Histidine-Controlled Homochiral and Ferroelectric Metal–Organic

Article pubs.acs.org/crystal

Histidine-Controlled Homochiral and Ferroelectric Metal−Organic Frameworks Lei Yu,†,# Xiu-Ni Hua,†,# Xi-Jie Jiang,‡ Lan Qin,† Xiao-Zhi Yan,† Lai-Hui Luo,‡ and Lei Han*,† †

Institute of Inorganic Materials, School of Materials Science and Chemical Engineering, and ‡Department of Microelectronic Science and Engineering, Ningbo University, Ningbo, Zhejiang 315211, China S Supporting Information *

ABSTRACT: A new multifunctional enantiopure ligand, (S)-2-(1,8-naphthalimido)-3-(4-imidazole)propanoate (s-nip), containing a homochiral center derived from L-histidine and a strong π···π stacking 1,8-naphthalimide synthon, has been used to prepare three novel metal−organic frameworks. The frameworks of [Zn(s-nip)2]n (1) and {[Co(s-nip)2]·(H2O)0.5}n (2) are isostructural three-dimensional (3D) homochiral supramolecular structures organized one-dimensional (1D) ribbons by strong hydrogen bonds and π···π interactions, which display ferroelectric behavior at room temperature. The complex [Cu(nia)2· (H2O)5]n (3) was constructed under a hydrothermal in situ ligand synthesis reaction, in which the new ligand 2-(1,8naphthalimido)-3-(4-imidazole)acrylate (nia) was formed from the s-nip ligand via a dehydrogenation reaction. The twodimensional network of 3 stacks into a 3D structure via π···π interactions resulting in 1D hydrophilic channels.

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INTRODUCTION Chiral metal−organic frameworks (MOFs) have attracted great attention due to their potential applications in nonlinear optics,1,2 enantioselective separation,3,4 asymmetric catalysis,5−7 and ferroelectric materials.8,9 Recently, several biomolecules, such as amino acids,10,11 nucleobases,12,13 and peptides,14,15 were used as organic linkers in MOF synthesis because they can afford homochiral frameworks and enhance the structural and chemical diversity. Histidine is one of the naturally amino acids and is often found at the active site of proteins. Compared to other amino acids, one unique structural feature of histidine is that its side chain bears a basic imidazole group. The use of histidine as a bridging ligand for the construction of homochiral MOFs is rarely known due to its strong tendency to form metal chelates, as well as its zwitterionic structure sensitive to acid− base.15−18 The derivatives of amino acids with new coordination functional groups introduced at N-substituted site have been considered as an important synthetic strategy to create MOFs because of the diversity of their metal binding sites.19,20 On the other hand, the incorporation of robust supramolecular synthons, such as π stacking, into the amino acids also attracts particular attention,21,22 desiring physical or chemical proper© XXXX American Chemical Society

ties of the constructed networks can be achieved. The electron deficient 1,8-naphthalimide group is an important supramolecular synthon and has strong π-stacking capabilities. Furthermore, the photophysical properties of 1,8-naphthalimide derivatives were extensively utilized by incorporating this moiety into a large variety of chemosensors and other devices.23−25 Recently, a series of coordination frameworks containing 1,8-naphthalimide synthon have been constructed with highly organized supramolecular structures.26−34 However, the multifunctional molecules based on histidine and 1,8naphthalimide have not been exploited to the benefit of crystal engineering. Here we report the synthesis, coordination chemistry, and in situ dehydrogenation of a new enantiopure ligand, (S)-2-(1,8naphthalimido)-3-(4-imidazole)propanoate (s-nip, Scheme 1), containing a homochiral center derived from L-histidine and a strong π···π stacking 1,8-naphthalimide synthon. Three MOFs were prepared from s-nip. The frameworks of [Zn(s-nip)2]n (1) and {[Co(s-nip)2]·(H2O)0.5}n (2) are isostructural homochiral Received: September 14, 2014 Revised: December 14, 2014

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Crystal Growth & Design Scheme 1. Ligand s-nip and nia

