zn(II) ions are regarded as 4-connected nodes and the organic ligands as linkers (figure 2c).

Figure 2a) View of the coordination environment of Zn2+ in compound 2 (30% probability). All of the H atoms are omitted for clarity (Symmetry codes: (i) x, -y, 0.5+z; (ii) 1+x, y, z); 2b) View of the 2D pleat layer along the ac plane; 2c) View of the 4-connected ‘sql’ topological net of 2 with the Schläfli symbol of (42·62), (cyan: Zn node); 2d) Packing diagram of 2.

Both the structures of 1 and 2 contain 1-D chains. Zigzag chains exist in 1, whereas linear chains are observed in 2. The difference originates from the different connective forms between the intrachains. In compound 1, the adjacent chains are connected together by hydroxide groups through the intervals of Zn atoms and form the zigzag chains, and then leading to the 2D layer formation. At the same time, one of coordination site on each Zn2+ ion still remains. So the adjacent layers can be linked to each other through the residual coordination sites of Zn2+ ions and the bridging metz– ligands, and resulting

ACS Paragon Plus Environment

Page 6 of 13

Page 7 of 13

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

Crystal Growth & Design

in the 3D framework in 1. While in structure 2, adjacent chains are linked together through bridging phtz- ligands along two different directions without intervals of Zn atoms, and then form a 2D layer. It is not like compound 1, no residual coordination sites of Zn2+ ions remain in 2. Although the synthesis was performed under the same reaction conditions, the bridging hydroxide group was not observed in compound 2 instead phtz- ligand was used as bridging ligand to connect the chains together to give 2D structure. The two distinctly different structures are probably a result of electronic and/or steric effects of the tetrazole-based ligand. The large steric hindrance of phtz- ligand leads to the formation of a 2D layered network. Powder X-ray diffraction and thermal stability The crystalline phase purities for 1 and 2 were confirmed by the PXRD patterns. As shown in the PXRD patterns (figure S2), the major peak positions of the PXRD patterns of the bulk solids of 1 and 2 matched well with the simulated patterns, which confirms the phase purity of the as-prepared products. In order to examine the thermal stabilities of the two compounds, thermogravimetric analyses(TGA) were carried out at a heating rate of 10℃/min under N2 atmosphere in the temperature range of 30 - 600 ℃. As shown in Figure S3, the TGA curves indicate that the two compounds are stable up to high temperature (300℃ for 1 and 320℃ for 2). Beyond this temperature, the skeletons of the structures collapse perhaps because of the decomposition of the organic ligands. The first weight loss is 2.23% (calcd 1.86%) between 30 ~ 120 ℃for 1, corresponding to the loss of the free water molecules. Nonlinear optical properties As is known, only the non-centrosymmetric structure might have a second-order nonlinear optical effect.7,69,70 Both of the two crystallized in an acentric space group (Ccc2 for 1 and Pc for 2). So the second-harmonic generation (SHG) measurements were investigated. Approximate estimations were carried out on a pulsed Q-switched Nd:YA Glaser at a wavelength of 1064 nm. The results obtained from a powdered sample (80-150 mm diameter) in the form of a pellet (Kurtz powder test)71 were compared with those obtained for urea. The preliminary experimental results revealed that compounds 1 and 2 display modest powder SHG efficiencies of 0.7 and 0.4 times that of urea (7 and 4 times that of KDP), respectively. Ferroelectric properties As mentioned above, both of the two compounds crystallize in the acentric space groups, C2v for 1, Cs for 2, both belong to the ten polar point groups (C1, Cs, C2, C2v, C4, C4v, C3, C3v, C6, C6v) required for the ferroelectric property.23,24,50,72 Our primarily experimental results reveal that there are electric hysteresis loops in compound 1 with remnant polarization (Pr) of 1.22-2.9 µC cm-2, coercive field (Ec) of 1.29-2.57 KV cm-1, and saturation spontaneous polarization (Ps) of 2.61-6.26 µC cm-2 (figure 3).

