Crystal Engineering of Acentric Styryl Quinolinium Crystals with

Article pubs.acs.org/crystal

Crystal Engineering of Acentric Styryl Quinolinium Crystals with Strongly Hydrogen-Bonded Phenolic Anions Ji-Soo Kim,† Jae-Hyeok Jeong,† Hoseop Yun,‡ Mojca Jazbinsek,§ Jun Wan Kim,⊥ Fabian Rotermund,⊥ and O-Pil Kwon*,† †

Department of Molecular Science and Technology, Ajou University, Suwon 443-749, Korea Department of Chemistry & Division of Energy Systems Research, Ajou University, Suwon 443-749, Korea § Rainbow Photonics AG, Farbhofstrasse 21, CH-8048 Zurich, Switzerland ⊥ Department of Physics & Division of Energy Systems Research, Ajou University, Suwon 443-749, Korea ‡

S Supporting Information *

ABSTRACT: We report on new acentric styryl quinolinium crystals with phenolic sulfonate counteranions and investigate their supramolecular interactions that affect their quadratic nonlinear optical properties. The phenolic group acting as an electron-donor as well as hydrogen-bond donor site is located at one end of the anion, while the sulfonate group acting as an electron-acceptor as well as hydrogen-bond acceptor site is located at the opposite end of the anion. New styryl quinolinium crystals with 4-hydroxybenzenesulfonate and 6-hydroxynaphthalene-2-sulfonate counteranions exhibit a large macroscopic optical nonlinearity with very efficient second harmonic generation (SHG) efficiency. In styryl quinolinium 4-hydroxybenzenesulfonate crystals, the styryl quinolinium cation chromophores exhibit an acentric ordering with a high order parameter close to 1.0, which is optimal for electro-optic applications or THz-wave generation. The 4-hydroxybenzenesulfonate counteranions form strong head-to-tail hydrogen bonds, and they are also packed in acentric layers. The direction of the polar axes in cation and anion layers is practically identical. Therefore, the introducing phenolic group acting as an electron-donor as well as hydrogen-bond donor to the sulfonate counteranion is a potential technique for crystal engineering to tailor molecular ordering as well as the physical properties of salt-type quinolinium derivatives. cation, has been developed.23−26 For example, 2-(4-hydroxy-3methoxystyryl)-1-methylquinolinium 4-methylbenzenesulfonate (HMQ-T) (see Figure 1) crystal exhibits excellent nonlinear optical properties leading to a high THz-wave generation efficiency.23 The main supramolecular interaction in HMQ-T crystal involves the Coulomb interaction between the 2-(4hydroxy-3-methoxystyryl)-1-methylquinolinium (HMQ) cation and 4-methylbenzenesulfonate anion,23,24 similar to that in DAST crystal, where the same counteranion is utilized. In addition, the phenolic −OH group at the end of the HMQ cation forms a strong hydrogen bond with the −O−S− of the sulfonate group on benzenesulfonate anions.23,24 Until now, introduction of an additional polar substituent acting as a strong hydrogen-bond donor has not been reported yet for the counteranions combined with the HMQ cation. For styryl pyridinium derivatives, such attempts often resulted in centrosymmetric crystal structures.9,11

1. INTRODUCTION An understanding of supramolecular interactions including secondary bonds in organic crystals is very important to achieve preferred molecular arrangements in the crystalline state leading to desired physical properties.1 In particular, for second-order (quadratic) nonlinear optical applications, a noncentrosymmetric molecular arrangement in the crystalline state is crucial.2−5 Noncentrosymmetric crystals based on heteroaromatic pyridinium cations exhibit excellent nonlinear optical properties. Since the reporting of 4-(4-(dimethylamino)styryl)-1-methylpyridinium 4-methylbenzenesulfonate (DAST) crystal in 1989,6 based on the Coulomb interaction between a pyridinium cation and a sulfonate anion, with large macroscopic optical nonlinearities,7,8 many styryl pyridinium derivatives with various counteranions have been reported.9−22 In order to optimize the molecular ordering of styryl pyridinium chromophores in the crystalline state and their crystal characteristics, various hydrogen-bonded groups such as hydroxyl, carboxyl, and amine groups have been incorporated in aromatic sulfonate anions.9−13 For obtaining large macroscopic optical nonlinearities in ionic salt crystals, an alternative cation, styryl quinolinium © 2013 American Chemical Society

