A Distorted [Mn2(COO)4N2] Cluster Based MetalâOrganic Framework

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A distorted [Mn2(COO)4N2] cluster based MOF with (3,3,6) Topology and Selective Adsorption of CO2 Jingjing Jiang, Qian Wang, Mingxing Zhang, and Junfeng Bai Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b00206 • Publication Date (Web): 09 Mar 2017 Downloaded from http://pubs.acs.org on March 15, 2017

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Crystal Growth & Design

A distorted [Mn2(COO)4N2] cluster based MOF with (3,3,6) Topology and Selective Adsorption of CO2 Jingjing Jiang,1 Qian Wang,2 Mingxing Zhang1 and Junfeng Bai*,2,1 1

State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China 2

School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119, China

Supporting Information Placeholder ABSTRACT: Based on the ligand of 5-(pyridin-3-yl)isophthalic acid (H2L), a new distorted [Mn2(COO)4N2] cluster based MOF with (3,3,6) topology, [Mn2(L)2DMF]•DMF•MeOH (NJU-Bai33), was synthesized, which exhibits a new point (Schläfli) symbol of (4•62)2(42•68•85), contains open metal sites, and shows selective adsorption of CO2 over N2 and CH4 with the CO2 uptake amounts high up to 7.9 and 4.2 wt% at 0.15 bar and at 273 and 298 K, respectively.

Global warming is one of our great concerns due to the rapid growth of CO2 emission.1-4 To reduce the anthropogenic CO2 emission, great efforts have been devoted to the development of diverse CO2 capture materials and many porous solids have been intensively investigated, such as zeolites and carbons, et al.5-7 Recently, metal-organic frameworks (MOFs), emerging as a new class of porous materials for CO2 capture and sequestration (CCS), have attracted great attention because of their crystalline nature, fascinating structure, extraordinary surface area, functionalizable pore surface, tunable pore size and shape.1, 8-12 One of our research focus is the construction of novel MOFs with potential application in the CO2 capture from rigid and flexible multidentate ligands which contain both a homodonor and a heterodonor.13-22 For example, very recently, based on the organic ligand of 5-(pyridin-3-yl)isophthalic acid (H2L), a (3,6)-connected MOFs with rtl topology, NJU-Bai7, was designed, in which the inorganic SBU of the 6-connected Cu-paddlewheel is one of the most common molecular building blocks.22 To further enrich our work, manganese ion (Mn2+) was selected to construct the versatile MOFs because it may lead to the different 6-connected metal clusters in comparison to Cu2+ because of its changeable coordinating number and coordination geometry.23-29 Herein, a new distorted [Mn2(COO)4N2] cluster based MOF with (3,3,6) topology, NJU-Bai33, was presented, which exhibits a new point (Schläfli) symbol of (4•62)2(42•68•85), contains open metal sites after removal of ligated solvent, and shows selective adsorption of CO2 over N2 and CH4 with the CO2 uptake amounts high up to 7.9 and 4.2 wt% at 0.15 bar and at 273 and 298 K, respectively.

Solvothermal reaction of MnCl2·4H2O with H2L in N,N- dimethylformamide/methanol containing hydrochloric acid afforded a

high yield of colourless block crystals of NJU-Bai33. Single X-ray crystal structure reveals that it crystalizes in monoclinic space group Cc. In the asymmetric unit of NJU-Bai33, there are two crystallographically independent Mn(II) ions (Mn1 and Mn2), two different kinds of H2L with different coordination modes (L1 and L2) and one coordinated DMF solvent molecule (Fig. S1). The Mn1 atom is six-coordinated by five oxygen atoms from four different H2L ligands and one nitrogen atom from another H2L ligand to form a distorted

Fig. 1 (a) The ball and stick model of the distorted [Mn2(COO)4N2] cluster with coordinated DMF molecule. The gray, red, rose and blue spheres represent carbon, oxygen, manganese and nitrogen atoms, respectively. (b) The coordination environment of the distorted [Mn2(COO)4N2] cluster; (c) The coordination modes of the organic ligand, H2L.