110 °C for 2 days. After the mixture was cooled to room temperature, colorless block crystals were obtained in 61% yield (based on Zn). Anal. Calcd for C36H24ZnN6O8 (%): C 58.90, H 3.30, N 11.45; found (%): C 58.75, H 3.41, N 11.27. IR data (cm−1, KBr): 3402(m), 3133(w), 2937(w), 2819(w), 2365(w), 1703(s), 1657(vs), 1585(s), 1512(w), 1434(m), 1375(s), 1349(s), 1237(m), 1178(w), 1112(w), 1027(w), 968(w), 850(w), 778(s), 660(w), 535(w). Synthesis of Complex 2. A mixture of Co(NO3)2·6H2O (0.0375 g, 0.129 mmol), s-nip (0.0225 g, 0.067 mmol) in ethanol (3 mL), and DMF (3 mL) mixed solution was stirred for half an hour. The mixture was sealed into a 25 mL Teflon-lined stainless autoclave and heated at 90 °C for 2 days. After the mixture was cooled to room temperature, red block crystals were obtained in 85% yield (based on Co). Anal. Calcd for C36H25CoN6O4.5 (%): C 64.29, H 3.75, N 12.50; found (%): C 64.60, H 3.66, N 12.66. IR data (cm−1, KBr): 3378(m), 3196(m), 3138(w), 2922(w), 2367(w), 1704(s), 1663(vs), 1588(vs), 1505(w), 1431(m), 1389(s), 1331(s), 1248(s), 1190(m), 1107(m), 1033(w), 966(w), 842(w), 770(s), 668(w), 635(w), 527(w). Synthesis of Complex 3. A mixture of CuSO4·5H2O (0.0440 g, 0.176 mmol) and s-nip (0.0240g, 0.072 mmol) in H2O (4 mL) solution was stirred for half an hour. The mixture was sealed into a 25 mL Teflon-lined stainless autoclave and heated at 120 °C for 2 days. After the mixture was cooled to room temperature, colorless block crystals were obtained in 72% yield (based on Cu). Anal. Calcd for C36H30CuN6O13 (%): C 52.84, H 3.70, N 10.27; found (%): C 52.59, H 3.44, N 10.39. IR data (cm−1, KBr): 3542(m), 3453(m), 3153(m), 2997(w), 2848(w), 2599(w), 2350(w), 1696(s), 1654(vs), 1621(s), 1588(vs), 1497(w), 1439(w), 1389(s), 1339(s), 1248(m), 1182(w), 1116(w), 1033(w), 942(w), 850(w), 776(s), 660(m), 536(w). Crystallographic Studies. X-ray diffraction data were collected on a Bruker SMART APEX CCD detector with graphite monochromatized Mo−Kα radiation (λ = 0.71073 Å).35 The data frames were integrated using SAINT and merged to give a unique data set for the structure determination. Absorption correction was applied using multiscan program SADABS.36 The structure was solved by direct methods and refined on F2 by full-matrix least-squares using the SHELXL-97 program package.37 All non-hydrogen atoms were refined with anisotropic displacement parameters. The hydrogen atoms were refined isotropically and assigned idealized positions and included as riding atoms. Even though the electron densities of some guest solvent molecules were found in compound 3, those could not be well modeled in the refinement because of severe disorder. Final refinement was performed with modification of the structure factors for contribution of the disordered solvent electron densities using the SQUEEZE option of PLATON.38 Details of the data collection for the structures are listed in Table 1. Selected bond lengths and angles are listed in Table S1, Supporting Information. The hydrogen bonds in complexes 1 and 2 are listed in Tables S2−S3, Supporting Information.

supramolecular networks, which display ferroelectric behavior. The complex [Cu(nia)2·(H2O)5]n (3) was constructed with in situ ligand synthesis, in which the new ligand 2-(1,8naphthalimido)-3-(4-imidazole)acrylate (nia, Scheme 1) was formed from s-nip ligand via a dehydrogenation procedure. The thermal stabilities and photoluminescences for three complexes have also been investigated.

