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High Proton Conduction in Two CoII and MnII Anionic MOFs Derived from 1,3,5-Benzenetricarboxylic Acid Sui-Jun Liu, Chen Cao, Fan Yang, Mei-Hui Yu, Shui-Li Yao, TengFei Zheng, Wei-Wei He, Hai-Xia Zhao, Tong-Liang Hu, and Xian-He Bu Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b00776 • Publication Date (Web): 11 Nov 2016 Downloaded from http://pubs.acs.org on November 13, 2016
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Crystal Growth & Design
High Proton Conduction in Two CoII and MnII Anionic MOFs Derived from 1,3,5-Benzenetricarboxylic Acid Sui-Jun Liu,*,†,‡ Chen Cao,† Fan Yang,§ Mei-Hui Yu,‡ Shu-Li Yao,† Teng-Fei Zheng,*,† Wei-Wei He,‡ Hai-Xia Zhao,∥ Tong-Liang Hu,*,‡ and Xian-He Bu‡ †
School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, P.R. China ‡ Shool of Materials Science and Engineering, National Institute for Advanced Materials, Tianjin Key Laboratory of Metal and Molecule-Based Material Chemistry, Nankai University, Tianjin 300350, P.R. China § Beijing Key Laboratory for Green Catalysis and Separation and Department of Chemistry and Chemical Engineering, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124, P.R. China ∥
State Key Laboratory of Physical Chemistry of Solid Surfaces and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P.R. China Supporting Information Placeholder ABSTRACT: Two isostructural CoII- and MnII-organic frameworks with anionic frameworks and counterions (Me2NH2)+, namely {[M2Cl2(BTC)4/3]·(Me2NH2)+2·4/3H2O}n (M = Co (1) and Mn (2)), have been constructed by one-pot synthesis. Complexes 1 and 2 take paddle-wheel-like dinuclear metal clusters based three-dimensional structures. TGAs and variable temperature PXRD spectra suggested that 1 displays better thermal stability than 2. Both of them exhibit relatively high proton conductivities at 65% relative humidity (RH) and room temperature (σ > 2.5×10-4 S cm-1), however, complex 1 possesses the better cycling capability and stability with Ea = 0.21 eV under 65% RH condition.
INTRODUCTION Proton conductivities of inorganic, organic or inorganicorganic hybrid compounds, such as metal oxide, Nafion and metal-organic frameworks (MOFs), have been researched due to their applications in sensors and fuel cells.1-4 Generally, proton carriers H3O+/H+ provided by acid or OH groups are needed in these materials.5-6 Besides, proton-conducting pathways comprised of H-bond network are also required for conducting proton.7-8 Recently, MOFs as an intriguing class of crystalline and inorganic-organic hybrid materials have attracted much attention not only for their conventional properties in gas storage and selective separation, but for catalytic properties and electrical conductivity, in particular, proton conductivity.9-14 According to previous works, to obtain MOFs with high proton conductivities, one of the simplest and most effective methods is to introduce proton carriers such as (Me2NH2)+, H3O+, and HSO4- as counterions directly into the pores of MOFs.15-16 Because of the synthetic challenge of anionic frameworks, MOFs with high proton conductivities have less been reported.17-19 Among various synthetic methods, solvothermal technique is effective and easy to be carried out, and in situ reaction of organic solvents and ligands usually occurs.20-22 Therefore, the introduction of (Me2NH2)+ becomes easily and fast through the solvothermal reaction. According to the literatures, (Me2NH2)+ could be generated in situ by the addition of N,N′-dimethylacetamide (DMAc) or N,N′dimethylformamide (DMF) under solvothermal conditions.23-25
It is well known that 1,3,5-benzenetricarboxylic acid (H3BTC) has been widely used to prepare functional MOFs due to the unique structural symmetry and various coordination modes.26-27 In order to obtain MOFs with proton conductivity, our approach is to introduce (Me2NH2)+ as counterions into the pores of MOFs. Herein, two CoII and MnII namely anionic MOFs derived from H3BTC, {[Co2Cl2(BTC)4/3]·(Me2NH2)+2·4/3H2O}n (1) and {[Mn2Cl2(BTC)4/3]·(Me2NH2)+2·4/3H2O}n (2), have been successfully constructed and structurally characterized. Reddish-brown (1) and colorless crystals (2) were obtained by the solvothermal reaction of CoCl2·6H2O/MnCl2·4H2O, H3BTC and DMAc/CH3CN at 160 °C. The synthetic methods are applicable to the assembly of other related functional MOFs. It is revealed that both of them exhibit good proton conductivities and different conductivities under distinct conditions.