ACS Paragon Plus Environment

Crystal Growth & Design

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

Similarly, as illustrated in figure 3, the Pr, Ec, and Ps of compound 2 are 2.55-5.27 µC cm-2, 0.45-1.42 V cm-1, and 0.85-2.50 µC cm-2, respectively. The Ps values of the two compounds are comparable with that of the classical organic-inorganic ferroelectrics triglycine sulfate (TGS: Ps = 3.0µC cm-2) and NaKC4H4O6·4H2O (Rosal salt: Ps = 0.25µC cm-2). In order to confirm the ferroelectricity mentioned above for 1 and 2, the leakage currents are further investigated. As shown in figure S4, the leakage currents show no alterations and keep extremely low valves (less than 10-6 A for 1 and 10-5 for 2) under the employed conditions, so the observed hysteresis loop is clearly due to ferroelectricity.

Figure 3 Electric hysteresis loops of powder pellet samples of 1 and 2 recorded at room temperature.

Fluorescent properties Owing to the excellent luminescence properties of zinc complexes, the solid-state fluorescent properties of the two compounds were investigated at room temperature. As illustrated in Figure 4, upon excitation of these solid samples at 323 nm for 1 and 313nm for 2, the intense broad emission bands at 446 nm for 1, 393, 454 and 488 nm for 2 are observed. The free Hnic exhibits fluorescent emission bands at 379 and 512 nm (λex = 330 nm) (figure S5), while free Hatz ligand presents a weak photoluminescence emission at 325nm according to the reported literature.52,73 Taking the emission bands of these free organic ligands into consideration, the emissions of 1 may also be ascribed to the cooperative effects of intraligand emission and ligand-to-metal charge transition (LMCT). The fluorescence differences between the two compounds may be ascribed to the different substituents at the 5-position of the tetrazole ligands of zinc ions and/or their local coordination environments.74,75 Combining with their high thermal stabilities, compounds 1 and 2 can be considered as potential candidates for blue-light-emitting materials.

ACS Paragon Plus Environment

Page 8 of 13

Page 9 of 13

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

Crystal Growth & Design

Figure 4 Solid-state fluorescence spectra of compounds 1 and 3 at RT (λex : 323 nm for 1 and 313nm for 2).

Conclusion In summary, two new multifunctional zinc coordination polymers have been successfully prepared and structurally characterized. The synergetic effect of both the symmetric and asymmetric ligands endows the materials with unique structures and properties. This work indicates that combining the asymmetric bridging ligand with the tetrazole-based ligand can be an efficient method to generate multifunctional material with NLO-active, ferroelectric behaviors and fluorescent properties. The strategy can be a general method for the searching for interesting multifunctional organic-inorganic hybrid materials. Acknowledgments This work is supported by the NSFC (21461012 and 21361012), the Natural Science Jiangxi Province (143ACB21025, 20142BAB203002), and Department of Education of Jiangxi Province (GJJ14556, JXJG-14-9-17). Supporting Information Crystallographic data; IR spectrum, PXRD patterns; solid-state excitation and emission spectra for Hnic; thermal stability and CCDC reference numbers 1055365 for 1 and 105536 for 2. This information is available free of charge via the Internet at http://pubs.acs.org.

