Metal–Organic Frameworks - American Chemical Society

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Interpenetration Control, Sorption Behavior, and Framework Flexibility in Zn(II) Metal−Organic Frameworks Ji Hye Park,‡ Woo Ram Lee,‡ Yeonga Kim, Hye Jin Lee, Dae Won Ryu, Won Ju Phang, and Chang Seop Hong* Department of Chemistry, Research Institute for Natural Sciences, Korea University, Seoul 136-713, Korea S Supporting Information *

ABSTRACT: Three Zn(II) frameworks [Zn(H2L)(bdc)]·1.4DEF· 0.6H2O (1; H2L = 1,4-di(1H-imidazol-4-yl)benzene, H2bdc = terephthalic acid), [Zn(H2L)(bdc)]·1.5DMF·1.2H2O (2), and [Zn(H2L)(L)0.5(bdc)0.5]·formamide·H2O (3) were prepared under the solvothermal conditions in DEF/H2O, DMF/H2O, and formamide/ H2O solvent pairs, respectively. All compounds are commonly based on the adamantanoid three-dimensional networks that are mutually entangled to form a 3-fold (1) to 4-fold (2) to 5-fold interpenetrating dia structure (3). The solvent pairs used in the reactions are primarily responsible for the variation of such interpenetration degree. It is noted that the reaction time, temperature, and reactant ratio applied in the present system (2) did not lead to the interpenetration change. The activated sample (1a) shows the gas uptake of N2, H2, and CO2, characteristic of permanent porosity in the flexible framework, while the gases of N2 and H2 are not adsorbed on 2 and 3. The porous compound (1) also exhibits the reversible inclusion and release of I2 in MeOH. Interestingly, 2 reveals the reversible structural transformation during the activation−resolvation process where the solid can be activated through two routes (solvent exchange/desolvation and direct desolvation). However, there is no appreciable structural flexibility upon solvent exchange in 3 with 5-fold interpenetration, indicating that this framework is more robust, compared to 1 and 2 with lower interpenetration degrees.

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interpenetration degrees.9,43−45,48,49 However, a wider range of interpenetration needs to be explored in order to understand the role of the solvent during interpenetration. Along with this, it should be also interesting to investigate framework flexibility contingent on the interpenetration degree. In this regard, we attempted to discover a series of MOFs that show a solventdependent control of framework interpenetration. Herein we report the syntheses, structures, and properties of three-dimensional interpenetrated frameworks [Zn(H2L)(bdc)]·1.4DEF·0.6H2O (1; H2L = 1,4-di(1H-imidazol-4-yl)benzene, H2bdc = terephthalic acid), [Zn(H2L)(bdc)]· 1.5DMF·1.2H2O (2), and [Zn(H2L)(L)0.5(bdc)0.5]·formamide·H2O (3). As the size of the solvent molecules is reduced from DEF to DMF to formamide, the frameworks undergo a systematic change from 3- to 4- to 5-fold interpenetration, which is seldom demonstrated in coordination networks.36 The flexible framework of 1 exhibits gas and I2 sorption associated with guest molecule exchange. Notably, 2 undergoes unique reversible structural transformations via solvent exchange/ desolvation/resolvation and desolvation/resolvation processes,

INTRODUCTION Metal−organic frameworks (MOFs) are crystalline solids with a high surface area and possess potential applications in, for instance, gas storage and separation,1−4 catalysis,5 and sensing.6−8 Currently, a great number of MOFs exhibit interpenetration, which is a complicated pattern of entanglement.4,9 A porous coordination material containing long spacers can be energetically stabilized when it has a sufficiently large opening in an individual net to accommodate another net.10−17 The construction of interpenetrated nets is not based on chemical bonds, but rather they are formed via supramolecular interactions such as hydrogen bonding, π−π stacking contacts, and van der Waals forces. Interpenetration occurs in coordination polymers and result in either homo-interpenetrating nets by combining the same types of dimensionalities10,18−33 or hetero-interpenetrating systems composed of networks with different dimensionalities (0D + 1D, 1D + 2D, 1D + 3D, and 2D + 3D).21,24,34−40 Interpenetration can be controlled by parameters such as temperature,41 concentration, template,9 ligand modification,42 and solvent removal/addition.17,43−47 For template-directed interpenetration, solvents serve as templates to build up noninterpenetrated or interpenetrated nets. Most examples concerning the sizes of solvent molecules6,7 involve a comparison between two types of frameworks with different © 2014 American Chemical Society