EXPERIMENTAL SECTION Materials and Physical Measurements. All metal salts, H3BTC and organic solvents were of reagent grade and employed as purchased. The powder X-ray diffraction (PXRD) spectra were obtained under a Rigaku D/Max-2500 diffractometer with a Cu-target tube and a graphite monochromator. The variable-temperature PXRD was recorded on a PANalytical X’pert PRO diffractometer at 40 kV and 30 mA with a Cu-target tube and a graphite monochromator. The simulated PXRD spectra were from the single-crystal data and the Mercury (Hg) program obtained free from the website at http://www.iucr.org. IR spectra were
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obtained in 4000-400 cm-1 on a Bruker Tensor 27 OPUS FTIR spectrometer employing KBr pellets. Thermogravimetric analyses (TGAs) were carried out on a Rigaku standard TGDTA analyzer under N2 atmosphere with a heating rate of 10 °C min-1, employing an empty Al2O3 crucible as reference. Alternating current (AC) impedance measurements with sample pellets (6 mm in diameter) were performed by the conventional quasi-four-probe method on the Zennium electrochemical workstation employing silver paste and silver wires. The frequency range of AC source is 1−4×106 Hz. The amplitude of AC voltage is 100 mV. The humidity is controlled by different saturated aqueous salt solutions.28-29 Synthesis of {[Co2Cl2(btc)4/3]·(Me2NH2)+2·4/3H2O}n (1): CoCl2·6H2O (1 mmol, 238 mg) and H3btc (0.5 mmol, 105 mg) were dissolved in 10 mL mixed solvent (VDMAc : VMeCN = 6 : 4). The reaction mixture was then heated to 160 °C for 72 h sealed in a Teflon-lined stainless steel autoclave. Upon cooling to room temperature (RT) during 12 h, reddish-brown crystal blocks were obtained with a yield of ~50% based on CoII. Synthesis of {[Mn2Cl2(btc)4/3]·(Me2NH2)+2·4/3H2O}n (2). The synthetic procedure for complex 2 was similar to complex 1 except that CoCl2·6H2O was substituted by MnCl2·4H2O (1 mmol, 197 mg). Colorless block crystals were collected with ~40% yield based on MnII. IR (KBr, cm-1): 3356m, 3188m,
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2935w, 2780m, 1652s, 1438s, 1366s, 1093m, 1011m, 947m, 765s, 712s, 562w, 438m. X-ray Data Collection and Structure Determinations. The X-ray single-crystal diffraction data of 1 and 2 were measured under a Rigaku SCX-mini diffractometer at 293(2) K with Mo-Kα radiation (λ = 0.71073 Å) by the mode of ω scan. Program CrystalClear was utilized for integration of the diffraction profiles. Direct method was used to solve the structure through the SHELXS program of the SHELXTL package, and the structure was refined by full-matrix leastsquares methods with SHELXL.30 The non-H atoms were identified by successive difference Fourier syntheses and refined with anisotropic thermal parameters on F2. The H atoms of H3BTC were added theoretically on the specific atoms. Because of the limitation on the crystal quality, the H atoms in H2O and (Me2NH2)+ were not assigned. A summary of the crystal data and structure refinements for 1 and 2 is given in Table 1. The selected bond lengths and angles are provided in Tables S1 and S2 (SI). To obtain better crystal data, complexes 1 and 2 were also measured on a Bruker D8 QUEST diffractometer at 100(2) K with Mo-Kα radiation by ω scan mode. The solvent molecules and disordered organic cations in 1 and 2 are removed by SQUEEZE program in PLATON.31
Table 1. Crystal data and structure refinements for 1 and 2 1
1-squeeze
2
2-squeeze
molecular formula
C16H68/3Co2Cl2N2O28/3
C6H2CoClO4
C16H68/3Mn2Cl2N2O28/3
C6H2MnClO4
Mr
581.13
232.46
573.14
228.47
T [K]
293(2)
100(2)
293(2)
100(2)
crystal system
Cubic
Cubic
Cubic
Cubic
space group
Fm-3m
Fm-3m
Fm-3m
