Diamondoid Porous Organic Salts toward Applicable Strategy for

Article pubs.acs.org/crystal

Diamondoid Porous Organic Salts toward Applicable Strategy for Construction of Versatile Porous Structures Atsushi Yamamoto,† Shinji Uehara,† Tomoya Hamada,† Mikiji Miyata,† Ichiro Hisaki,† and Norimitsu Tohnai*,†,‡ †

Department of Material and Life Science, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan ‡ PRESTO, Japan Science and Technology Agency (JST), Japan S Supporting Information *

ABSTRACT: To achieve efficient construction of organic porous materials with versatile properties, we propose a widely applicable novel strategy using organic salts comprising triphenylmethylamine (TPMA) and sulfonic acids. We demonstrate that TPMA and sulfonic acids having polyaromatic moieties give a new class of porous structures consisting of diamond networks, named as diamondoid porous organic salts (d-POSs). In the d-POSs, TPMA and the sulfonic acids are assembled into stable tetrahedral supramolecular clusters via charge-assisted hydrogen bonding as primary building blocks. Subsequently, the clusters are accumulated by π−π interactions between the polyaromatic moieties to yield the d-POSs through formation of the diamond networks. Large steric hindrance of the clusters prevents the diamond networks from constructing highly interpenetrated structures, giving continuous open channels. It should be noted that the interpenetration degree of the diamond networks is controlled by tuning the bulkiness of the cluster with alteration of sulfonic acids. Anthracene-2-sulfonic acid (2-AS) constructs a 3-fold structure with onedimensional channels, whereas pyrene-1-sulfonic acid (1-PyS) yields a 2-fold structure having two-dimensional channels. Furthermore, the organic salt of TPMA and 2-AS also give polymorphic structures in response to host−guest ratio and guest species, indicating not only their stability but the flexibility of the d-POSs.

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INTRODUCTION The construction of porous structures using small organic compounds has been attracting a great deal of interest due to the wide variety of applications in not only gas and molecular storage1 but also guest-responsive materials such as chemical sensors.2 Recently, strategic construction of porous structures such as metal−organic frameworks (MOFs)3 and covalent− organic frameworks (COFs)4 has been receiving attention because of their concise strategy and molecular compatibility. These structures are strongly constructed by either coordination bonding or covalent bonding. In comparison with these materials, organic porous structures formed by weak noncovalent bonding are also attractive due to their processing advantage and good workability.5 In this context, we focus on organic salts comprising ammonium sulfonates to design porous structures.6 The organic salt systems in which two components are combined enable systematic design of resultant structures by changing the combination. Furthermore, the ion pairs of ammonium sulfonates produce strong intermolecular interactions such as hydrogen bonds and electrostatic interactions. The strong interactions make possible formation of the pairs invariably. In the past two decades, Ward et al. have best investigated a variety of nanoporous structures based on guanidine and disulfonic acids.7 In these structures, twodimensional hydrogen-bonding sheets comprising guanidinium © 2012 American Chemical Society

ions and the sulfonate ions are connected by disulfonate pillars to yield grid-like structures with one-dimensional open channels. On the other hand, we previously reported the preparation of organic structures, called porous organic salts (POSs), consisting of sulfonic acids and aliphatic amines.8 For example, biphenyl-4,4′-disulfonic acid and aliphatic primary amines construct POSs with layer networks via charge-assisted hydrogen bonding.8a The size and shape of the void space can be readily modulated by alteration of the amine used. We expect that the POS system is also a suitable system for producing a variety of organic porous structures with versatile functionalities, by combinatorial diversity of sulfonic acids and amines. In this Article, we propose a novel efficient strategy for constructing porous structures having diamond networks by the POS system. The construction of such structures is fascinating due to not only their highly symmetrical and shapely networks but also their stiffness, stability, and large void space. Since the first report of stable organic diamond networks of tetrahedral tetracarboxylic acid derivatives by Ermer in 1988,9 some porous structures have been prepared utilizing similar single tetrahedral Received: June 12, 2012 Revised: July 11, 2012 Published: July 12, 2012 4600