Received: October 23, 2013 Revised: January 6, 2014 Published: January 9, 2014 699

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were restrained by SIMU. All hydrogen atoms except for hydrogens bound to water oxygens were calculated at idealized positions and refined with the riding models. Crystal data of 1 (squeezed): empirical formula = C20H14N4O4Zn, Mr = 439.72, monoclinic, space group P21/ c, a = 11.8037(6) Å, b = 20.4941(11) Å, c = 13.6817(7) Å, β = 96.031(3)o, V = 3291.4(3) Å3, Z = 4, Dcalc = 0.887 g cm−3, μ = 0.767 mm−1, 28883 reflections collected, 7986 unique (Rint = 0.0931), R1 = 0.0669, wR2 = 0.1606 [I > 2σ(I)]. Crystal data of 2 (squeezed): empirical formula = C20H14N4O4Zn, Mr = 439.72, monoclinic, space group P21/n, a = 11.608(3) Å, b = 15.781(4) Å, c = 14.682(4) Å, β = 90.824(18)o, V = 2689.3(12) Å3, Z = 4, Dcalc = 1.086 g cm−3, μ = 0.938 mm−1, 23 764 reflections collected, 6710 unique (Rint = 0.0999), R1 = 0.0684, wR2 = 0.1682 [I > 2σ(I)]. Crystal data of 3: empirical formula = C23H21N7O4Zn, Mr = 524.84, triclinic, space group P1,̅ a = 7.8005(2) Å, b = 11.2947(3) Å, c = 13.1552(4) Å, α = 82.719(2)o, β = 80.499(2)o, γ = 83.194(2)o, V = 1128.26(5) Å3, Z = 2, Dcalc = 1.545 g cm−3, μ = 1.135 mm−1, 18 629 reflections collected, 5508 unique (Rint = 0.0444), R1 = 0.0579, wR2 = 0.1298 [I > 2σ(I)]. CCDC-949421 (1), 949420 (2), and 949349 (3) contain the supplementary crystallographic data for this paper.

contrary to the framework robustness of 3 with a higher interpenetration degree upon solvent exchange.