Received: August 20, 2013 Revised: October 3, 2013 Published: October 14, 2013 5085

dx.doi.org/10.1021/cg401261z | Cryst. Growth Des. 2013, 13, 5085−5091

Crystal Growth & Design

Article

6-hydroxynaphthalene-2-sulfonate (HMQ-HNS) exhibit a large macroscopic optical nonlinearity with very efficient second harmonic generation (SHG). The influence of phenolic benzenesulfonate anion on supramolecular interactions in the crystalline state was investigated, and the macroscopic optical nonlinearities were characterized by considering the arrangement of both the cation and anion.

2. EXPERIMENTAL SECTION 2.1. Synthesis. The new compounds, HMQ-OH and HMQ-HNS were synthesized by metathesization of 2-(4-hydroxy-3-methoxystyryl)-1-methylquinolinium iodide (1 equiv) with the corresponding sodium precursors (3 equiv), sodium 4-hydroxybenzenesulfonate for HMQ-OH and sodium 6-hydroxynaphthalene-2-sulfonate for HMQHNS, according to ref 23, 24. Methanol was used as the solvent. HMQ-OH. Yield = 45%. 1H NMR (400 MHz, DMSO-d6, δ): 10.02 (s, 1H, OH), 9.43 (s, 1H, OH), 8.94 (d, 1H, J = 9.2 Hz, C5H2N), 8.51 (d, 1H, J = 9.2 Hz, C6H4), 8.50 (d, 1H, J = 9.2 Hz, C5H2N), 8.29 (d, 1H, J = 8.0 Hz, C6H4), 8.17 (d, 1H, J = 15.6 Hz, CH), 8.12 (m, 1H, C6H4), 7.90 (t, 1H, J = 7.6 Hz, C6H4), 7.70 (d, 1H, J = 15.6 Hz, CH), 7.59 (s, 1H, C6H3), 7.41 (d, 1H, C6H3), 7.37 (d, 2H, J = 6.8 Hz, C6H4SO3−), 6.91 (d, 1H, J = 8.4 Hz, C6H3), 6.87 (d, 2H, J = 8.8 Hz, C6H4SO3−), 4.52 (s, 3H, NCH3), 3.89 (s, 3H, OCH3). Elemental

Figure 1. Chemical structure of styryl quinolinium chromophores.

In this study, we design, synthesize, and characterize new acentric styryl quinolinium derivatives based on the HMQ cation with phenolic sulfonate counteranions (see Figure 1) to better understand their supramolecular interactions in the crystalline state and physical properties. The phenolic group, acting as an electron-donor as well as hydrogen-bond donor site, is located at one end of the anion, while the sulfonate group acting as an electron-acceptor as well as hydrogen-bond acceptor site is located at the opposite end of the anion. New styryl quinolinium crystals, namely, 2-(4-hydroxy-3-methoxystyryl)-1-methylquinolinium 4-hydroxybenzenesulfonate (HMQOH) and 2-(4-hydroxy-3-methoxystyryl)-1-methylquinolinium

Figure 3. Crystal packing diagram of HMQ-T obtained from ref 23: (a) projected along the b-axis and (b) projected along the a-axis. The thick dotted lines in (b) present strong hydrogen bonds between phenolic −O−H group on cation and −S−O− group of sulfonate on anion. The shadow green lines present the layers formed by anions only. (c) Anion layer with weak hydrogen bonds between −S−O−··· H−C- groups on anions, presented by thin dotted lines. The solid vectors in (b) present the direction of the first-order hyperpolarizability along the main charge-transfer direction of cations and anions.

Figure 2. Crystal packing diagram of DAST obtained from CCDC:7 (a) projected along the c-axis and (b) projected along the b-axis. The shadow green lines present the layers formed by anions only. (c) Anion layer with weak hydrogen bonds between −S−O−···H−C− groups on anions, presented by dotted lines. The solid vectors in (b) present the direction of the first-order hyperpolarizability along the main charge-transfer direction of cations and anions. 5086



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Figure 5. A photograph of as-grown HMQ-OH crystal grown by rapid cooling method.