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Fig. 2 (a) The metal cluster is linked by the ligand with L2 mode leading to the formation of 2D hcb topological layer, which is further pillared by the ligand with L1 mode giving the formation of 3D NJU-Bai33 (top and middle); (middle) In NJU-Bai33, the 2D hcb topological layer adopts the packing way of AB stacking model; (bottom) The topological network of NJU-Bai33 with the point symbol of (4·62)2(42·68·85), in which organic ligands with two different coordination modes of L1 (lime) and L2 (gold) can be simplified as two different kinds of 3-connected nodes; (b) In NJUBai33, two similar 1D channels along the directions of (a+b) and (a-b) are formed, respectively, and both of their pore sizes are 4.0 × 4.8 Å2. H atom and the coordinated DMF molecule are omitted for clarity.

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octahedral geometry (Fig. 1a). The Mn2 is also six-coordinated and surrounded by four oxygen atoms from three distinct H2L ligands, one oxygen atom from one DMF molecule and one nitrogen atom from a different H2L ligand. Thus, different from the Cu-paddlewheel unit of NJU-Bai7,22 the new binuclear cluster of [Mn2(COO)4N2] with coordinated DMF molecule in NJU-Bai33 is composed of four carboxyl groups, two nitrogen atoms and one DMF molecule. In the Mn-cluster, four oxygen atoms of two carboxyl groups from two ligands with L1 mode are coordinated to two Mn(II) ions by adopting bridging and bridging-chelate modes, respectively (Fig. 1b). Two oxygen atoms of one carboxyl group from one ligand with L2 mode are attached to the two Mn(II) ions by the bridging mode. Two other oxygen atoms of one carboxyl group from another ligand with L2 mode chelates Mn1 atom, and two nitrogen atoms from other two H2L with distinct coordination modes of L1 and L2, are bound to Mn1 and Mn2, respectively. In addition, one oxygen atom from DMF solvent molecule is coordinated to Mn2 atom. It is interesting to note that, as shown in Fig. 1c, the H2L ligand in NJU-Bai33 has two different types of coordination modes, L1 and L2, which are different from the only one coordination mode of H2L ligand in NJU-Bai722. The ligand with L1 mode bridges three Mn-clusters through two carboxyl groups with one adopting the bridging-chelating mode, another using the chelating one, and one N atom. Meanwhile, the ligand with L2 mode links three Mn-clusters through two carboxyl groups with one adopting the bridging mode, another using the chelating one, and one N atom. Compared with the structure of NJU-Bai7 from the paddlewheel unit linked through the isophthalic acid moiety of H2L followed by the pillaring of pyridyl group,22 in the structure of NJUBai33, the binuclear [Mn2(COO)4N2] cluster is connected through the ligand with L2 mode leading to the formation of twodimensional layers with hcb topology (Fig. 2a, S2), which is further pillared by the ligand with L1 mode giving the formation of 3D porous framework. Along the opposite direction of c axis, the hcb topological layer adopts the packing way of AB stacking model, in which layer of B can be turned from layer of A by a reflection of ac mirror (Fig. S2). Thus, different from the only one type of 1D channel formed in NJU-Bai7,22 two similar onedimensional channels along the directions of (a+b) and (a-b) are generated in NJU-Bai33, respectively (Fig. 2b, S3,4). With the coordinated DMF molecule removed, both of their pore sizes are about 4.0 × 4.8 Å2 determined by the van der waals diameter of the inserted pseudoatom, which are larger than that of 3.4 × 3.4 Å2 in NJU-Bai7. From the viewpoint of structural topology, in NJUBai33, the binuclear Mn-clusters can be viewed as 6-connected nodes, and organic ligands with two different coordination modes of L1 and L2, can be simplified as two different kinds of 3connected nodes. Therefore, its overall framework may be simplified as a new (3,3,6)-connected network (Fig. 2a), which is different from the (3,6)-connected topological net in NJU-Bai7. Topological analysis by the TOPOS program suggests that the point (Schläfli) symbol of the network is (4·62)2(42·68·85), which represents a new topology. Moreover, the total potential solvent accessible volumes in desolvated NJU-Bai33 after removal of guest solvates and coordinated DMF molecule is around 33.5% as determined by the PLATON/SOLV program30 giving a calculated density of 1.109 g cm-3 for the desolvated framework. To investigate the permanent porosity of NJU-Bai33, the N2 adsorption isotherm was measured at 77 K. As shown in Fig. S8, the N2 uptake amount is 302.5 cm3 g-1 (STP) at 1 bar. The N2 gas adsorption shows a reversible type I isotherm without hysteresis on desorption, which is characteristic of microporous material. The Brunaer-Emmett-Teller (BET) and Langmuir surface area of desolvated NJU-Bai33 were estimated to be 884.8 and 1072.5 m2 g-1, respectively. Furthermore, its H-K (Horvath-Kawazoe) pore diameter is 4.66 Å, which is almost consistent with the pore size