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EXPERIMENTAL SECTION

Reagent. 1,4-Di(1H-imidazol-4-yl)benzene (= H2L) was prepared according to a literature procedure.50 All the other chemicals and solvents in the synthesis were reagent grade and used as received. All manipulations were performed under aerobic conditions. [Zn(H2L)(bdc)]·1.4DEF·0.6H2O (1). Zn(NO3)2·6H2O (21 mg, 0.071 mmol), terephthalic acid (= H2bdc) (12 mg, 0.071 mmol), and H2L (15 mg, 0.071 mmol) were put in a 10 mL vial and dissolved in DEF/ H2O (3:1 v/v, 6 mL). The vial was placed in a preheated oven (100 °C) and reacted for 16 h. Colorless rod crystals were formed, which were washed with DEF/EtOH and dried in air. Yield: 50%. Anal. Calcd for C28.2H33N5.4O6Zn: C, 55.62; H, 5.46; N, 12.42. Found: C, 55.24; H, 5.40; N, 12.80. Compound 1 was immersed in MeOH for 24 h and then evacuated at 100 °C for 30 min to give the activated sample (1a). We also prepared a CHCl3-exchanged sample for activation, but the MeOH-exchanged sample exhibited greater gas adsorption. [Zn(H2L)(bdc)]·1.5DMF·1.2H2O (2). The identical reaction conditions except for the use of the DMF/H2O solvent pair instead of DEF/H2O were employed to produce colorless rod crystals. Yield: 52%. Anal. Calcd for C24.5H26.9N5.5O6.7Zn: C, 51.53; H, 4.75; N, 13.49. Found: C, 51.12; H, 4.40; N, 13.36. Compound 2 was soaked in CHCl3 for 24 h to produce the CHCl3-exchanged sample (2a). 2a was evacuated at 100 °C for 1 h to give the desolvated sample (2b). The activated sample was also obtained by heating 2 at 200 °C under a vacuum for 3 h. The activated sample of 2b was immersed in DMF/ H2O (2:1, v/v) for 24 h to produce the resolvated sample. [Zn(H2L)(L)0.5(bdc)0.5]·formamide·H2O (3). The identical reaction conditions except for the use of the formamide/H2O solvent pair instead of DEF/H2O were applied to give colorless crystals with some unidentified impurities. Compound 3 was also obtained with the ratio of Zn2+/H2L/H2bdc = 1:1.5:0.5. Yield: 7%. Anal. Calcd for C22.1H20.7N6.1O4.3Zn: C, 52.47; H, 4.12; N, 16.89. Found: C, 52.23; H, 3.95; N, 16.50. Physical Measurements. Elemental analyses for C, H, and N were performed at the Elemental Analysis Service Center of Sogang University. Infrared spectra were obtained from KBr pellets with a Bomen MB-104 spectrometer. Thermogravimetric analyses were carried out at a ramp rate of 10 °C/min in a N2 flow using a Scinco TGA N-1000 instrument. Powder X-ray diffraction (PXRD) data were recorded using Cu Kα (λ = 1.5406 Å) on a Rigaku Ultima III diffractometer with a scan speed of 2°/min and a step size of 0.01°. Gas Sorption Measurements. Gas sorption isotherms of 1a were measured using a BEL Belsorp mini II gas adsorption instrument up to 1 atm of gas pressure. The highly pure N2 (99.999%), H2 (99.999%), and CO2 (99.999%) were used in the sorption experiments. N2 and H2 gas isotherms were measured at 77 K and CO2 was measured at 195 K. The additional uptake isotherms were obtained at 88 K for H2 and at 273 and 298 K for CO2. Crystallographic Structure Determination. X-ray data for 1−3 were collected on a Bruker SMART APEXII diffractometer equipped with graphite monochromated Mo Kα radiation (λ = 0.71073 Å). Preliminary orientation matrix and cell parameters were determined from three sets of ω/ϕ scans at different starting angles. Data frames were obtained at scan intervals of 0.5° with an exposure time of 10 s per frame. The reflection data were corrected for Lorentz and polarization factors. Absorption corrections were carried out using SADABS. The structures of 1−3 were solved by direct methods and refined by full-matrix least-squares analysis using anisotropic thermal parameters for non-hydrogen atoms with the SHELXTL program. Guest molecules in 1 and 2 are significantly disordered and could not be modeled properly; thus, the program SQUEEZE, a part of the PLATON package of crystallographic software, was used to calculate the solvent disorder area and remove its contribution to the overall intensity data. For 1, the Zn atoms were disordered over two sites (0.71:0.29) for Zn1A and Zn1B, respectively, by using PART. Anisotropic displacement parameters of the disordered Zn atoms

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RESULTS AND DISCUSSION Crystal Structures and Interpenetration Control. A solvothermal reaction of Zn2+ and organic spacer ligands, H2bdc and H2L, in a mixed DEF/H2O solvent was conducted at 100 °C for 16 h, yielding white crystals of 1. The Zn center in 1 is tetrahedrally coordinated by two N atoms from H2L and two O atoms from bdc with lengths ranging from 1.913 to 2.038 Å, and the long-spacer ligand H2L links two adjacent Zn atoms (Figure 1a). To analyze the network structure, the organic linkers of H2L and bdc are represented by sticks; the Zn atoms are located at the joints (Figure S1, Supporting Information). One network extracted from the whole framework leads to a 4-connected uninodal net with a point symbol of {66} (Figure S2, Supporting Information). The extension of the adamantanoid cages generates the diamond (dia) network with large hexagonal channels.51,52 The adamantanoid 3D structures are interpenetrated, and a 3-fold architecture (full interpenetration vectors, Class Ia) eventually forms (Figure 1b).53 The entangled nets are assisted by multiple hydrogen bonding interactions between carboxylate oxygens from the bdc ligands and free N−H groups from H2L (O2−N2 = 2.721 Å and O4−N3 = 2.729 Å). Such multiple hydrogen bonds likely account for the stabilization of the resultant dia framework with pores (Figures S3 and S4, Supporting Information). The solvent-accessible void volume calculated by PLATON is 53.6%. To inspect the role of solvent size on the degree of interpenetration, the DMF/H2O solvent pair was employed instead of DEF/H2O under the same experimental conditions to yield 2. When the solvent was changed from DEF to DMF, the local and overall structural features are significantly affected. The Zn center in 2 adopts a distorted tetrahedral geometry composed of two N atoms from H2L and two O atoms from bdc, similar to the central coordination situation of 1 (Figure 1c). The free carboxylate oxygen atoms (O1 and O4) in 2 weakly interact with the Zn ion (Zn1−O1 = 2.759(1) Å and Zn1−O4 = 2.772(1) Å), which differs from the interaction involving 1. The simplified structure reveals that there are four interpenetrating nets in 2 (Figures 1d and S5, Supporting Information). The 4-fold dia net with the translating interpenetration vectors (Class IIIa) is stabilized by hydrogen bonding between the carboxylate oxygens (O4) from bdc in one diamondoid net and the N−H moieties (N2) from H2L in the adjacent net (Figure S6, Supporting Information).53 It is 700