Figure 4. UV−vis absorption spectra in methanol: (a) the chromophores and (b) anion precursors, sodium 4-hydroxybenzenesulfonate for HMQ-OH, sodium 6-hydroxynaphthalene-2-sulfonate for HMQ-HNS, silver 4-methylbenzenesulfonate for HMQ-T.

analysis for C25H23NO6S: Calcd. C 64.50, H 4.98, N 3.01, O 20.62, S 6.89; Found: C 64.33, H 5.08, N 3.01, S 6.85. HMQ-HNS. Yield = 41%. 1H NMR (400 MHz, DMSO-d6, δ): 10.06 (s, 1H, OH), 9.75 (s, 1H, OH), 8.95 (d, 1H, J = 8.8 Hz, C5H2N), 8.52 (d, 1H, J = 9.2 Hz, C6H4), 8.51 (d, 1H, J = 8.8 Hz, C5H2N), 8.29 (d, 1H, J = 8.0 Hz, C6H4), 8.17 (d, 1H, J = 15.2 Hz, CH), 8.12 (m, 1H, C6H4), 7.96 (s, 1H, C10H6SO3−), 7.90 (t, 1H, J = 7.4 Hz, C6H4), 7.76 (d, 1H, J = 8.4 Hz, C10H6SO3−), 7.71 (d, 1H, J = 15.6 Hz, CH), 7.60 (s, 1H, C10H6SO3−), 7.56 (s, 1H, C6H3), 7.55 (m, 1H, C10H6SO3−), 7.41 (d, 1H, C6H3), 7.05 (m, 2H, C10H6SO3−), 6.91 (d, 1H, J = 8.0 Hz, C6H3), 4.52 (s, 3H, NCH3), 3.89 (s, 3H, OCH3). Elemental analysis for C29H25NO6S: Calcd. C 67.56, H 4.89, N 2.72, O 18.62, S 6.22; Found: C 67.60, H 4.88, N 2.78, S 6.27. 2.2. Crystal Structure Analysis. HMQ-OH. Single crystals were grown by slow evaporation method in methanol. C51H52N2O14S2, Mr = 981.07, monoclinic, space group Pc, a = 11.2479(4) Å, b = 14.1825(6) Å, c = 15.5718(6) Å, β = 108.490(1)°, V = 2355.8(1) Å3, Z = 2, T = 290(1) K, crystal dimension 0.06 × 0.03 × 0.02 mm3, μ(Mo Kα) = 0.185 mm−1. Of 9995 reflections collected in the θ range 3.0−25.0° using an ω scans on a Rigaku R-axis Rapid S diffractometer, 4998 were unique reflections (Rint = 0.041, completeness = 93.0%). The structure was solved and refined against F2 using SHELX97,27 637 variables, wR2 = 0.181, R1 = 0.053 (Fo2 > 2σ(Fo2)), GOF = 1.08, Flack parameter x = 0.10(10), and max/min residual electron density 0.62/−0.40 e·Å−3. Further details of the crystal structure investigation(s) may be obtained from the Cambridge Crystallographic Data Center (CCDC, 12 Union Road, Cambridge CB2 1EZ (UK); tel.: (+44)1223-336-408, fax: (+44)1223-336-033, e-mail: [email protected]) on quoting the depository number CCDC-940996.

Figure 6. Crystal packing diagram of HMQ-OH projected along the crystallographic a-axis (a), b-axis (b), and c-axis (c).

3. RESULTS AND DISCUSSION 3.1. Synthesis and Characterization. In heteroaromatic salt-type crystals, the contributions of cation and anion molecules to nonlinear optical properties are often considered independently. Moreover, it is often considered that the relatively large size styryl cation with strong electron-donor and electron-acceptor groups, similar to the cation of DAST, mainly contributes to quadratic nonlinear optical properties, and the contribution of a smaller counteranion is ignored.22,23,28 In principle, in the crystalline state, when the effective charge transfer axis of cations is parallel to that of anions, the quadratic nonlinear optical response can be enhanced by combining the contribution of cations and anions. 5087



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Figure 7. Molecular arrangement of HMQ-OH crystals: (a) strong hydrogen bonds with a distance of less than 2.5 Å, projected along the b-axis and (b) the anion layer projected along the a-axis. The distance of strong hydrogen bonds is less than 2.5 Å. (c) Methanol forms only weak intermolecular interactions; hydrogen bonds with a distance of less than 3.1 Å are indicated.