dx.doi.org/10.1021/cg300796u | Cryst. Growth Des. 2012, 12, 4600−4606

Crystal Growth & Design

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molecules as building blocks.10 However, it still remains difficult to achieve the desired variety in such structures using this conventional strategy. This is because the structural design of diamond networks often restricts the molecular configuration to a tetrahedral shape, which prevents any further modification. Moreover, these diamond networks tend to form highly interpenetrating structures,11 resulting in small or absent void space, because of the “less-bulkiness” building blocks. To overcome these problems, we conceive a supramolecular-based strategy, where tetrahedral supramolecules formed by simple molecules serve as building blocks to construct diamond networks (Figure 1a). The tetrahedral supramolecule is

jutting out in the tetrahedral direction would also serve as supramolecular glue to connect the clusters through π−π interactions,13 forming not only rigid but also flexible (amphoteric) diamond networks and porous structures. These amphoteric structures are expected to show more static and dynamic responses to external stimuli than those observed in some flexible MOFs.2b,c,3c In addition, the size, shape, and functionalities of the cluster should be easily tuned by arranging the sulfonic acid derivatives. We combined different three sulfonic acid derivatives with TPMA: napthalene-2-sulfonic acid (2-NS), anthracene-2-sulfonic acid (2-AS), and pyrene-1sulfonic acid (1-PyS) (Figure 1b,ii). The organic salts produced from 2-AS or 1-PyS yield diamond networks and porous interpenetrated structures including the aromatic molecules. Interestingly, the degree of interpenetration of the diamond networks is controlled by tuning the bulkiness of the cluster, which resulted in the formation of different size and dimensional void space. Furthermore, the diamond networks of 2-AS also alter their structures in response to host−guest ratio and guest species.

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RESULTS AND DISCUSSION Hierarchical Construction of d-POS. The organic salt comprising 2-AS and TPMA yielded yellow crystals by recrystallization from a mixture of ethanol and a nonpolar solvent such as an aromatic hydrocarbon. Single crystals suitable for X-ray crystallographic analysis were obtained by recrystallization from a mixed solvent of ethanol and 1,2,4trichlorobenzene (TCB). The X-ray analysis revealed that the crystal has a porous structure based on a diamond network, named diamondoid porous organic salt (d-POS) (d-POS 1a, Figure 2a). The crystallographic parameter is also shown in Table 1. d-POS 1a is hierarchically constructed starting from 2AS and TPMA (Figure 2c). First, 2-AS and TPMA are assembled into [4 + 4] supramolecular clusters by chargeassisted hydrogen bonding. The hydrogen-bonding distances between oxygen atoms of 2-AS and nitrogen atoms of TPMA range from 2.735 to 2.863 Å (Figure S1). Although the hydrogen bonding constructs a cubic-like network, the clusters have a tetrahedral shape because the anthracenyl groups are sufficiently longer than the triphenylmethyl groups (the longest distance between the sulfur atom and any carbon atoms is 9.1 Å) (Figures 1b, 2c). The longest distance between neighboring sides of the tetrahedral cluster is approximately 26 Å. Next, the anthracenyl groups form π−π stacking, acting as linkers to arrange the clusters into the resulting diamond network (Figure 2c). The mean plane distance between the aromatic moieties is 3.384 Å (Figure S2). The diamond network contains a very large void space with 35 × 36 Å hexagonal windows. Hence, three independent diamond networks are interpenetrated to fill the void space. Nevertheless, the interpenetrated structure still has one-dimensional (1D) void space including TCB molecules used for recrystallization solvent as guest molecules (Figure 2c and a, right). The bulkiness of the supramolecular cluster at the tetrahedral nodes plays a key role in generating such void space. The sphere-like core covered with triphenylmethyl groups in the cluster is approximately 16 Å in diameter. This bulkiness causes a large steric hindrance between the nodes, preventing the formation of highly interpenetrating structure and complete filling of the void space. The volume of the void space is 30% (calculated by PLATON/VOID15), with the largest space of 10.7 × 10.7 Å and the smallest space of 6.1 × 6.1 Å (Figure 2a, right). In the void space, four TCB molecules are included per

Figure 1. (a) Proposed supramolecular-based strategy. (b) [4 + 4] supramolecular cluster constructed of TPMA and sulfonic acid derivatives (i) and chemical structures of sulfonic acid derivatives and guest molecules (ii). The distances are defined between a carbon or sulfur atom and any carbon atoms.