Fm-3m
a[Å]
26.647(3)
26.4492(13)
26.771(3)
26.7199(7)
b[Å]
26.647(3)
26.4492(13)
26.771(3)
26.7199(7)
c[Å]
26.647(3)
26.4492(13)
26.771(3)
26.7199(7)
β[°]
90
90
90
90
V[Å3]
18921(4)
18502.8(16)
19186(4)
19076.8(9)
ρ[g cm-3]
1.224
1.001
1.191
0.955
Z
2
48
2
48
F(000)
7088
5472
6992
5376
µ[mm-1]
1.258
1.268
0.993
0.981
collected reflections
39084
60245
41009
71792
unique reflections
897
876
905
897
R(int)
0.1566
0.0893
0.1015
0.0450
0.1153/0.3157
0.0803/0.2385
0.0976/0.2857
0.0893/0.2657
a
b
R1 /wR2 [I>2σ(I)]
2
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Crystal Growth & Design R1a/wR2b (all data) 2
GOF on F
0.1203/0.3197
0.0891/0.2487
1.113
1.073 b
a
0.0985/0.2865
0.0949/0.2732
1.130
1.077
2
2 2
2 2 1/2
R = Σ(||F0| – |FC||)/Σ|F0|. Rw = [Σw(|F0| – |FC| ) /(Σw|F0| ) ] . no adsorption capability and the frameworks are not stable after vacuum degassing (Figure S1, SI). From topological RESULTS AND DISCUSSION point of view, 1 is a typical (3,4)-connected 3D tbo framework with a point symbol of (62.82.102)3(63)4 if each Co2 cluster Description of crystal structure. Complexes 1 and 2 are serves as a 4-connected node and each BTC group regards as isostructural with a similar structure as Cu3(BTC)2 (HKUST3-connected node, respectively (Figure 1d). 1)32-33 and include a paddle-wheel-like Co2 or Mn2 cluster as secondary building unit (SBU), thus herein only the structure of 1 is represented shortly. In 1, unlike HKUST-1, the chloride ions replace oxygen atoms to make the framework negative and (Me2NH2)+ as counterions exist in the pores. It crystallizes in the high-symmetry space group Fm-3m of cubic system. The calculated result by employing SHAPE 2.0 indicates that the geometry of the five-coordinative CoII or MnII could be viewed as spherical square pyramid (SSP)34 (Table 2), accomplished by four O atoms from BTC3- ligands and one Cl atom. Two adjacent CoII ions are linked by four carboxylate groups (Figure 1a). The structure of 1 comprises an infinite number of dinuclear cobalt paddlewheel SBUs interconnected by the tricarboxylate ligand, leading to a 3D framework bearing 3D channels (Figure 1b). Besides, the guest water molecules and disorderly protonated dimethylamine cations exist in the pores (Figure 1c). The porosity of 1 calculated by Figure 1 ． Views of 1 (a) the dinuclear cobalt unit; (b) the PLATON31 is 46.9% of the unit cell (water molecules were structure along a direction (H atoms omitted for clarity); (c) the removed). However, N2 adsorption isotherms of activated 1 water molecules and (Me2NH2)+ cations in the pores; (d) the (3,4)and 2 measured at 77 K suggest that both of them have almost connected tbo framework. Table 2. SHAPE analysis of the CoII ion in 1 and MnII ion in 2 Complex
Label
Shape
Symmetry
Distortion (τ)
1
PP-5
Pentagon
D5h
33.464
1
vOC-5
Vacant octahedron
C4v
1.654
1
TBPY-5
Trigonal bipyramid
D3h
5.450
1
SPY-5
Spherical square pyramid
C4v
0.118
1
JTBPY-5
Johnson trigonal bipyramid J12
D3h
8.579
2
PP-5
Pentagon
D5h
33.567
2
vOC-5
Vacant octahedron
C4v
2.374
2
TBPY-5
Trigonal bipyramid
D3h
5.423
2
SPY-5
Spherical square pyramid
C4v
0.156
2
JTBPY-5
Johnson trigonal bipyramid J12
D3h
8.866
Notably, the peak differences in intensity between the simulated and the experimental patterns may result from the preferred orientation of the lattice face.35 Moreover, the simulated PXRD pattern of 1 agrees with the measured one after being soaked in familiar solvents (such as MeOH, EtOH and CH2Cl2) for 24 h, implying the good solvent stability of 1 (Figure S3a, SI). Variable-temperature PXRD shows that the samples retain their crystallinity up to about 250 °C and 200 °C for 1 and 2, respectively (Figures S3b and S3c, SI).