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solvothermal reactions under different temperatures, reaction times, and reactant ratios, and collected PXRD data of the prepared samples (Figure S9, Supporting Information). At a reaction temperature of 70 °C, the formed phase was identical to that of 2. When the reaction time changed from 24 h to 3 days, the same phase of 2 also resulted. At a reactant ratio of Zn2+/H2L/H2bdc = 1:1:0.5, the phase of 2 was maintained, while some unidentified phase emerged at a ratio of 1:0.5:0.5. Since the applied reaction conditions afforded 2 as a major phase, these data suggest that the interpenetration degree in this system is primarily governed by solvents used. However, when a bulkier solvent system of DBF/H2O pair was employed, unidentified mixed phases precipitated. Therefore, the interpenetration ranging from 3- to 5-fold seems to be viable in the current reaction system. Gas Sorption Properties. In the thermogravimetric (TG) analysis of the as-prepared sample of 1 (Figure S10, Supporting Information), a weight loss of 25.4% in the temperature range 30−270 °C corresponds to the decomposition of 1.4DEF and 0.6H2O (25.7%). Then, 1 was soaked in MeOH for 24 h to replace DEF with a more volatile solvent. The weight loss for the MeOH exchanged sample is 22.9%, which is consistent with 4MeOH (22.6%). The PXRD data indicate that the structure of 1 remains nearly unaltered in the MeOH-exchanged phase (Figure S11, Supporting Information). The MeOH-exchanged sample was maintained at 100 °C for 30 min under a vacuum to remove all the lattice solvents. The PXRD pattern of the activated phase (1a) is quite different from that of the MeOHexchanged sample, and the peaks shift toward higher angles, which suggest that the removal of the lattice molecules triggers the structural shrinkage. The N2 sorption isotherms at 77 K for 1a show the typical type I behavior, thus confirming permanent microporosity (Figure 2a). The Brunauer−Emmett−Teller (BET) surface

Figure 1. (a) Coordination environment around Zn for 1. (b) Schematic representation of 3-fold interpenetrated diamondoid net for 1. (c) Coordination environment around Zn for 2. (d) Schematic representation of 4-fold interpenetrated diamondoid net for 2. (e) Coordination geometry around Zn for 3. (f) Schematic representation of 5-fold interpenetrated diamondoid net for 3.

worth noting that 1 and 2 are interpenetration isomers because the constituents in the frameworks are the same. Further, we utilized formamide (having a smaller molecular size than DMF) and conducted the reaction using the formamide/H2O solvent pair under identical reaction conditions to produce 3 (Figure S7, Supporting Information). The environment around Zn is made up of one bdc and three bisimidazole ligands, and the resultant structure is completely different from that of the others (Figure 1e). Remarkably, the simplification process shows that 3 can be viewed as a dia net with the 5-fold interpenetration (Figures 1f and S8, Supporting Information). In spite of the structural disparity, it appears that the amide molecules with different sizes behave as templates of the framework growth, during which the larger solvent molecules permit the formation of a MOF with larger pores and a lower degree of interpenetration. Formamide is the smallest one among amide solvents, so a higher degree of interpenetration than 5-fold may be not feasible with this strategy in the current system. The above structural results support that solvent sizes have an impact on interpenetration degree. To test the effect of other reaction conditions on the phase stability, a solvent pair of DMF/H2O, which is the reaction solvent for the synthesis of 2, was selected as a representative. We carried out a series of

Figure 2. (a) N2 uptake isotherms at 77 K for 1a. (b) CO2 uptake isotherms at the indicated temperatures for 1a. 701