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EXPERIMENTAL SECTION

Materials and Physical Measurements. All chemicals were of reagent grade quality and purchased from commercial sources. The 1H NMR spectra and 13C NMR spectra were recorded on a Bruker Avance DRX 400 spectrometer. Infrared spectrum were recorded on Nicolet 6700 spectrophotometer in the wavenumber range 4000−400 cm−1 by using KBr pallets. Elemental analyses were carried out on an Elementar Vario EL III analyzer. The fluorescence spectra of the solid state were obtained on F-4600 FL spectrophotometer. Powder X-ray diffraction (PXRD) intensities were measured at room temperature on a Rigaku D/max-IIIA diffratometer (Cu Kα, λ = 1.54056 Å) with a scan rate of 3°/min in the range of 2−54°. Simulated patterns were produced using the Mercury Version 1.4 software (http://www.ccdc. cam.ac.uk/products/mercury/) and single-crystal reflection diffraction data. Thermogravimetric analysis curve were measured on SII TG/ DTA 7300 instrument at a heating rate of 10 °C/min. The polarization−voltage curves were carried out on powder sample with a Premier II ferroelectric tester. The temperature dependences of dielectric constant in the frequency range of 104−107 Hz were measured in the temperature range of 200−450 K by a dielectric impedance analyzer, Concept 80 system. Synthesis of Ligand (s-nip). L-Histidine (1.5516 g, 10 mmol) was dissolved in water (25 mL) and was allowed to stir for half an hour, and then an ethanol solution (75 mL) of 1,8-naphthalic anhydride (1.9817 g, 10 mmol) was added. The mixed solution was heated 100 °C for 8 h. The reaction mixture was cooled to room temperature, and white precipitate was filtered and air-dried to yield 2.656 g (7.92 mmol, 79.2%). Anal. Calcd for C18H13N3O4 (%): C 64.47, H 3.91, N 12.53; found (%): C 64.58, H 3.93, N 12.44. 1H NMR (400 MHz, DMSO-d6): δ 8.43 (q, J = 4.1 Hz, 4H, napht), 7.83 (t, J = 8.0 Hz, 2H, napht), 7.48 (s, 1H, 2-imidazole), 6.71 (s, 1H, 5-imidazole), 5.79 (q, J = 5.2 Hz, 1H, α-CH), 3.42 (m, 2H, β-CH2). 13C NMR (400 MHz, DMSO-d6): δ 26.24 (β-CH2), 53.82 (α-CH), 117.58 (imidazole), 122.06 (napht), 127.76 (naphth), 131.53 (imidazole), 133.61 (naphth), 135.09 (naphth), 163.5 (CO), 171.23 (COOH). IR data (cm−1, KBr): 3444(m), 3146(m), 3006(w), 2599(w), 2367(w), 1961(w), 1704(s), 1663(vs), 1588(vs), 1448(w), 1382(s), 1233(s), 1175(w), 1083(w), 1034(w), 950(w), 860(w), 777(s), 669(w), 635(w), 519(w). Synthesis of Complex 1. A mixture of Zn(NO3)2·6H2O (0.0306 g, 0.103 mmol), s-nip (0.0186 g, 0.056 mmol) in methanol (2 mL), and H2O (2 mL) mixed solution was stirred for half an hour. The mixture was sealed into a 25 mL Teflon-lined stainless autoclave and heated at B

DOI: 10.1021/cg5013796 Cryst. Growth Des. XXXX, XXX, XXX−XXX

2 C36H25N6O4.5Co 672.55 298(2) monoclinic P21 8.026(4) 15.446(7) 14.588(7) 90 103.873(8) 90 1755.7(14) 2 1.515 826 5.105 27.53/2.61 −10 ≤ h ≤ 10, −20 ≤ k ≤ 20, −18 ≤ l ≤ 18 19484/7960 [R(int) = 0.0427] 99.5 0.043 7960/1/505 1.001 R1 = 0.0563, wR2 = 0.1218 R1 = 0.0810, wR2 = 0.1370 0.212/−0.384

1 C36H24N6O8Zn 734.02 298(2) monoclinic P21 7.9371(16) 15.359(3) 14.644(3) 90 103.76 90 1734.0(6) 2 1.406 752 0.769 27.46/3.00 −9 ≤ h ≤ 10, −19 ≤ k ≤ 19, −18 ≤ l ≤ 18 16853/7819 [R(int) = 0.0451] 99.6 0.0451 7819/1/460 1.153 R1 = 0.0536, wR2 = 0.1362 R1 = 0.0995, wR2 = 0.1970 0.702/−1.041

compound

empirical formula formula weight temperature/K crystal system space group a/Å b/Å c/Å α/° β/° γ/° volume/Å3 Z ρcalc, mg/mm3 F(000) absorption coefficient (mm−1) θmax/θmin index ranges reflections collected completeness, % Rint data/restraints/parameters goodness-of-fit on F2 final R indexes [I > 2σ(I)] final R indexes (all data) largest diff peak/hole/e Å−3