TGAs and PXRD patterns. To corroborate the thermal stability of 1 and 2, TGAs were carried out. The results suggest that almost all of the guest molecules were removed below ~350 °C, and no further weight loss was observed until 440 °C and 520 °C, respectively (Figure S2, SI). The PXRD patterns of of 1 and 2 with crushed crystalline state were performed to confirm their phase purities before proton conductive measurements. As shown in Figure 2, the PXRD patterns at ambient temperature of 1 and 2 are consistent with the simulated ones from the single-crystal diffraction data, respectively, revealing that the phase purity of the samples.
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S cm-1 (35 °C), 9.48×10-4 S cm-1 (40 °C), 1.03×10-3 S cm-1 (45 °C) and 1.19×10-3 S cm-1 (50 °C), respectively, which is comparable to the reported MOFs (Figure 3b and Table 3). The activation energy (Ea) for the proton transfer derive d from the bulk conductivity of 1 was estimated from the impedance spectra recorded at 65% RH between 19 and 50 °C to be 0.21 eV. The proton conductivities of 1 at 53% and 33% RH (19 °C) have also been measured (Figures S4a and S4b, SI) and the σ values are 9.21×10-8 S cm-1 and 4.45×10-6 S cm-1, respectively, indicating that the higher RH is conducive to the increase of proton conductivities if the MOFs are stable enough. In addition, the PXRD pattern of the tested sample matches well with the simulated one, suggesting that the tested sample stays the same and it exhibits good cycling ability (Figure 2a).
(a)
(a) (b) Figure 2．The PXRD patterns of (a) 1 and (b) 2.
Proton Conduction The free protonated organic amine cations as proton carriers and water chains as proton-conducting pathways makes 1 and 2 suitable for potential proton-conducting solid materials. Generally, proton-conducting property of MOFs is influenced by two main factors: relative humidity (RH) and temperature.23 Thus, the proton conductivities of the solid samples are investigated by AC impedance spectroscopy. Most of the studies on proton conductivity were carried out under the conditions of 98% or 95% RH, while the samples at relatively low RH has less been investigated.36 For 1, we aimed to obtain conductivity in the form of Nyquist plots (Zʹ versus Z'') at different temperatures under relatively low humidity conditions (65% RH) employing a compacted pellet of the powder sample, as shown in Figure 3. They display one semicircle with a characteristic spur at low frequencies, indicating the blocking of H+ ions at the silver electrodes. The conductivities of the samples were derived from the impedance values by employing the following equation.37 σ=
(b) Figure 3．(a) Temperature-dependent Nyquist diagrams of 1 at 65% RH. (b) Arrhenius pattern of proton conductivity of 1.