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area and total pore volume are 277 m2/g and 0.121 cm3/g, respectively. The obtained pore volume is much smaller than that (0.604 cm3/g) calculated from X-ray data, which is due to the reduced volume of the activated phase of 1a after the lattice solvents were eliminated. The desolvated 1a also adsorbs H2, and the maximum uptake amounts to 62 cm3/g at 1 atm and 77 K (Figure S12, Supporting Information). From the additional data for H2 at 87 K, the isosteric heat of adsorption (−Qst) was estimated using a virial-type equation, and it ranges from 4.9 to 5.9 kJ/mol (Figure S13, Supporting Information). For CO2 adsorption (Figure 2b), the gate-opening pressure at P = 0.13 bar is observed in the isotherm curve at 195 K, suggesting that the framework is flexible upon CO2 uptake, as verified by the PXRD data.9 The CO2 uptake data at 273 and 298 K were used to roughly determine the isosteric heat of CO2 adsorption, which is in the range 40.2−55.5 kJ/mol (Figure S14, Supporting Information). The estimated values are similar to those of other MOFs.54 The gases of H2 and N2 were not adsorbed on the activated samples of 2 and 3, while CO2 was adsorbed on 2 (Figures S15 and S16, Supporting Information). I2 Diffusion into 1. The luminescent properties of the organic linkers and 1−3 were recorded in water (Figure S17, Supporting Information). The emission spectra indicate that the broad peak at around 353 nm for 1−3 is ligand-based because the peak position is similar to the bands from the ligands. The luminescent lifetime needs to be measured for the samples. Since only 1 shows gas adsorption capability, we investigated I2 inclusion in 1 by monitoring the process with color change, photoluminescence, and other techniques. Figure 3a depicts the photographs of time-dependent I2 diffusion into

this result, we can confirm that I2 slowly diffuses into 1 to form a solid impregnated with I2 (I2⊂1). When the 36-h sample was soaked in MeOH, I2 was released, and the color reversibly returned white after 1 h (Figures 3a and S18, Supporting Information). The dried solids containing I2 were dispersed into water, and their luminescence spectra were then collected (Figure 3b). The signals in the luminescence data around 353 nm weakened as I2 was diffused into the sample. After 36 h, the intensity of the signal remained constant, which suggests that I2 is saturated in the system. The amount of I2 in I2⊂1 after 36 h was roughly estimated to be 0.24I2 per Zn by elemental analysis and TGA. The peak intensity of the MeOH-soaked solid started to be restored, which is due to the release of I2 from 1 during immersion in MeOH. The observation indicates that the quenching of the band at around 353 nm occurs when I2 is incorporated into the solid. In the UV−vis spectrum of I2 in water (Figure S19, Supporting Information), an absorption band at 350 nm appears, which is responsible for the quenching of the emission band of I2⊂1. The PXRD data show that a new peak at 2θ = 10° is visible for I2⊂1 at 6, 12, and 36 h, and the peak disappears when I2⊂1 was immersed in MeOH (Figure S20, Supporting Information). Note that the overall patterns of I2⊂1 at the different times resemble that of 1, which supports the postulation that the structure is maintained upon the inclusion and removal of I2 into 1. Structural Flexibility. The TG curves of 2 show that 22.5% of the mass is lost within the temperature range 30−200 °C, which coincides with the corresponding removal of 1.5DMF and H2O (22.5%), as shown in Figure S21, Supporting Information. The framework is thermally stable up to 385 °C, above which the framework undergoes complete decomposition. The lattice molecules were exchanged by soaking 2 in CHCl3 for 24 h. The weight loss of 20% in the CHCl3-exchanged sample (2a) is found at 125 °C, which agrees with the decomposition (19.6%) of 0.9CHCl3. The PXRD profile of 2a is different from that of 2 (Figure 4), indicating that the exchanged phase undergoes a structural transformation. The activation of 2a was conducted by heating 100 °C under a vacuum for 1 h to produce the desolvated phase of 2b. The structure of the activated form is not identical to that of 2a.