expected to work as a “sterically bulky” node to inhibit the diamond networks from constructing highly interpenetrating structures. Previously, we reported specific supramolecules named [4 + 4] supramolecular clusters, which are constructed from organic salts comprising triphenylmethylamines (TPMA) and monosulfonic acid derivatives (Figure 1b,i).12 Within the clusters, the sulfonic acid derivatives are always arranged tetrahedrally via cubic-like charge-assisted hydrogen bonding. In this respect, we designed tetrahedral supramolecular clusters as building blocks for the diamond networks that combine TPMA with monosulfonic acid derivatives having polycyclic aromatic moieties. We expect that the long aromatic moieties 4601



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Figure 2. Crystal structures of d-POSs. Top view and void space of d-POSs composed of 2-AS and TPMA including TCB (d-POS 1a) (a) and 1-PyS and TPMA including TMB (d-POS 2) (b). In the top view, guest molecules are omitted for clarity. In the sky-blue-colored void space, guest molecules are represented by green balls and sticks. Hydrogen atoms are omitted for clarity except in the space-filling model of a cluster. Hierarchical interpretation of d-POS 1a (c) and 2 (d). In the diamond networks and interpenetrated structures, triphenylmethyl groups are omitted for clarity. The independent diamond networks are indicated by orange, green, and blue.

PyS and TPMA also form tetrahedral supramolecular clusters by charge-assisted hydrogen bonding in the structure (Figure 2d). The longest distance between neighboring sides of the cluster is approximately 25 Å. The clusters are arranged in a diamond network by π−π stacking between the pyrenyl groups. The diamond network also has large void space with 29 × 32 Å hexagonal windows and constructs an interpenetrated structure. However, it is noteworthy that only two independent diamond networks are interpenetrated, unlike the 3-fold interpenetrated structure of d-POS 1a. Accordingly, the structure has 2D void space (Figure 2b, right). The 1D void space with the largest space of 7.1 × 5.1 Å and the smallest space of 5.7 × 5.7 Å are connected by small orthogonal channels (calculated volume of the void space is 29%). TMB molecules used for recrystallization solvent are included in the main 1D void space as guest molecules. The differences in these void spaces arise from the shape and size variations of the substituents of the sulfonic acid derivatives. The longest distance between the sulfur atom and any carbon atoms in 1-PyS is 7.8 Å, which is slightly shorter than that of 2-AS (Figure 1b,ii). Therefore, the hexagonal window in the diamond network of d-POS 2 is smaller than that of 1a. In contrast, the width of 1-PyS is larger than that of

cluster. Interestingly, these guest molecules are arranged almost parallel to each other (Figure 2a, right and Figure S3). The distance between centroids of neighboring molecules is 3.930 Å. The guest molecules also adjust their alignment to the void space through CH−Cl contacts with the void surface, which is covered by aromatic rings. The effective CH−Cl contacts between the guest molecules and the walls well contribute to the specific parallel alignment. Highly interpenetrated structures are generally regarded as unfavorable structures due to compression of the void space. However, the characteristic arrangement of the guest molecules is confined by the 1D void space formed by the interpenetration of the diamond networks. Such 1D arrays of molecules may give rise to unique properties such as polarization performance and anisotropic conductivity of charge.16 Structural Diversification of d-POS Depending on Sulfonic Acids. As well as the organic salt containing 2-AS, the organic salt composed of 1-PyS and TPMA also forms a type of d-POS 2 by a similar hierarchical process (Figure 2b,d). Single crystals for X-ray crystallographic analysis were obtained by recrystallization from a mixed solvent of ethanol and 1,3,5trimethylbenzene (TMB). According to the X-ray analysis, 14602



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Table 1. Crystallographic Parameters of d-POSs formula fw crystal system space group a [Å] b [Å] c [Å] α [deg] β [deg] γ [deg] V [Å3] Z dcalcd [g m−3] T [K] reflns observed reflns unique R1 (I > 2.0σ(I)) Rw (all data) CCDC no.a a

2AS-TPMA TCB (d-POS 1a)

1-PyS-TPMA TMB (d-POS 2)

2AS-TPMA TMB (d-POS 1b)

2-AS-TPMA TMB (d-POS 1c)

C39H30NO3SCl3 711.10 tetragonal I41/a 30.5283(2) 30.5283(2) 14.09420(10) 90 90 90 13 135.47(15) 16 1.438 93 5509 5509 0.0684 0.1769 880742