ACS Paragon Plus Environment

Crystal Growth & Design

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

References (1) Lines, M. E.; Glass, A. M. Principles and Applications of Ferroelectrics and Related Materials (Oxford Univ. Press, New York, 1977). (2) Piezoelectric Nanomaterials for Biomedical Applications; G. Ciofani, A. Menciassi, Ed., Springer-Verlag Berlin Heidelberg, 2012. (3) Ramesh, R. Nature 2009, 461, 1218-1219. (4) Scott, J. F. Science 2007, 315, 954-959. (5) Guillaume, R.; Nathalie, V.; Marc, D. Angew. Chem., Int. Edit. 2010, 49, 1921-1923. (6) Evans, O. R.; Lin, W. Acc. Chem. Res. 2002, 35, 511-522. (7) Ok, K. M.; Chi, E. O.; Halasyamani, P. S. Chem. Soc. Rev. 2006, 35, 710-717. (8) Wang, C.; Zhang, T.; Lin, W. Chem. Rev. 2012, 112, 1084-1104. (9) Long, N. J. Angew. Chem., Int. Ed. 1995, 34, 21-38. (10) Zyss, J.; Chemla, D. S. Nonlinear Optical Properties of Organic Molecules and Crystals; Academic Press: New York, 1989; Vol. 1. (11) Nonlinear Optical Effects and Materials; Günter, P., Ed.; Springer: Berlin, Germany, 2000; Vol. 72. (12) Agullo-Lopez, F.; Cabrera, J. M.; Agullo-Rueda, F. Electrooptics: Phenomena, Materials and Applications, Academic Press: New York, 1994. (13) Fu, D.-W.; Cai, H.-L.; Liu, Y.; Ye, Q.; Zhang, W.; Zhang, Y.; Chen, X.-Y.; Giovannetti, G.; Capone, M.; Li, J.; Xiong, R.-G. Science 2013, 339, 425-428. (14) Zhang, W.; Xiong, R.-G. Chem. Rev. 2012, 112, 1163-1195. (15) Duan, H.-B.; Zhao, H.-R.; Ren, X.-M.; Zhou, H.; Tian, Z.-F.; Jin, W.-Q. Dalton Trans. 2011, 40, 1672-1683. (16) Horiuchi, S.; Tokunaga, Y.; Giovannetti, G.; Picozzi, S.; Itoh, H.; Shimano, R.; Kumai, R.; Tokura, Y. Nature 2010, 463, 789-792. (17) Akutagawa, T.; Koshinaka, H.; Sato, D.; Takeda, S.; Noro, S.-I.; Takahashi, H.; Kumai, R.; Tokura, Y.; Nakamura, T. Nat Mater 2009, 8, 342-347. (18) Serra-Crespo, P.; van der Veen, M. A.; Gobechiya, E.; Houthoofd, K.; Filinchuk, Y.; Kirschhock, C. E. A.; Martens, J. A.; Sels, B. F.; De Vos, D. E.; Kapteijn, F.; Gascon, J. J. Am. Chem. Soc. 2012, 134, 8314-8317. (19) Lee, H. N.; Hesse, D.; Zakharov, N.; Gösele, U. Science 2002, 296, 2006-2009. (20) Long, J.; Rouquette, J.; Thibaud, J.-M.; Ferreira, R. A. S.; Carlos, L. D.; Donnadieu, B.; Vieru, V.; Chibotaru, L. F.; Konczewicz, L.; Haines, J.; Guari, Y.; Larionova, J. Angew. Chem. 2015, 127, 2264-2268. (21) Yu, L.; Hua, X.-N.; Jiang, X.-J.; Qin, L.; Yan, X.-Z.; Luo, L.-H.; Han, L. Cryst. Growth Des. 2015, 15, 687-694. (22) Ishow, E.; Bellaïche, C.; Bouteiller, L.; Nakatani, K.; Delaire, J. A. J. Am. Chem. Soc. 2003, 125, 15744-15745. (23) Guo, Z.; Cao, R.; Wang, X.; Li, H.; Yuan, W.; Wang, G.; Wu, H.; Li, J. J. Am. Chem. Soc. 2009, 131, 6894-6895. (24) Fu, D.-W.; Zhang, W.; Xiong, R.-G. Dalton Trans. 2008, 3946-3948. (25) Tian, C.-B.; He, C.; Han, Y.-H.; Wei, Q.; Li, Q.-P.; Lin, P.; Du, S.-W. Inorg. Chem. 2015, 54, 2560-2571. (26) Duan, X.; Meng, Q.; Su, Y.; Li, Y.; Duan, C.; Ren, X.; Lu, C. Chem. Eur. J. 2011, 17, 9936-9943. (27) Rijnders, G.; Blank, D. H. A. Nature 2005, 433, 369-370. (28) Lee, H. N.; Christen, H. M.; Chisholm, M. F.; Rouleau, C. M.; Lowndes, D. H. Nature 2005, 433, 395-399. (29) Horiuchi, S.; Tokura, Y. Nat Mater 2008, 7, 357-366. (30) Li, L.; Ma, J.; Song, C.; Chen, T.; Sun, Z.; Wang, S.; Luo, J.; Hong, M. Inorg. Chem. 2012, 51, 2438-2442. (31) Crassous, J. Chem. Soc. Rev. 2009, 38, 830-845. (32) Li, X.-L.; Gao, Y.-L.; Feng, X.-L.; Zheng, Y.-X.; Chen, C.-L.; Zuo, J.-L.; Fang, S.-M. Dalton Trans. 2012, 41, 11829-11835. (33) Gong, Y.; Zhang, M. M.; Hua, W.; Sun, J. L.; Shi, H. F.; Jiang, P. G.; Liao, F. H.; Lin, J. H. Dalton Trans. 2014, 43, 145-151. (34) Cheng, L.; Zhang, L.-M.; Gou, S.-H.; Cao, Q.-N.; Wang, J.-Q.; Fang, L. CrystEngComm 2012, 14, 4437-4443. (35) Wang, Y.-T.; Fan, H.-H.; Wang, H.-Z.; Chen, X.-M. Inorg. Chem. 2005, 44, 4148-4150.