Figure 3. (a) Photographs of time-dependent I2 sorption in 1. The colors of solids indicate sorption of I2 into 1 and release in MeOH. (b) Emission spectra of 1 after immersion in 0.02 M I2 in hexane for the given time and dispersion into H2O.

the solid 1.55,56 The white powder 1 was kept in a vial with a 0.02 M hexane solution of I2 and maintained for the indicated times. The I2-sorbed solids (I2⊂1) were obtained by filtering, washing with hexane, and then air-drying the residues. The colors of solutions became pale as the immersion time increased; meanwhile, the solids turned deep brown. From

Figure 4. PXRD profiles of as-synthesized, CHCl3-exchanged, activated, and resolvated samples of 2. Inset shows phase transformations during the solvation−desolvation process. 702

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Interestingly, the structural type of the activated sample (2b) was obtained by directly desolvating the as-prepared sample at 200 °C under a vacuum for 3 h, as confirmed by the PXRD data (Figure 4). Remarkably, the original phase (2) was formed when 2b was resolvated in DMF/H2O. This observation clearly reveals that the reversible structural transformation occurs during the activation−resolvation process in which the material can be activated via two routes: solvent exchange/desolvation and direct desolvation. The solvent exchange in 3 was performed to scrutinize the dynamic nature of the framework, as observed in 2. We immersed the as-synthesized form of 3 in chloroform or MeOH for 24 h. The PXRD data of the dried samples unveil that the structural phases of the exchanged ones coincide with that of 3 (Figures S22 and S23, Supporting Information). This result demonstrates that the structure of 3 is more robust upon solvent exchange, compared to those of 1 and 2 where the solvent exchange engenders a significant change in the framework structure.

CONCLUSIONS Three Zn(II) frameworks have been prepared under the solvothermal conditions. The variation of the solvent pair from DEF/H2O to DMF/H2O to formamide/H2O causes the respective interpenetration change from 3- (1) to 4- (2) to 5-fold (3). This trend is primarily due to the solvent pairs used in the reactions. For 2, the interpenetration degree was not affected by the reaction time, temperature, and reactant ratio applied in the DMF/H2O solvent pair system. The 3-fold (1) and 4-fold (2) interpenetrating systems show gas uptake properties, while the 5-fold system (3) is found to be nonporous. The porous solid (1) also demonstrates that I2 is diffused into the solid and released reversibly. The reversible structural conversion occurs in 2 during the activationresolvation process. Comparatively, structural flexibility upon solvent exchange is not involved in 3, indicating the robustness of the framework with the higher degree of interpenetration. This work suggests that solvent size serves as an essential factor influencing interpenetration degree and contributes to the understanding of the framework flexibility depending on the interpenetration level. ASSOCIATED CONTENT

S Supporting Information *

X-ray crystallographic files in CIF format, additional structural data for the complexes. This material is available free of charge via the Internet at http://pubs.acs.org.