C79H66N2O6S2 1203.52 tetragonal I41/a 27.0647(6) 27.0647(6) 35.4072(9) 90 90 90 25 935.7(11) 16 1.257 103 124 789 11 853 0.1172 0.3712 880741

C264H216O24N8S8 4141.13 monoclinic P21/n 26.1730 31.95700(10) 32.73900(10) 90 111.6200 90 25 456.78(11) 4 1.080 93 62 437 56 289 0.0841 0.2642 881390

C396H322O36N12S12 6209.68 monoclinic P21/c 31.2919(6) 41.6841(8) 31.9775(13) 90 90.7570(8) 90 41 707.1(13) 4 0.989 123 323 245 72 781 0.1047 0.2678 881391

See ref 14.

Figure 3. Crystal structures of d-POSs composed of 2-AS and TPMA including TMB. Top view of d-POS 1b (a) and 1c (b). In the top view, guest molecules and hydrogen atoms are omitted for clarity except for in the space-filling model of one supramolecular cluster. Visualization of the void space in d-POS 1b (c) and 1c (d). Void spaces are indicated in sky blue, and guest molecules are represented by green sticks. Hydrogen atoms of the guests are omitted for clarity. Schematic representation of the interpenetration manners of the diamond networks in d-POS 1b (e) and 1c (f).

2-AS, with the longest distance between any two carbon atoms being 4.9 and 2.8 Å, respectively (Figure 1b,ii). Thus, 1-PyS and TPMA form a more sterically bulky cluster than 2-AS and TPMA to cause more effective prevention of the interpenetration (Figure 2d). These results demonstrate that the relative ratio of the diameter of the cluster’s cores to the length of the polyaromatic groups should have a great influence on the avoidance of highly interpenetrated structures. The shorter length and wider width of polyaromatic groups provide a larger relative ratio of the cores of the clusters. Consequently, the resultant tetrahedral clusters cause larger steric hindrance to

avoid interpenetrated structures of the yielded diamond networks. On the other hand, the organic salt composed of 2-NS and TPMA did not form any diamond networks and porous structures (Figure S4). This is because the naphthyl group of 2-NS (the longest distance between the sulfur atom and any carbon atoms is 6.7 Å) is too short to jut out in the tetrahedral direction from the cluster and to affect π−π interactions between each other. Therefore, the clusters form a close-packed structure without the formation of any diamond networks. These results indicate that the diamond networks 4603



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and the degree of their interpenetration can be readily tuned by selection of suitable sulfonic acid derivatives. Structural Diversification of d-POS Depending on Guest Molecules. Interestingly, the diamond network also shows structural flexibility depending on species and amount of the guest molecule. Here, we show a representative example of the previously mentioned organic salt composed of 2-AS and TPMA. The organic salt also gave two other pseudopolymorphic crystals, d-POS 1b and 1c, by recrystallization from a mixture of ethanol and TMB. Slow recrystallization gave d-POS 1b, whereas quick recrystallization gave mainly 1c. Crystallographic studies revealed that these crystals are also d-POSs containing TMB molecules used for recrystallization solvent in 1D void space as guest molecules (Figure 3a,b). d-POS 1b has indented 1D void space with the maximum size of a crosssection in the void space being 10.6 × 9.6 Å and the minimum size being 4.5 × 3 Å (Figure 3c). The void space is calculated to be 29% per unit cell (PLATON/VOID). In contrast, d-POS 1c possesses comparatively straight 1D void space (Figure 3d). The largest size in the void space is found to be 11.2× 9.9 Å, whereas the smallest is 6.5 × 6.0 Å. As compared to d-POS 1b, the void space in d-POS 1c is slightly larger and without any pocket (36% calculated by PLATON/VOID). These d-POSs are constructed via the same hierarchical process described above. That is to say, three independent diamond networks, topologically the same, are interpenetrated within the structures. These results indicate that stable diamond networks can form regardless of the guests. Interestingly, however, the shape and size of the diamond networks are significantly different. The diamond network in d-POS 1b has 31 × 36 Å hexagonal windows, while that in 1c has 35 × 37 Å hexagonal windows (Figure 3e,f, inset). Such expansion and contraction of the diamond networks are related to the host−guest ratio. In dPOS 1b, three guest molecules are included per cluster. In contrast, four guest molecules are included per cluster in d-POS 1c. Furthermore, the guest species also affected the structure of the diamond networks. d-POS 1c has slightly larger hexagonal windows than those in the former d-POS including TCB molecules (Figure 2a,c) despite the same host−guest ratio. This may be because TMB is slightly larger than TCB. These results indicate that the diamond networks are both stable and flexible in response to the guest molecules, which is distinctly different from conventional diamond networks constructed by strong interactions such as covalent bonding. The flexibility of the diamond networks is derived from not only the conformational flexibility of the clusters themselves but also the orientational flexibility of π−π stacking between the clusters. The manner of the interpenetration of the networks is also shown to be variable (Figure S5). These phenomena are attributed to surprising stability and reproducibility of the cubic-like hydrogen bonding network. As demonstrated in a previous paper, the cubic-like networks are formed universally regardless of sulfonic acid derivatives.12 Therefore, π−π stacking should be preferentially affected from the guest molecules to provide a variety of forms and void space. The structural flexibility leads to high inclusion ability and external stimuli-responsiveness of the porous structures. Structure Transformability of d-POS on Guest Release. To clarify the porous property of the d-POSs, we investigated structure stability upon guest release. Thermal gravimetric analysis (TGA) data of single crystals of d-POS 1a−c show different guest release profiles (Figure 4). The first steps in all TGA data indicate guest release from the d-POSs.