similar to as in DAST derivatives. However, the effective charge transfer axis of anions is almost parallel to that of cations, as shown in Figure 3a,b. Therefore, styryl quinolinium derivatives based on HMQ cation and benzenesulfonate-type anion have a strong tendency to form acentric ordering of cations and anions in the crystalline state and align the effective charge transfer axes of cation and anion layers parallel to each other. The chemical structures of new styryl quinolinium derivatives that were synthesized are shown in Figure 1 and consist of HMQ cation and analogous anions, 4-hydroxybenzenesulfonate and 6-hydroxynaphthalene-2-sulfonate. To maintain the main supramolecular interactions of previously reported HMQ derivatives,23−26 the same cation was used, and most of the anion structure was kept unchanged. A polar phenolic substituent was incorporated to the benzenesulfonate- and naphthalenesulfonatebased anions, which can act as strong hydrogen-bond donor as well as electron-donor. New compounds, HMQ-OH and HMQ-HNS were synthesized by metathesis reaction of 2-(4hydroxy-3-methoxystyryl)-1-methylquinolinium iodide with 3 equiv of sodium precursors, that is, sodium 4-hydroxybenzenesulfonate and sodium 6-hydroxynaphthalene-2-sulfonate in methanol, according to refs 23 and 24. Figure 4a shows the absorption spectra of HMQ derivatives in methanol. In HMQ-OH and HMQ-HNS chromophores, the

For example, in the case of acentric styryl pyridinium cations, for example, DAST and its many known derivatives, the effective charge transfer axis of the anions is often not parallel to that of the cations. The molecular arrangement of cations and anions in a DAST crystal is shown in Figure 2. The crystal structure of DAST was obtained from Cambridge Crystallographic Data Center (CCDC).7 The anions such as 4-methylbenzenesulfonate,7 2,4-dimethylbenzenesulfonate,10 2,4,6-trimethylbenzenesulfonate,14 and naphthalene-2-sulfonate15 with only weak electron-donor groups and weak hydrogen-bond donor sites form acentric anion layers (see Figure 2c). However, the effective charge transfer axis of anions is almost antiparallel to that of cations, as shown in Figure 2a,b. When incorporating anions with a strong polar substituent (acting as strong electron-donor as well as strong hydrogen-bond donor) at the opposite end of the sulfonate group, for example, as in 4-hydroxybenzenesulfonate9,11 and 4-amino-1-naphthalenesulfonate,10 their styryl pyridinium crystals exhibit centrosymmetric crystal structures and are thus not interesting materials for quadratic nonlinear optics. In styryl quinolinium HMQ derivatives, the anions such as 4methylbenzenesulfonate23,24 and naphthalene-2-sulfonate26 with a weak electron-donor group and weak hydrogen-bond donor sites, also form acentric anion layers (see Figure 3c), 5088