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REFERENCES

(1) Li, J. R.; Sculley, J.; Zhou, H. C. Chem. Rev. 2012, 112, 869−932. (2) Suh, M. P.; Park, H. J.; Prasad, T. K.; Lim, D. W. Chem. Rev. 2012, 112, 782−835. (3) Sumida, K.; Rogow, D. L.; Mason, J. A.; McDonald, T. M.; Bloch, E. D.; Herm, Z. R.; Bae, T. H.; Long, J. R. Chem. Rev. 2012, 112, 724− 781. (4) Nugent, P.; Belmabkhout, Y.; Burd, S. D.; Cairns, A. J.; Luebke, R.; Forrest, K.; Pham, T.; Ma, S.; Space, B.; Wojtas, L.; Eddaoudi, M.; Zaworotko, M. J. Nature 2013, 495, 80−84. (5) Yoon, M.; Srirambalaji, R.; Kim, K. Chem. Rev. 2012, 112, 1196− 1231. (6) Li, C. P.; Wu, J. M.; Du, M. Chem.Eur. J. 2012, 18, 12437− 12445. (7) Li, C.-P.; Chen, J.; Liu, P.-W.; Du, M. CrystEngComm 2013, 15, 9713−9721. (8) Kreno, L. E.; Leong, K.; Farha, O. K.; Allendorf, M.; Van Duyne, R. P.; Hupp, J. T. Chem. Rev. 2012, 112, 1105−1125. (9) Bureekaew, S.; Sato, H.; Matsuda, R.; Kubota, Y.; Hirose, R.; Kim, J.; Kato, K.; Takata, M.; Kitagawa, S. Angew. Chem., Int. Ed. 2010, 49, 7660−7664. (10) Wu, H.; Yang, J.; Su, Z. M.; Batten, S. R.; Ma, J. F. J. Am. Chem. Soc. 2011, 133, 11406−11409. (11) Rowsell, J. L.; Yaghi, O. M. Angew. Chem., Int. Ed. 2005, 44, 4670−4679. (12) Ryan, P.; Broadbelt, L. J.; Snurr, R. Q. Chem. Commun. 2008, 4132−4134. (13) Ma, S.; Eckert, J.; Forster, P. M.; Yoon, J. W.; Hwang, Y. K.; Chang, J. S.; Collier, C. D.; Parise, J. B.; Zhou, H. C. J. Am. Chem. Soc. 2008, 130, 15896−15902. (14) Ma, S.; Sun, D.; Ambrogio, M.; Fillinger, J. A.; Parkin, S.; Zhou, H.-C. J. Am. Chem. Soc. 2007, 129, 1858−1859. (15) Rowsell, J. L. C.; Millward, A. R.; Park, K. S.; Yaghi, O. M. J. Am. Chem. Soc. 2004, 126, 5666−5667. (16) Sun, D.; Ma, S.; Ke, Y.; Collins, D. J.; Zhou, H.-C. J. Am. Chem. Soc. 2006, 128, 3896−3897. (17) Kim, J.; Yang, S.-T.; Choi, S. B.; Sim, J.; Kim, J.; Ahn, W.-S. J. Mater. Chem 2011, 21, 3070−3076. (18) Baburin, I. A.; Blatov, V. A.; Carlucci, L.; Ciani, G.; Proserpio, D. M. J. Solid State Chem. 2005, 178, 2452−2474. (19) Luo, F.; Zheng, J. M.; Batten, S. R. Chem. Commun. 2007, 3744−3746. (20) Fan, J.; Sun, W.-Y.; Okamura, T.-a.; Zheng, Y.-Q.; Sui, B.; Tang, W.-X.; Ueyama, N. Cryst. Growth Des. 2004, 4, 579−584. (21) Carlucci, L.; Ciani, G.; Proserpio, D. M. Cryst. Growth Des. 2005, 5, 37−39. (22) Hoskins, B. F.; Robson, R.; Slizys, D. A. J. Am. Chem. Soc. 1997, 119, 2952−2953. (23) Carlucci, L.; Ciani, G.; Moret, M.; Proserpio, D. M.; Rizzato, S. Chem. Mater. 2002, 14, 12−16. (24) Liu, J.-Q.; Wang, Y.-Y.; Liu, P.; Dong, Z.; Shi, Q.-Z.; Batten, S. R. CrystEngComm 2009, 11, 1207−1209. (25) Chen, B.; Ma, S.; Zapata, F.; Fronczek, F. R.; Lobkovsky, E. B.; Zhou, H.-C. Inorg. Chem. 2007, 46, 1233−1236. (26) Mir, M. H.; Kitagawa, S.; Vittal, J. J. Inorg. Chem. 2008, 47, 7728−7733. (27) Xue, M.; Ma, S.; Jin, Z.; Schaffino, R. M.; Zhu, G.-S.; Lobkovsky, E. B.; Qiu, S.-L.; Chen, B. Inorg. Chem. 2008, 47, 6825−6828. (28) Cheon, Y. E.; Suh, M. P. Chem.Eur. J. 2008, 14, 3961−3967. (29) Mulfort, K. L.; Farha, O. K.; Malliakas, C. D.; Kanatzidis, M. G.; Hupp, J. T. Chem.Eur. J. 2010, 16, 276−281. (30) Xie, L. H.; Suh, M. P. Chem.Eur. J. 2011, 17, 13653−13656. (31) Deng, Z.-P.; Zhu, Z.-B.; Zhang, X.-F.; Huo, L.-H.; Zhao, H.; Gao, S. CrystEngComm 2011, 13, 3895−3899. (32) Xu, J.; Bai, Z.-S.; Chen, M.-S.; Su, Z.; Chen, S.-S.; Sun, W.-Y. CrystEngComm 2009, 11, 2728−2733. (33) Yang, J.; Ma, J.-F.; Batten, S. R.; Ng, S. W.; Liu, Y.-Y. CrystEngComm 2011, 13, 5296−5298.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Author Contributions ‡

J.H.P. and W.R.L. contributed equally.