ACS Paragon Plus Environment

Page 10 of 13

Page 11 of 13

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

Crystal Growth & Design

(36) Wang, Y.-T.; Tang, G.-M.; Wei, Y.-Q.; Qin, T.-X.; Li, T.-D.; He, C.; Ling, J.-B.; Long, X.-F.; Weng Ng, S. Cryst. Growth Des. 2010, 10, 25-28. (37) Wei, Y.; Yu, Y.; Wu, K. Cryst. Growth Des. 2007, 7, 2262-2264. (38) Han, Z.-B.; He, Y.-K.; Tong, M.-L.; Song, Y.-J.; Song, X.-M.; Yang, L.-G. CrystEngComm 2008, 10, 1070-1073. (39) Lan, Y.-Q.; Li, S.-L.; Su, Z.-M.; Shao, K.-Z.; Ma, J.-F.; Wang, X.-L.; Wang, E.-B. Chem. Commun. 2008, 58-60. (40) Braverman, M. A.; LaDuca, R. L. Cryst. Growth Des. 2007, 7, 2343-2351. (41) Wang, X.-Y.; Scancella, M.; Sevov, S. C. Chem. Mater. 2007, 19, 4506-4513. (42) Brown, K. A.; Martin, D. P.; LaDuca, R. L. CrystEngComm 2008, 10, 1305-1308. (43) Li, W.; Jia, H.-P.; Ju, Z.-F.; Zhang, J. Dalton Trans. 2008, 5350-5357. (44) Hu, S.; Zou, H.-H.; Zeng, M.-H.; Wang, Q.-X.; Liang, H. Cryst. Growth Des. 2008, 8, 2346-2351. (45) Hou, L.; Zhang, J.-P.; Chen, X.-M.; Ng, S. W. Chem. Commun. 2008, 4019-4021. (46) Li, W.; Barton, P. T.; Burwood, R. P.; Cheetham, A. K. Dalton Trans. 2011, 40, 7147-7152. (47) Gao, E.-Q.; Yue, Y.-F.; Bai, S.-Q.; He, Z.; Yan, C.-H. J. Am. Chem. Soc. 2004, 126, 1419-1429. (48) Gao, E.-Q.; Bai, S.-Q.; Wang, Z.-M.; Yan, C.-H. J. Am. Chem. Soc. 2003, 125, 4984-4985. (49) Evans, O. R.; Lin, W. Chem. Mater. 2001, 13, 3009-3017. (50) Hang, T.; Fu, D.-W.; Ye, Q.; Xiong, R.-G. Cryst. Growth Des. 2009, 9, 2026-2029. (51) Liao, J.-Z.; Chen, D.-C.; Li, F.; Chen, Y.; Zhuang, N.-F.; Lin, M.-J.; Huang, C.-C. CrystEngComm 2013, 15, 8180-8185. (52) Wang, X. W.; Chen, J. Z.; Liu, J. H. Cryst. Growth Des. 2007, 7, 1227-1229. (53) He, X.; Lu, C. Z.; Yuan, D. Q. Inorg. Chem. 2006, 45, 5760-5766. (54) Xue, X.; Abrahams, B. F.; Xiong, R. G.; You, X. Z. Aust. J. Chem. 2002, 55, 495-497. (55) Liu, D.-S.; Sui, Y.; Wang, T.-W.; Huang, C.-C.; Chen, J.-Z.; You, X.-Z. Dalton Trans. 2012, 41, 5301 5306. (56) Wang, T.-W.; Liu, D.-S.; Huang, C.-C.; Sui, Y.; Huang, X.-H.; Chen, J.-Z.; You, X.-Z. Cryst. Growth Des. 2010, 10, 3429-3435. (57) Zhao, X.-L.; Sun, W.-Y. CrystEngComm 2014, 16, 3247-3258. (58) Sui, Y.; Fang, X.-N.; Hu, R.-H.; Li, J.; Liu, D.-S. Inorg. Chim. Acta 2014, 423, Part A, 540-544. (59) Sui, Y.; Liu, D.-S.; Hu, R.-H.; Chen, H.-M. J. Mater. Chem. 2011, 21, 14599–14603. (60) Sui, Y.; Li, D.-P.; Li, C.-H.; Zhou, X.-H.; Wu, T.; You, X.-Z. Inorg. Chem. 2010, 49, 1286-1288. (61) Sheldrick, G. M. SHELXS-97, Program for Crystal Structure Refinement; University of Göttingen,Germany, 1997. (62) Ma, L.; Qiu, Y.