For 2, the conductivity data at 53%, 33% and 65% RH (19 °C) have been collected (Figures S4c, S4d and S2e, SI) and the σ values are 7.26×10-8 S cm-1, 7.01×10-6 S cm-1 and 2.60×10-4 S cm-1 (d = 0.224 cm and S = 0.2826 cm2). To confirm the cycling capability and stability, the PXRD spectrum of the tested sample (65% RH) has been obtained. The result show that the tested sample has changed and complex 2 displays poor cycling capability and stability, leading to difficulty to obtained temperature-dependent proton conductivities and the Ea value.
d Z ⋅S
where σ is the conductivity (S cm-1), d is thickness (cm) of the measured sample, S stands for the electrode area (cm2) and Z represents the impedance (Ω). For 1, d and S are 0.201 cm and 0.2826 cm2 and thus the σ values are 5.93×10-4 S cm-1 (19 °C), 6.77×10-4 S cm-1 (25 °C), 7.26×10-4 S cm-1 (30 °C), 8.08×10-4
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Crystal Growth & Design
Table 3. Proton conduction performances at low RH of some
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
E-mail:
[email protected] (S.-J. Liu),
[email protected] (T.-F. Zheng),
[email protected] (T.-L. Hu). Tel: +86-797-8312204.
selected MOFs Selected MOFs
Conductivity -1
(S cm )
Measurement
Notes
condition
VNU-1538
2.9×10-2
95 °C & 60% RH
1
5.93×10-4
19 °C & 65% RH
2 {[Ca(D-Hpmpc) (H2O)2]·2HO0.5}n29 JUK-239 {[Cd2L3(DMF)(NO3) ]·2DMF·3H2O}n40 {NEt3(CH2COOH)} [MaIIMbIII(ox)3]41
2.60×10-4
19 °C & 65% RH
6.9×10-6
25 °C & 53% RH
4×10-6
25 °C & 50% RH
∼1×10-7
25 °C & 60% RH
∼1×10-7
25 °C & 65% RH
The authors declare no competing financial interest.
ACKNOWLEDGMENTS This work was financially supported by the NNSF of China (Nos. 21371102 and 21501077), the China Postdoctoral Science Foundation (No. 2016M592107), the Postdoctoral Preferred Project of Jiangxi Province of China (No. 2015KY34), the NSF of Jiangxi Province of China (Nos. 20151BAB213003 and 20161ACB21013), the Project of Jiangxi Provincial Department of Education (No. GJJ150634), and the Program for Qingjiang Excellent Young Talents, JXUST. We also thank Dr. Shao-Wei Zhang at Hunan University of Science and Technology for the calculation of geometry of the metal ions.
Because 1 and 2 are isostructural, they should exhibit the similar proton conductivities. Indeed, the results show the values of σ are the same order of magnitude at the same RH. Complex 1 shows better proton conduction and cycling capability. The increase of the conductance is due to the adsorption of the water molecules and the origin of conductivity may be originated from proton-transfer, where water molecules serve as proton-donors.