Notes

The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS This work was supported by the Korea CCS R&D Center (KCRC) grant funded by the Korea government (The Ministry of Science, ICT & Future Planning (MSIP)) (NRF2013M1A8A1035849) and by the Priority Research Centers Program (NRF20110018396). 703

dx.doi.org/10.1021/cg401583v | Cryst. Growth Des. 2014, 14, 699−704

Crystal Growth & Design

Article

(34) Hou, L.; Zhang, J.-P.; Chen, X.-M. Cryst. Growth Des. 2009, 9, 2415−2419. (35) Lee, H.-J.; Cheng, P.-Y.; Chen, C.-Y.; Shen, J.-S.; Nandi, D.; Lee, H. M. CrystEngComm 2011, 13, 4814−4816. (36) Jiang, H.-L.; Makal, T. A.; Zhou, H.-C. Coord. Chem. Rev. 2013, 257, 2232−2249. (37) Mok Shin, D.; Su Lee, I.; Keun Chung, Y.; Soo Lah, M. Chem. Commun. 2003, 1036−1037. (38) Carlucci, L.; Ciani, G.; Proserpio, D. M. Chem. Commun. 2004, 380−381. (39) Carlucci, L.; Ciani, G.; Proserpio, D. M. Coord. Chem. Rev. 2003, 246, 247−289. (40) Carlucci, L.; Ciani, G.; Maggini, S.; Proserpio, D. M. Cryst. Growth Des. 2008, 8, 162−165. (41) Jiang, H.-L.; Tatsu, Y.; Lu, Z.-H.; Xu, Q. J. Am. Chem. Soc. 2010, 132, 5586−5587. (42) Roberts, J. M.; Farha, O. K.; Sarjeant, A. A.; Hupp, J. T.; Scheidt, K. A. Cryst. Growth Des. 2011, 11, 4747−4750. (43) Wang, Q.; Zhang, J.; Zhuang, C.-F.; Tang, Y.; Su, C.-Y. Inorg. Chem. 2009, 48, 287−295. (44) Ma, L.; Lin, W. J. Am. Chem. Soc. 2008, 130, 13834−13835. (45) Guo, M.; Sun, Z.-M. J. Mater. Chem 2012, 22, 15939−15946. (46) Hao, H.-J.; Sun, D.; Liu, F.-J.; Huang, R.-B.; Zheng, L.-S. Cryst. Growth Des. 2011, 11, 5475−5482. (47) Nijem, N.; Veyan, J.-F.; Kong, L.; Li, K.; Pramanik, S.; Zhao, Y.; Li, J.; Langreth, D.; Chabal, Y. J. J. Am. Chem. Soc. 2010, 132, 1654− 1664. (48) Song, F.; Wang, C.; Falkowski, J. M.; Ma, L.; Lin, W. J. Am. Chem. Soc. 2010, 132, 15390−15398. (49) Falkowski, J. M.; Wang, C.; Liu, S.; Lin, W. Angew. Chem., Int. Ed. 2011, 50, 8674−8678. (50) van Leusen, A. M.; Schaart, F. J.; van Leusen, D. Rec. Trav. Chim. Pays-Bas. 1979, 98, 258−262. (51) Chen, S.-S.; Fan, J.; Okamura, T.-a.; Chen, M.-S.; Su, Z.; Sun, W.-Y.; Ueyama, N. Cryst. Growth Des. 2010, 10, 812. (52) Zhang, J.; Wojtas, L.; Larsen, R. W.; Eddaoudi, M.; Zaworotko, M. J. J. Am. Chem. Soc. 2009, 131, 17040−17041. (53) Park, J. H.; Lee, W. R.; Ryu, D. W.; Lim, K. S.; Jeong, E. A.; Phang, W. J.; Koh, E. K.; Hong, C. S. Cryst. Growth Des. 2012, 12, 2691−2698. (54) Li, C. P.; Du, M. Chem. Commun. 2011, 47, 5958. (55) Sumida, K.; Rogow, D. L.; Mason, J. A.; McDonald, T. M.; Bloch, E. D.; Herm, Z. R.; Bae, T. H.; Long, J. R. Chem. Rev. 2012, 112, 724−781. (56) Liu, Q. K.; Ma, J. P.; Dong, Y. B. Chem. Commun. 2011, 47, 7185−7187.

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