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3.2. Crystal Structure. In order to analyze the crystal structure, single crystals are grown from a solution. HMQ-OH single crystals were obtained by slow evaporation method at 40 °C in methanol as well as by the rapid cooling method at a saturation temperature of 40 to −24 °C in methanol. Both HMQ-OH crystals grown by slow evaporation method and rapid cooling methods show identical X-ray diffraction (XRD) patterns. A photograph of the as-grown HMQ-OH single crystal is shown in Figure 5. Owing to poor solubility (0.33 g/ 100 g methanol at 50 °C) and poor crystal growth characteristics of HMQ-HNS, dendritic small crystals were obtained by the slow evaporation method; therefore, only the structure of HMQ-OH crystals was analyzed. In single crystal X-ray analysis, HMQ-OH crystals exhibit an acentric monoclinic space group symmetry Pc. Figures 6 and 7 show the crystal packing diagram and molecular ordering in HMQ-OH crystal. The unit cell consists of four HMQ cations and four anions with two methanol and two water molecules. One of the main supramolecular interactions involves the Coulomb interaction between the quinolinium cation and sulfonate anion. As shown in Figures 6a and 7a, the average plane of HMQ cations is perpendicular to the plane of the phenyl ring on 4-hydroxybenzenesulfonate anion, which is similar to that in both DAST and HMQ-T crystals (see Figures 2a and 3a, respectively). Owing to the combination of Coulomb interactions between the cations and anions and strong π−π stacking forces between the HMQ cations, HMQ cation layers are packed alternatively with sulfonate anion layers, which are shown by shadowed green lines in Figure 6b,c. Additional important supramolecular interactions involve hydrogen bonds. The phenolic −OH group on HMQ cation forms strong hydrogen bonds with the −O−S- of sulfonate group on anions with distances of 1.833 Å, 2.349 Å, and 2.416 Å (see Figure 7a); similar bonds were observed in HMQ-T crystal (a distance of 1.944 Å, see Figure 3b).23 Figure 7b shows the molecular arrangement of 4-hydroxybenzenesulfonate anions having phenolic OH groups. Similar to the phenolic OH group on a HMQ cation, the phenolic OH group on an anion forms strong hydrogen bonds with other sulfonate anions. As shown in Figure 7b, four strong hydrogenbonds are shown in the anion layer. The phenolic −OH group acts as a hydrogen-bond donor (also electron-donor) and the sulfonate group acts as a hydrogen-bond acceptor (also electron-acceptor). The phenolic OH and sulfonate groups are located at the opposite ends of the anion, and therefore, they show a strong tendency to form head-to-tail hydrogenbonds. The hydrogen bond of −O9−H···−O12−S− with a distance of 1.949 Å forms acentric polymer-like chains, shown by red dotted lines in Figure 7b. The other acentric polymerlike chains are formed by two hydrogen-bonds shown by blue dotted lines, in which water is also involved: the hydrogen bond of −O3−H···O−H (water) with a distance of 1.885 Å and −S− O6−···H−O (water) with a distance of 1.951 Å. These two acentric polymer-like anion chains are linked by weaker hydrogen bonds of −S−O10−···H−O (water) with a distance of 2.135 Å, shown by green dotted lines. The methanol molecules with space-filling characteristics30 form only relatively weak hydrogen bonds with the anion chains (see Figure 7c). 3.3. Optical Nonlinearities. In order to evaluate macroscopic optical nonlinearities in a more quantitative manner, first, only the orientation of HMQ cations in the crystalline state was considered. HMQ-OH crystals have two conformers

Figure 8. (a) Molecular conformation of two conformers of HMQ cations. Orientation of HMQ cations in the crystalline state projected along the b-axis (b) and the a-axis (c). The solid vectors present the directions of first hyperpolarizability of HMQ cations. For clarity, all hydrogen atoms are omitted except for the hydrogen atoms on the phenolic group.

main charge transfer involves the π−π* transition of the HMQ cation with the wavelength of maximum absorption λmax of 439 nm, which is practically identical also for HMQ-T. The molar absorptivity also shows similar values.23 Figure 4b shows the absorption spectra of the anion precursors, that is, sodium 4-hydroxybenzenesulfonate for HMQ-OH, sodium 6-hydroxynaphthalene-2-sulfonate for HMQ-HNS, and silver 4-methylbenzenesulfonate for HMQ-T in methanol. The aryl sulfonate anions with phenolic OH groups exhibit a higher γmax than the aryl sulfonate anion with methyl group, as shown in Figure 4b. This confirms that, as expected, the phenolic OH group on the aryl sulfonate anion is a stronger electron donor than a methyl group. In order to screen the macroscopic quadratic optical nonlinearities in the crystalline state, a powder second harmonic generation (SHG) test is performed.29 A pump laser light with a pulse duration of 120 fs, central wavelength of 1240 nm, and full width at half-maximum (fwhm) spectral bandwidth of 14 nm was used. The SHG intensity at 620 nm was roughly estimated through monitoring by the naked eye. For checking the existence of two-photon fluorescence, the intensity of the scattered light was recorded using a spectrometer. Crystalline powders obtained from recrystallization in methanol were used. Both HMQ-OH and HMQ-HNS crystals generated quite strong SHG signals (see Figure S1 in the Supporting Information), which are comparable to that of HMQ-T crystals. Thus, both HMQ-OH and HMQ-HNS crystals exhibit acentric crystal structures that gave great potential for quadratic nonlinear optical applications. 5089