Table 1. Selected Crystallographic Details and Refinement Parameters for 1, 2, 3 C36H30N6O13Cu 818.21 298(2) orthorhombic Pbcn 12.4110(11) 19.5709(17) 15.6611(13) 90 90 90 3804.0(6) 4 1.271 1484 0.629 25.02/2.34 −14 ≤ h ≤ −11, −23 ≤ k ≤ 22, −18 ≤ l ≤ 18 18223/3361 [R(int) = 0.0731] 99.9 0.0731 3361/0/231 1.070 R1 = 0.0917, wR2 = 0.2483 R1 = 0.1339, wR2 = 0.2639 0.602/−0.436

3

Crystal Growth & Design Article

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Figure 1. (a) 1D ribbon structure of 1. (b) 3D supramolecular structure of 1 organized by hydrogen bondings and π···π stacking interactions.

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RESULTS AND DISCUSSION The ligand s-nip was synthesized from L-histidine and 1,8naphthalic anhydride by a one-step procedure. The complexes 1 and 2 were synthesized from s-nip and corresponding inorganic salts under a different solvothermal reaction. They are isostructural compounds and crystallize in monoclinic, chiral P21 space group; only the structure of 1 is discussed in detail as a representative. As shown in Figure 1a, the Zn center in 1 adopts a distorted tetrahedron atmosphere that is composed of two O atoms from two carboxylic groups with Zn−O bond distances from 1.969(4) to 2.016(4) Å, and two N atoms from two imidazole groups with Zn−N bond distances from 1.967(5) to 1.988(6) Å. The four-coordinated Zn atom is chelated by one s-nip ligand and bridged by the other two s-nip ligands to form an infinite centipede-like ribbon along the a axis. The Zn···Zn separation is 7.937(4) Å, and the width distance of this ribbon is about 2.0 nm. The intramolecular hydrogen bondings are observed in the bridging s-nip ligands with a N5−H···O5 distance of 2.811(7) Å. Additionally, the intermolecular hydrogen bonds locate neighboring ribbons with a N2−H···O1 distance of 2.994(8) Å and N2−H···O1 angle of 155°, which generate the two-dimensional (2D) hydrogen bonding sheet in the ab plane. Finally, robust π···π stacking

interactions between the 1,8-naphthalimide groups organize sheets into a three-dimensional (3D) architecture, as shown in Figure 1b. The perpendicular distance between two naphthalimide rings is 3.40 Å, and the dihedral angle between two planes is 1.49°. The neighboring sheets mutually interdigitate together by 1,8-naphthalimide π-stacking synthons, perfectly. In complex 2, the Co center adopts a distorted tetrahedron atmosphere that is composed of two O atoms from two carboxylic groups with Co−O bond distances from 1.963(3) to 1.985(3) Å, and two N atoms from two imidazole groups with Co−N bond distances from 1.986(4) to 1.987(4) Å. The perpendicular distance between two naphthalimide rings is 3.42 Å, and the dihedral angle between two planes is 1.28°. The complex 3 was synthesized from s-nip and CuSO4·5H2O under hydrothermal conditions. The crystal structure of 3 crystallizes in orthorhombic, Pbcn space group. Unexpectedly, by in situ synthesis, the ligand s-nip transformed into a new ligand, 2-(1,8-naphthalimido)-3-(4-imidazole)acrylate (nia, Scheme 1). Single crystal X-ray crystallographic analyses revealed that each copper(II) center is linked to four nia ligands, as shown in Figure 2a, and adopts approximate square plane, with the Cu−N bond distances of 1.988(6) Å and Cu−O bond distances of 1.932(5) Å. All bridging nia ligands are D

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Crystal Growth & Design

Figure 2. (a) 2D (4,4)-net of 3. (b) View of 3D structure of 3 organized by π···π stacking interactions. (c) View of 1D channels in 3 along the c axis.