Figure 4. TGA data of the d-POSs composed of 2-AS and TPMA: (a) 1a, (b) 1b, and (c) 1c.

The second steps over 200 °C following to large weight loss indicate decomposition of the components for the host frameworks. As shown in Figure 4a, d-POS 1a completely releases the guest molecules of TCB before 100 °C. After that, no weight loss is observed up to 200 °C. On the other hand, TGA data of d-POS 1b display gradual weight loss up to decomposition of the components over 200 °C, although those of 1c show a guest release profile of TMB similar to that of 1a. These differences are probably due to the shape differences of the void space. The void space of d-POS 1b has protruded pockets incorporating the guest molecule, whereas those of 1a and 1c do not have any pockets. The pockets of the void space enable the structure to keep the guest molecules more tightly, resulting in gradual guest release up to high temperature. As shown in Figure 5, powder X-ray diffraction (PXRD)

Figure 5. PXRD patterns of the d-POSs composed of 2-AS and TPMA: (a) 1a, (b) 1b, (c) 1c, and (d) 1b after guest release.

measurements revealed good crystallinity of these crystals even after guest release. The PXRD measurements also indicate that all d-POSs transform to the same structure upon guest release. Before guest release, the PXRD patterns of d-POS 1b and 1c display one sharp peak at 2θ = 5.46° (d = 16.2 Å) and 5.52° (d = 16.0 Å) corresponding to distances between the channels, respectively. These peaks disappear and new two peaks appear at 6.02° (d = 14.7 Å) and 6.62° (d = 13.3 Å) after 4604



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The single crystals were picked from the solution by filtration and used for the measurements. Crystallographic Analysis of Single Crystals. X-ray diffraction data of the crystals of d-POS 1a and 1c were collected by using synchrotron radiation (λ = 0.7000 Å) via the BL38B1 in the SPring-8 with the approval of JASRI (Proposal No. 2007B1988, 2005, 2039, and 2008A1422). The cell refinements were performed by HKL2000 software.19 X-ray diffraction data of other crystals were measured on a Rigaku R-AXIS RAPID diffractometer with a 2-D area detector using graphite-monochromatized Cu Kα radiation (λ = 1.54187 Å). Direct methods (SIR-2004 and SHELXS-97) were used for the structure solution.20,21 All calculations were performed with the observed reflections [I > 2σ(I)] by the program CrystalStructure crystallographic software packages22 except for refinement, which was performed using SHELXL-97. All non-hydrogen atoms were refined with anisotropic displacement parameters, and hydrogen atoms were placed in idealized positions and refined as rigid atoms with the relative isotropic displacement parameters. The data were also refined by using the SQUEEZE routine function in PLATON15,23 to solve the structures without the influence of the disordered guest molecules. The CIF files of the crystal structures of d-POS-1a and 1b including disordered guest molecules can be also obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac. uk/data_request/cif. Thermoanalysis Measurements. Thermal gravimetric analyses (TGA) were performed on a Rigaku Thermoplus TG8120, ca. 1−2 mg from 30 to 300 °C at a heating rate of 5 °C min−1. Powder X-ray Diffraction Analysis. Powder X-ray diffraction (PXRD) patterns were measured via a Rigaku Ultima IV using graphite monochromatized Cu Kα radiation (λ = 1.54187 Å) at room temperature.

guest release, indicating anisotropic shrinkage of the structures. By considering the contraction degree of the distance (approximately 1.5−3.0 Å) between the channels, the transformed structure could have void space, although molecular arrangement and unit cell of the transformed structure were not determined from the PXRD pattern. These results indicate that the d-POSs have a potential utility for both molecular and gas storage.