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Figure 9. (a) Molecular orientation of two conformers of 4-hydroxybenzenesulfonate anions in the crystalline state projected along the a-axis. The solid vectors present the directions of first hyperpolarizability of anion molecules. (b) The combined contributions of cations and anions, projected along the a-axis. The long and the short solid vectors present the directions of first hyperpolarizability of cations and anions, respectively.

of HMQ cation, as shown in Figure 8a. For styryl quinolinium chromophores, it has been shown that their molecular optical nonlinearity is not sensitive to twisting between the phenyl ring and the methylquinolinium ring.23,26 Because the plane of the phenolic ring is only slightly twisted to the plane of the methylquinolinium ring on HMQ cation in both the conformers, the molecular optical nonlinearity of the HMQ cation in HMQ-OH crystals is expected to be similar to that of the previously reported HMQ analogous crystals.23,26 Therefore, the direction and amplitude of the first-order hyperpolarizability can be considered along the main charge transfer direction βmax of HMQ cation, as previously determined by quantum mechanical calculations22,31 using finite field-density functional theory (FF-DFT) based on B3LYP/6-311+G*32,33 for HMQ analogous crystals.23,26 As shown in Figure 8b,c, the directions of the first-order hyperpolarizability of the four HMQ cations are aligned almost perfectly parallel in the ac mirror plane. Therefore, the molecular-ordering angle of βmax of HMQ cation with respect to the crystal polar axis is almost zero, and therefore, the order parameter of HMQ cations is close to the maximum value of 1.0. Therefore, the macroscopic nonlinear optical response, considering the orientation of HMQ cations is very large with a diagonal component of effective hyperpolarizability tensor of βeff iii in the range of 145− 178 × 10−30 esu, which is comparable to best organic nonlinear optical crystals known to date.6,22,23,34 4-Hydroxybenzenesulfonate anions are considered in a similar manner as HMQ cations in the crystalline state. The anion consists of a π-conjugated phenyl group linked in

between the hydroxyl electron-donor and sulfonate electronacceptor. Figure 9a shows the molecular orientation of the two conformers of 4-hydroxybenzenesulfonate anions projected along the a-axis. Although compared to the methyl group of 4-methylbenzenesulfonate anion in DAST and HMQ-T crystals, the hydroxyl group exhibits an increased electrondonor strength and higher dipole moment, 4-hydroxybenzenesulfonate anions still pack in an acentric arrangement, as shown in Figure 9a. The solid vectors show the directions of the first hyperpolarizability of the anion molecules. The effective firsthyperpolarizability direction of the anion molecules is also close to the crystallographic c-axis, similar to that of cations. Figure 9b shows the contribution of both cations and anions, projected along the a-axis. The polar axis of anions is parallel to that of cations. Therefore, the styryl quinolinium derivatives with anions having phenolic group acting as strong hydrogenbond donor and electron-donor are excellent candidates for obtaining an acentric arrangement in the crystalline state with large quadratic optical nonlinearity.

4. CONCLUSIONS We have investigated new acentric styryl quinolinium crystals, namely, HMQ-OH and HMQ-HNS with phenolic sulfonate counteranions, 4-hydroxybenzenesulfonate and 6-hydroxynaphthalene-2-sulfonate, respectively. Both HMQ-OH and HMQHNS crystals exhibit large macroscopic optical nonlinearity with efficient SHG. In HMQ-OH crystals, HMQ cations exhibit an acentric ordering with optimal crystal packing for electrooptic applications. In the anions, the phenolic group acts as 5090