thermogravimetric analysis (TGA), solvent molecules were proposed to be five water molecules. In situ ligand reactions have attracted great attention for the discovery of new organic reactions and elucidation of their mechanisms. To date, more than 10 types of in situ ligand synthesis have been found in coordination polymer fields.39 It is worthwhile to mention that the s-nip ligand occurred in the in situ dehydrogenation reaction in the synthetic reaction of 3, and the C−C single bond transformed into a CC double bond (Scheme 1). As shown in Figure 2a, the C2−C15 bond length in the nia ligand is shortened as 1.340(13) Å. The dihedral angle between the 1,8-naphthalimide ring and imidazole ring of the s-nip ligand in 1 is 73.573°, and the dihedral angle between the two rings of the nia ligand in 3 increases to 81.687°. As a result, the flexible chiral s-nip ligand became the rigid achiral nia ligand. The feasible mechanism of

coordinated by Cu atoms to generate the 2D (4,4)-net polymer. The Cu···Cu separation is 9.991(5) Å. The 1,8naphthalimide groups locate the 2D sheet up and down, respectively. There are weak π···π stacking interactions in the sheet among 1,8-naphthalimide groups, the perpendicular distance between two naphthalimide rings is 3.71 Å, and the dihedral angle between two planes is 9.013°. Moreover, the strong π···π stacking interactions between neighboring sheets organize 2D sheets into a 3D architecture, as shown in Figure 2b. The perpendicular distance between two naphthalimide rings is 3.49 Å, and the dihedral angle between two planes is 0°. Interestingly, the 3D supramolecular framework of 3 has onedimensional (1D) hydrophilic channels viewed along the c axis (Figure 2c). The total solvent-accessible volume in the framework of 3 accounts for approximately 23.8% of the whole crystal volume as estimated by PLATON.38 According to E

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Figure 3. (a) The TGA curves of complexes 1, 2, and 3. (b) Emission spectra of s-nip, complexes 1, 2, and 3.

Figure 4. Room-temperature electric hysteresis loop for complex 1 (a) and 2 (b). Temperature dependence of the dielectric constant of 1 (c) and 2 (d) at 10 KHz to 10 MHz.

this in situ reaction is that the dehydrogenation is catalyzed by the CuII ion.40,41 To the best of our knowledge, the in situ dehydrogenation ligand reaction is the first detected in histidine under hydrothermal conditions. Powder X-ray diffraction (PXRD) experiments on the bulk materials of 1, 2, and 3 show that all major peaks match well with simulated PXRD, indicating their crystalline phase purity (Figure S2, Supporting Information). Thermogravimetric analysis (TGA) experimental results (Figure 3a) indicate that complexes 1 and 2 are stable up to 370 °C, and the one-step weight loss from 370 to 570 °C corresponds to the removal of the organic species. The final residual weight of 1 is 10.43%, which corresponds to ZnO (calcd. 11.09). The TGA curve of complex 3 indicates that the first weight loss of 12.29% from 30 to 146 °C corresponds to the removal of five water guest molecules (calcd. 12.36%). In the next step, the framework decomposes upon 246 °C.

In view of the important photophysical properties of 1,8naphthalimide groups, the solid-state emission spectra of 1−3 and the ligand s-nip were measured and are depicted in Figure 3b. The s-nip ligand shows an emission maximum at 417 nm (λex= 326 nm). Complexes 1 and 2 display the same emission maximum at 402 nm under the exciation maximum at 329 and 324 nm, respectively. Complex 3 displays an emission maximum at 409 nm (λex = 326 nm). The blue shift may be due to the ligand-to-metal charge transfer (LMCT), and the broad emission of 3 can be considered as the new nia ligand. Interestingly, complex 1 crystallizes in space group P21, C2 point group, which belongs to the 10 polar point groups (C1, Cs, C2, C2v, C3, C3v, C4, C4v, C6, and C6v) that are required for ferroelectric behavior.8,9 To detect the ferroelectricity, the hysteresis loops of electric polarization were measured on a powder sample of 1 at room temperature at different voltages. Figure 4a shows a remnant polarization (Pr) of ca. 0.035 μC F