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CONCLUSIONS In summary, we have achieved the construction of a new class of porous structure with diamond networks, diamondoid porous organic salts (d-POSs), by a supramolecular-based strategy. The sterically hindered tetrahedral clusters suppress the excessive interpenetration of the diamond networks and yielded porous structures. Furthermore, these diamond networks are easily tuned by alteration of the sulfonic acid, resulting in a change in interpenetration degree and void space. In addition, flexible accumulation of the clusters gives not only stability but flexibility to the diamond networks. Our proposed strategy opens up the possibility to construct organic porous structures with a variety of functionalities. The tetrahedral cluster is a good platform for arranging ubiquitous organic molecules into tetrahedral geometries, even if the organic molecules themselves do not have tetrahedral configurations. This applicability contributes to the easy modification and functionalization of the structures. For example, introduction of polyaromatic groups in porous structures is expected to result in the achievement of fluorescent properties in response to guest molecules. Furthermore, the porous properties (e.g., pore size) can also be controlled by selecting molecular combination. We are currently investigating actively the extension of this strategy to other sulfonic acid derivatives for the construction of unique functional organic porous structures.

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ASSOCIATED CONTENT

S Supporting Information *

Additional figures for the crystals and X-ray crystallographic files in cif format for the d-POSs. This material is available free of charge via the Internet at http://pubs.acs.org.

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EXPERIMENTAL SECTION

AUTHOR INFORMATION

Corresponding Author

Preparation of the Organic Salt of 2-NS and TPMA. Commercially available naphthalene-2-sulfonic acid, 2-NS, and triphenylmethylamine (TPMA) were mixed in methanol in a 1:1 molar ratio to yield an organic salt. The solution was evaporated under reduced pressure, and the white precipitate of the salt was obtained. Preparation of the Organic Salt of 2-AS and TPMA. The potassium salt of anthracene-2-sulfonic acid was prepared according to the published procedure.17 The potassium salt was converted to the acid form, 2-AS, by passing its aqueous solution through an ionexchange column filled with an Amberlite IR 120B NA resin (Organo). The aqueous solution of 2-AS was mixed immediately with the methanol solution of TPMA in a 1:1 molar ratio to yield an organic salt. The solution was evaporated under reduced pressure, and the white precipitate of the salt was obtained. Preparation of the Organic Salt of 1-PyS and TPMA. The pyrene-1-sulfonic acid, 1-PyS, was prepared according to the published procedure.18 1-PyS and TPMA were mixed in methanol in a 1:1 molar ratio to yield an organic salt. The solution was evaporated under reduced pressure, and the white precipitate of the salt was obtained. Preparation of Single Crystals. The organic salt comprising 2-AS and TPMA was dissolved in ethanol, and then 1,2,4-trichlorobenzene (TCB) was added to the solution. Slow evaporation of the solvent at room temperature gave the single crystals of d-POS 1a. Slow cooling of the solution mixed with ethanol and 1,3,5-trimethylbenzene (TMB) almost gave the block crystals of d-POS 1b, whereas fast cooling yielded columnar crystals of d-POS 1c. The organic salt comprising 1PyS and TPMA was dissolved in ethanol, and then 1,3,5trimethylbenzene (TMB) was added to the solution. Slow evaporation of the solvent at room temperature gave the single crystals of d-POS 2.

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was financially supported by the Research fellowships of the Japan Society for the Promotion of Science (JSPS) for Young Scientists and Grant-in-Aids for Scientific Research on Innovative Areas “Coordination Programming” (area 2107, no. 24108723) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan. The synchrotron radiation experiments were performed at BL38B1 in the Spring8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal nos. 2007B1988, 2005, 2039, and 2008A1422).

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REFERENCES

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