-C.; Peng, G.; Cai, J.-B.; Deng, H. Eur. J. Inorg. Chem. 2011, 2011, 3446-3453. (63) Liu, D.-S.; Chen, W.-T.; Xu, Y.-P.; Shen, P.; Hu, S.-J.; Sui, Y. J. Solid State Chem. 2015, 226, 186-191. (64) An, Z.; Gao, J.; Zhu, L. J. Mol. Struct. 2013, 1054-1055, 234-238. (65) Liu, D.-S.; Huang, X.-H.; Huang, C.-C.; Huang, G.-S.; Chen, J.-Z. J. Solid State Chem. 2009, 182, 1899-1906. (66) Ye, Q.; Li, Y.-H.; Song, Y.-M.; Huang, X.-F.; Xiong, R.-G.; Xue, Z. Inorg. Chem. 2005, 44, 3618-3625. (67) Sun, Y.-X.; Sun, W.-Y. CrystEngComm 2015, 17, 4045-4063. (68) Smith, J. V. Am. Mineral. 1978, 63, 960. (69) Huang, S. D.; Xiong, R.-G. Polyhedron 1997, 16, 3929-3939. (70) Xiong, R. G.; Xue, X.; Zhao, H.; You, X. Z.; Abrahams, B. F.; Xue, Z. L. Angew. Chem., Int. Edit. 2002, 41, 3800-3803. (71) Kurtz, S. K.; Perry, T. T. J. Appl. Phys. 1968, 39, 3798-3813. (72) Xu, G.; Li, Y.; Zhou, W.-W.; Wang, G.-J.; Long, X.-F.; Cai, L.-Z.; Wang, M.-S.; Guo, G.-C.; Huang, J.-S.; Bator, G.; Jakubas, R. J. Mater. Chem. 2009, 19, 2179-2183. (73) Liu, D.-S.; Huang, G.-S.; Huang, C.-C.; Huang, X.-H.; Chen, J.-Z.; You, X.-Z. Cryst. Growth Des. 2009, 9, 5117-5127. (74) Qiu, Y.; Li, Y.; Peng, G.; Cai, J.; Jin, L.; Ma, L.; Deng, H.; Zeller, M.; Batten, S. R. Cryst. Growth Des. 2010, 10, 1332-1340. (75) Yam, V. W.-W. Acc. Chem. Res. 2002, 35, 555-563.

For Table of Contents Use Only

ACS Paragon Plus Environment

Crystal Growth & Design

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

Two new nonlinear optical and ferroelectric Zn(II) compounds based on nicotinic acid and tetrazole derivative ligands Dong-Sheng Liu*a,b, Yan Sui a, Wen-Tong Chen a, Pingyun Feng* b a

Institute of Applied Chemistry, School of Chemistry & Chemical Engineering, Jinggangshan University,

Ji’an, Jiangxi 343009, P. R. China b

Department of Chemistry, University of California, Riverside, California 92521,USA

Two new noncentrosymmetric ZnII compounds have been prepared from mixing the asymmetric and symmetric bridging ligands. Both of them exhibit good NLO-activties, ferroelectric behaviors and fluorescent properties.

ACS Paragon Plus Environment

Page 12 of 13

Page 13 of 13

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

Crystal Growth & Design

Two new noncentrosymmetric ZnII compounds have been prepared from mixing the asymmetric and symmetric bridging ligands. Both of them exhibit good NLO-activties, ferroelectric behaviors and fluorescent properties. 423x171mm (96 x 96 DPI)

ACS Paragon Plus Environment