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Crystal Growth & Design cm−2 and coercive field (Ec) of ca. 4.08 kV cm−1. Saturation of the spontaneous polarization (Ps) is ca. 0.294 μC cm−2. The Ps value is equal to that of the typical ferroelectric compound Rochelle salt (NaKC4H4O6·4H2O, Ps = 0.25 μC cm−2).42 There are several compounds exhibiting good ferroelectricities that contain amino acid; the space group of the glycine-containing compound [Ag(NH3CH2COO)(NO3)] that changes from P21/a in the paraelectric phase to P21 in the ferroelectric phase is of a displactive type ferroelectric compound.43 The value is 0.60 μC cm−2 at 100 K. Complex 2 also crystallizes in space group P21, C2 point group. Figure 4b shows a remnant polarization (Pr) of ca. 0.013 μC cm−2 and coercive field (Ec) of ca. 3.68 kV cm−1. Saturation of the spontaneous polarization (Ps) is ca. 0.033 μC cm−2. The temperature dependence of the dielectric permittivity of 1 and 2 was further investigated under an applied electric field with frequencies of 10 KHz to 10 MHz. The real component of 1 shows a very large maxima dielectric anomaly close to 300 K (Figure 4c), and the component of 2 shows broad peaks from 225 to 450 K and a very large maxima dielectric anomaly close to 279 K (Figure 4d), corresponding to the existence of a ferroelectric phase transition.

(3) Kesanli, B.; Lin, W. Coord. Chem. Rev. 2003, 246, 305−326. (4) Li, J.-R.; Sculley, J.; Zhou, H.-C. Chem. Rev. 2012, 112, 869−932. (5) Banerjee, M.; Das, S.; Yoon, M.; Choi, H. J.; Hyun, M. H.; Park, S. M.; Seo, G.; Kim, K. J. Am. Chem. Soc. 2009, 131, 7524−7525. (6) Song, F.; Wang, C.; Falkowski, J. M.; Ma, L.; Lin, W. J. Am. Chem. Soc. 2010, 132, 15390−15398. (7) Dybtsev, D. N.; Nuzhdin, A. L.; Chun, H.; Bryliakov, K. P.; Talsi, E. P.; Fedin, V. P.; Kim, K. Angew. Chem., Int. Ed. 2006, 45, 916−920. (8) Zhang, W.; Xiong, R.-G. Chem. Rev. 2012, 112, 1163−1195. (9) Zhang, W.; Ye, H.-Y.; Xiong, R.-G. Coord. Chem. Rev. 2009, 253, 2980−2997. (10) Anokhina, E. V.; Jacobson, A. J. J. Am. Chem. Soc. 2004, 126, 3044−4045. (11) Anokhina, E. V.; Go, Y. B.; Lee, Y.; Vogt, T.; Jacobson, A. J. J. Am. Chem. Soc. 2006, 128, 9957−9962. (12) Stylianou, K. C.; Warren, J. E.; Chong, S. Y.; Rabone, J.; Bacsa, J.; Bradshaw, D.; Rosseinsky, M. J. Chem. Commun. 2011, 47, 3389− 3391. (13) An, J.; Farha, O. K.; Hupp, J. T.; Pohl, E.; Yeh, J. I.; Rosi, N. L. Nat. Commun. 2012, 3, 604−609. (14) Mantion, A.; Massüger, L.; Rabu, P.; Palivan, C.; McCusker, L. B.; Taubert, A. J. Am. Chem. Soc. 2008, 130, 2517−2526. (15) Katsoulidis, A. P.; Park, K. S.; Antypov, D.; Matrí-Gastaldo, C.; Miller, G. J.; Warren, J. E.; Robertson, C. M.; Blanc, F.; Darling, G. R.; Berry, N. G.; Purton, J. A.; Adams, D. J.; Rosseinsky, M. J. Angew. Chem., Int. Ed. 2014, 53, 193−198. (16) Chen, L.; Bu, X. H. Chem. Mater. 2006, 18, 1857−1860. (17) Fan, J.; Slebodnick, C.; Angel, R.; Hanson, B. E. Inorg. Chem. 2005, 44, 552−558. (18) Nomiya, K.; Takahashi, S.; Noguchi, R.; Nemoto, S.; Takayama, T.; Oda, M. Inorg. Chem. 2000, 39, 3301−3311. (19) Lou, B. Y.; Yuan, D. Q.; Wu, B. L.; Han, L.; Jiang, F. L.; Hong, M. C. Inorg. Chem. Commun. 2005, 8, 539−542. (20) Lou, B. Y.; Yuan, D. Q.; Wang, R. H.; Xu, Y.; Wu, B. L.; Han, L.; Hong, M. C. J. Mol. Struct. 2004, 698, 87−91. (21) Reger, D. L.; Semeniuc, R. F.; Elgin, J. D.; Rassolov, V.; Smith, M. D. Cryst. Growth Des. 2006, 6, 2758−2768. (22) Reger, D. L.; Horger, J.; Smith, M. D.; Long, G. J. Chem. Commun. 2009, 6219−6221. (23) Le, T. P.; Rogers, J. E.; Kelly, L. A. J. Phys. Chem. A 2000, 104, 6778−6785. (24) Rogers, J. E.; Weiss, S. J.; Kelly, L. A. J. Am. Chem. Soc. 2000, 122, 427−436. (25) Guo, X.; Qian, X.; Jia, L. J. Am. Chem. Soc. 2004, 126, 2272− 2273. (26) Reger, D. L.; Debreczeni, A.; Smith, M. D. Eur. J. Inorg. Chem. 2012, 712−719. (27) Reger, D. L.; Debreczeni, A.; Reinecke, B.; Rassolov, V.; Smith, M. D. Inorg. Chem. 2009, 48, 8911−8924. (28) Reger, D. L.; Debreczeni, A.; Horger, J. J.; Smith, M. D. Cryst. Growth Des. 2011, 11, 4068−4079. (29) Reger, D. L.; Sirianni, E.; Horger, J. J.; Smith, M. D. Cryst. Growth Des. 2010, 10, 386−393. (30) Reger, D. L.; Debreczeni, A.; Smith, M. D. Inorg. Chem. 2011, 50, 11754−11764. (31) Reger, D. L.; Horger, J. J.; Debreczeni, A.; Smith, M. D. Inorg. Chem. 2011, 50, 10225−10240. (32) Reger, D. L.; Debreczeni, A.; Smith, M. D. Inorg. Chem. 2012, 51, 1068−1083. (33) Reger, D. L.; Horger, J. J.; Smith, M. D. Chem. Commun. 2011, 47, 2805−2807. (34) Reger, D. L.; Horger, J. J.; Smith, M. D.; Long, G. J.; Grandjean, F. Inorg. Chem. 2011, 50, 686−704. (35) SAINT and SMART; Bruker AXS Inc.: Madison, WI, 2003. (36) Sheldrick, G. M. SADABS; University of Gottingen: Gottingen, Germany, 2001. (37) Sheldrick, G. M. Acta Crystallogr., Sect. A 2008, 64, 112−122. (38) PLATON program: Spek, A. L. Acta Crystallogr., Sect. A 1990, 46, 194−201.