REFERENCES (1) Sadakiyo, M.; Yamada, T.; Kitagawa, H. J. Am. Chem. Soc. 2009, 131, 9906-9907. (2) Yang, F.; Huang, H.; Wang, X.; Li, F.; Gong, Y.; Zhong, C.; Li, J.-R. Cryst. Growth Des. 2015, 15, 5827-5833. (3) Shigematsu, A.; Yamada, T.; Kitagawa, H. J. Am. Chem. Soc. 2011, 133, 2034-2036. (4) Sanda, S.; Biswas, S.; Konar, S. Inorg. Chem. 2015, 54, 12181222. (5) Mallick, A.; Kundu, T.; Banerjee, R. Chem. Commun. 2012, 48, 8829-8831. (6) Ponomareva, V. G.; Kovalenko, K. A.; Chupakhin, A. P.; Dybtsev, D. N.; Shutova, E. S.; Fedin, V. P. J. Am. Chem. Soc. 2012, 134, 15640-15643. (7) Pangon, A.; Tashiro, K.; Chirachanchai, S. J. Phys. Chem. B 2011, 115, 11359–11367. (8) Pogorzelec-Glaser, K.; Rachocki, A.; Ławniczak, P.; Pietraszko, A.; Pawlaczyk, C.; Hilczer, B.; Pugaczowa-Michalska, M. CrystEngComm 2013, 15, 1950-1959. (9) Chen, Q.; Chang, Z.; Song, W.-C.; Song, H.; Song, H.-B.; Hu, T.-L.; Bu, X.-H. Angew. Chem. Int. Ed. 2013, 52, 11550-11553. (10) Bai, Y.; Dou, Y.; Xie, L.-H.; Rutledge, W.; Li, J.-R.; Zhou, H.-C. Chem. Soc. Rev. 2016, 45, 2327-2367. (11) Sadakiyo, M.; Yamada, T.; Kitagawa, H. J. Am. Chem. Soc. 2014, 136, 13166–13169. (12) Planas, N.; Mondloch, J. E.; Tussupbayev, S.; Borycz, J.; Gagliardi, L.; Hupp, J. T.; Farha, O. K.; Cramer, C. J. J. Phys. Chem. Lett. 2014, 5, 3716–3723. (13) Zhang, D.-S.; Chang, Z.; Li, Y.-F.; Jiang, Z.-Y.; Xuan, Z.-H.; Zhang, Y.-H.; Li, J.-R.; Chen, Q.; Hu, T.-L.; Bu, X.-H. Sci. Rep. 2013, 3, 3312. (14) Zhang, X.; Zhang, Y.-Z.; Zhang, D.-S.; Zhu, B.; Li, J.-R. Dalton Trans. 2015, 44, 15697-15702. (15) Walrafen, G. E.; Yang, W.-H.; Chu, Y. C. J. Phys. Chem. A 2002, 106, 10162–10173. (16) Meng, X.; Song, S.-Y.; Song, X.-Z.; Zhu, M.; Zhao, S.-N.; Wu, L.-L.; Zhang, H.-J. Chem. Commun. 2015, 51, 8150-8152. (17) Pardo, E.; Train, C.; Gontard, G.; Boubekeur, K.; Fabelo, O.; Liu, H.; Dkhil, B.; Lloret, F.; Nakagawa, K.; Tokoro, H.; Ohkoshi, S.-i.; Verdaguer, M. J. Am. Chem. Soc. 2011, 133, 15328–15331. (18) Kim, S.; Dawson, K. W.; Gelfand, B. S.; Taylor, J. M.; Shimizu, G. K. H. J. Am. Chem. Soc. 2013, 135, 963–966. (19) Dybtsev, D. N.; Ponomareva, V. G.; Aliev, S. B.; Chupakhin, A. P.; Gallyamov, M. R.; Moroz, N. K.; Kolesov, B. A.; Kovalenko, K. A.; Shutova, E. S.; Fedin, V. P. ACS Appl. Mater. Interfaces 2014, 6, 5161–5167.
CONCLUSION By employing 1,3,5-benzenetricarboxylate as 3-node ligand, two functional 3D MOFs have been successfully obtained with solvothermal reactions. They have the similar structure with HKUST-1 containing paddle-wheel-like dimeric CoII or MnII clusters and exhibit high proton conductivities with dimethylamine cations as proton carriers and lattice water chain as proton-conducting pathways, especially for 1. The synthetic methods may provide a new way to synthesize other functional MOFs. Further studies of cluster-based MOFs with better proton conductivities are under way in our group.
ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.xxxxxxx. Supplementary tables, TG curves, the N2 sorption isotherms, PXRD patterns and Nyquist diagrams at room temperature and different RH. Accession Codes CCDC 917760 (1) and 917761 (2) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
[email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION Corresponding Author
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(20) Liu, S.-J.; Xie, X.-R.; Zheng, T.-F.; Bao, J.; Liao, J.-S.; Chen, J.-L.; Wen, H.-R. CrystEngComm 2015, 17, 7270-7275. (21) Zhao, J.-P.; Han, S.-D.; Jiang, X.; Liu, S.-J.; Zhao, R.; Chang, Z.; Bu, X.-H. Chem. Commun. 2015, 51, 8288-8291. (22) Han, S.-D.; Miao, X.-H.; Liu, S.-J.; Bu, X.-H. Chem. Asian J. 2014, 9, 3116-3120. (23) Li, Y.-W.; Zhao, J.-P.; Wang, L.-F.; Bu, X.-H. CrystEngComm 2011, 13, 6002-6006. (24) Ouellette, W.; Liu, H.; Whitenack, K.; O’Connor, C. J.; Zubieta, J. Cryst. Growth Des. 2009, 9, 4258–4261. (25) Li, C.-R.; Li, S.-L.; Zhang, X.-M. Cryst. Growth Des. 2009, 9, 1702–1707. (26) Cheng, D.; Khan, M. A.; Houser, R. P. Cryst. Growth Des. 2004, 4, 599-604. (27) Rao, X.; Song, T.; Gao, J.; Cui, Y.; Yang, Y.; Wu, C.; Chen, B.; Qian, G. J. Am. Chem. Soc. 2013, 135, 15559-15564. (28) Gil-Hernández, B.; Savvin, S.; Makhloufi, G.; Núñez, P.; Janiak, C.; Sanchiz, J. Inorg. Chem. 2015, 54, 1597-1605. (29) Liang, X.; Zhang, F.; Feng, W.; Zou, X.; Zhao, C.; Na, H.; Liu, C.; Sun, F.; Zhu, G. Chem. Sci. 2013, 4, 983–992. (30) Sheldrick, G. M. SHELXL97, Program for Crystal Structure Refinement; University of Göttingen: Göttingen, Germany, 1997. (31) Blatov, V. A.; Shevchenko, A. P.; Serezhkin, V. N. J. Appl. Cryst. 2000, 33, 1193.
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(32) Xiao, B.; Wheatley, P. S.; Zhao, X.; Fletcher, A. J.; Fox, S.; Rossi, A. G.; Megson, I. L.; Bordiga, S.; Regli, L.; Thomas, K. M.; Morris, R. E. J. Am. Chem. Soc. 2007, 129, 1203–1209. (33) Jeong, N. C.; Samanta, B.; Lee, C. Y.; Farha, O. K.; Hupp, J. T. J. Am. Chem. Soc. 2012, 134, 51-54. (34) Zhang, S.; Duan, E.; Cheng, P. J. Mater. Chem. A 2015, 3, 7157–7162 (35) Liu, S.-J.; Cao, C.; Xie, C.-C.; Zheng, T.-F.; Tong, X.-L.; Liao, J.-S.; Chen, J.-L.; Wen, H.-R.; Chang, Z.; Bu, X.-H. Dalton Trans. 2016, 45. 9209. (36) Yang, L.; Tang, B.; Wu, P. J. Mater. Chem. A 2015, 3, 1583815842 (37) Bureekaew, S. Horike, S.; Higuchi, M.; Mizuno, M.; Kawamura,T.; Tanaka, D.; Yanai, N.; Kitagawa, S. Nat. Mater. 2009, 8, 831-836. (38) Tu, T. N.; Phan, N. Q.; Vu, T. T.; Nguyen, H. L.; Cordova, K. E.; Furukawa, H. J. Mater. Chem. A 2016, 4, 3638–3641. (39) Matoga, D.; Oszajca, M.; Molenda, M. Chem. Commun. 2015, 51, 7637-7640. (40) Song, B.-Q.; Wang, X.-L.; Yang, G.-S.; Wang, H.-N.; Liang, J.; Shao, K.-Z.; Su, Z.-M. CrystEngComm 2014, 16, 6882–6888. (41) O̅kawa, H.; Sadakiyo, M.; Yamada, T.; Maesato, M.; Ohba, M.; Kitagawa, H. J. Am. Chem. Soc. 2013, 135, 2256-2262.
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Crystal Growth & Design
For Table of Contents Use Only High Proton Conduction in Two CoII and MnII Anionic MOFs Derived from 1,3,5-Benzenetricarboxylic Acid
Sui-Jun Liu,* Chen Cao, Fan Yang, Mei-Hui Yu, Shu-Li Yao, Teng-Fei Zheng,* Wei-Wei He, Hai-Xia Zhao, Tong-Liang Hu,* and Xian-He Bu
Two anionic metal-organic frameworks have been constructed with one-pot method, and they exhibit high proton conductivities due to the existence of lattice water molecules and Me2NH2+ cations, especially for 1.
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