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(16) Coe, B. J.; Harris, J. A.; Asselberghs, I.; Wostyn, K.; Clays, K.; Persoons, A.; Brunschwig, B. S.; Coles, S. J.; Gelbrich, T.; Light, M. E.; Hursthouse, M. B.; Nakatani, K. Adv. Funct. Mater. 2003, 13, 347. (17) Umezawa, H.; Tsuji, K.; Okada, S.; Oikawa, H.; Matsuda, H.; Nakanishi, H. Opt. Mater. 2002, 21, 75. (18) Matsukawa, T.; Takahashi, Y.; Miyabara, R.; Koga, H.; Umezawa, H.; Kawayama, I.; Yoshimura, M.; Okada, S.; Tonouchi, M.; Kitaoka, Y.; Mori, Y.; Sasaki, T. J. Cryst. Growth 2009, 311, 568. (19) Okada, S.; Masaki, A.; Matsuda, H.; Nakanishi, H.; Kato, M.; Muramatsu, R.; Otsuka, M. Jpn. J. Appl. Phys. 1990, 29, 1112. (20) Nunzi, F.; Fantacci, S.; Cariati, E.; Tordin, E.; Casatid, N.; Macchi, P. J. Mater. Chem. 2010, 20, 7652. (21) Matsukawa, T.; Mineno, Y.; Odani, T.; Okada, S.; Taniuchi, T.; Nakanishi, H. J. Cryst. Growth 2007, 299, 344. (22) Kim, P. J.; Jeong, J. H.; Jazbinsek, M.; Kwon, S. J.; Yun, H.; Kim, J. T.; Lee, Y. S.; Baek, I. H.; Rotermund, F.; Günter, P.; Kwon, O. P. CrystEngComm 2011, 13, 444. (23) Kim, P. J.; Jeong, J. H.; Jazbinsek, M.; Choi, S. B.; Beak, I. H.; Kim, J. T.; Rotermund, F.; Yun, H.; Lee, Y. S.; Günter, P.; Kwon, O. P. Adv. Funct. Mater 2012, 22, 200. (24) Chantrapromma, S.; Jindawong, B.; Fun, H. K. Acta Crystallogr. 2007, E63, o4928. (25) Chantrapromma, S.; Jindawong, B.; Fun, H. K.; Patil, P. S. Anal. Sci. 2007, 23, x81. (26) Kim, P. J.; Jabinsek, M.; Jeong, J. H.; Kim, J. T.; Lee, Y. S.; Jung, Y. M.; Lee, S. W.; Kwon, O. P. CrystEngComm 2012, 14, 3633. (27) Sheldrick, G. M. Acta Crystallogr. 2008, A64, 112. (28) Kim, J. T.; Kwon, O. P.; Jazbinsek, M.; Park, Y. C.; Seo, J. I.; Lee, Y. S. J. Phys. Chem. C 2011, 115, 23535. (29) Kurtz, K.; Perry, T. T. J. Appl. Phys. 1968, 39, 3798. (30) Choi, E. Y.; Kim, P. J.; Jazbinsek, M.; Kim, J. T.; Lee, Y. S.; Günter, P.; Lee, S. W.; Kwon, O. P. Cryst. Growth Des. 2011, 11, 3049. (31) Kwon, S. J.; Kwon, O. P.; Seo, J. I.; Jazbinsek, M.; Mutter, L.; Gramlich, V.; Lee, Y. S.; Yun, H.; Günter, P. J. Phys. Chem. C 2008, 112, 7846. (32) Perdew. J. P. Phys. Rev. B 1986, 33, 8822. (33) Becke, A. D. J. Chem. Phys. 1993, 98, 1372. (34) Kwon, O. P.; Kwon, S. J.; Jazbinsek, M.; Brunner, F. D.; Seo, J. I.; Hunziker, Ch.; Schneider, A.; Yun, H.; Lee, Y. S.; Günter, P. Adv. Funct. Mater. 2008, 18, 3242.

electron-donor as well as hydrogen-bond donor site, while the sulfonate group acts as electron-acceptor as well as hydrogenbond acceptor site. The counteranions 4-hydroxybenzenesulfonate form strong head-to-tail hydrogen bonds and polymerlike chains with an acentric ordering in the crystalline state. Moreover, the direction of polar axes of cation and anion layers is practically identical. Therefore, the introduction of phenolic group on the anion is a potential crystal engineering technique for tailoring molecular ordering and physical properties of salttype styryl quinolinium derivatives.

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ASSOCIATED CONTENT

S Supporting Information *

Spectral data of powder SHG measurement. This information 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]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS

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REFERENCES

This work has been supported by Agency for Defense Development and Defense Acquisition Program Administration funded by Ministry of National Defense, and Mid-career Researcher Program (NRF-2013R1A2A2A01007232), and Basic Science Research Program (No. 2009-0093826) through the National Research Foundation of Korea (NRF) funded by the Korea Government. J.W.K. and F.R. acknowledge support from the NRF (2011-0017494 and WCI 2011-001).

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