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CONCLUSION In summary, three novel MOFs were successfully synthesized from the chiral ligand derived from L-histidine and 1,8naphthalimide synthon. The discovery of ferroelectric properties of 1 and 2 contributes to open a new field in ferroelectric MOFs based on amino acid derivatives. Furthermore, in situ dehydrogenation ligand synthesis is the first detected in histidine under hydrothermal conditions, which has significance for the exploration of novel in situ reactions.

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ASSOCIATED CONTENT

S Supporting Information *

X-ray crystallographic information in CIF format and experimental details, IR spectra, and PXRD patterns. This material is available free of charge via the Internet at http:// pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Tel: +86-574-87600782. Author Contributions #

L.Y. and X.-N.H. contributed equally.

Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (No. 21071087, 91122012, 21471086), and the Social Development Foundation of Ningbo (No. 2014C50013), the Scientific Research Foundation for the Returned Overseas Chinese Scholars, the Outstanding Dissertation Growth Fundation of Ningbo University (No. PY2012017), and the K. C. Wong MagnaFund in Ningbo University.

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REFERENCES

(1) Evans, O. R.; Lin, W. Acc. Chem. Res. 2002, 35, 511−522. (2) Zang, S.; Yang, S.; Li, Y.; Ni, Z.; Meng, Q. Inorg. Chem. 2006, 45, 174−180. G

DOI: 10.1021/cg5013796 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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Crystal Growth & Design (39) Zhang, X.-M. Coord. Chem. Rev. 2005, 249, 1201−1219. (40) Chen, X.-M.; Tong, M.-L. Acc. Chem. Res. 2007, 40, 162−170. (41) Hu, B.; Wang, G.; You, W.; Huang, W.; You, X.-Z. Dyes Pigments 2011, 91, 105−111. (42) Valasek, J. Phys. Rev. 1921, 17, 475−481. (43) Choudhury, R. R.; Panicker, L.; Chitra, R.; Sakuntala, T. Solid State Commun. 2008, 145, 407−412.

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DOI: 10.1021/cg5013796 Cryst. Growth Des. XXXX, XXX, XXX−XXX