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as determined by the crystal structure. The pore volume given by Dubinin–Radushkevich (DR) equation is 0.35 cm3 g-1, close to theoretical value of 0.30 cm3 g-1 calculated using PLATON.31-32 Fig. 3 CO2, N2 and CH4 adsorption isotherms of NJU-Bai33 at 273 (a) and 298 K (b) (filled symbols, adsorption; open symbols, desorption).

Furthermore, its selective adsorption properties of CO2 versus N2 and CH4 were investigated. The CO2, N2 and CH4 adsorption measurements for NJU-Bai33 were carried out at 273 K and 298 K (Fig. 3). At 0.15 bar, the uptake amounts of CO2 are 40.3 and 21.6 cm3 g-1, corresponding to 7.9 and 4.2 wt% at 273 and 298 K, respectively, which are lower than the uptake amounts for CO2 of NJU-Bai7, 11.8 and 8.0 wt% at 0.15 bar and under 273 and 298 K,

respectively,22 but are substantially higher than those of the wellknown MOFs, such as ZIF-78 (6.4 and 3.4 wt% at 0.15 bar and under 273 and 298 K, respectively),33 NH2-MIL-53(Al) (3.2 wt%, at 298 K and 0.1 bar),34 en-Cu-BTTri (2.4 wt%, at 298 K and 0.15 bar),35 Cu-EBTC (5.9 wt%, at 273 K and 0.15 bar),36 SNU-4 (4.9 wt%, at 273 K and 0.15 bar)37 and MOF-5 (2.1 and 0.75 wt% at 0.15 bar and under 273 and 298 K, respectively) 8, 38. In addition, at 1 bar, the uptake amounts of CO2 are 86.2 and 65.6 cm3 g-1, corresponding to 16.9 and 12.9 wt% at 273 and 298 K, respectively, which are also comparable to the values of NJU-Bai7 (13.9 and 12.8 wt% at 1 bar and under 273 and 298 K, respectively). However, it is worthy of note that at 0.75 bar, NJU-Bai33 can only adsorb limited amounts of N2, 8.3 and 4.2 cm3 g-1, corresponding to 1.0 and 0.5 wt% at 273 and 298 K, respectively; and at 1 bar, the CH4 uptake amounts are also only 32.9 and 19.4 cm3 g-1, corresponding to 2.4 and 1.4 wt% at 273 and 298 K, respectively. Fig. 4 IAST predicted selectivity for CO2/N2 (0.15:0.85) and CO2/CH4 (1:1) mixture of NJU-Bai33 at 273 and 298 K.

The selectivity for CO2/N2 and CO2/CH4 of NJU-Bai33 at different temperatures were calculated by two different kinds of methods to evaluate its selective CO2 adsorption. As shown in Fig. 4, the selectivity predicted by ideal adsorbed solution theory (IAST) from the experimental single-component isotherms based on CO2/N2 (0.15:0.85) and CO2/CH4 (1:1) mixture are 58.7 and 9.7 at 273 K and 1 bar, respectively, and 40.3 and 8.9 at 298 K and 1 bar, correspondingly (Fig. 4). However, the values for NJUBai33 are still lower than those of NJFU-2 at 273 and 298 K and the selectivity for CO2 over N2 of NJU-Bai33 is also less than that of NJU-Bai32 at 298 K (Table S4). In addition, the separation

ratio of CO2 versus N2 and CH4 for NJU-Bai33 were also calculated from the ratio of the initial slopes based on the isotherms (Fig. S16, 17). The selectivity for CO2/N2 are 36.5 and 30.2 at 273 and 298 K, respectively, which are lower than 50.1 of ZIF-78 at 298 K, 33 but still higher than 25.5 and 19.0 of SYSU at 273 and 298 K (Table S4). Moreover, the selectivity for CO2/CH4 is 7.8 and 6.8 at 273 and 298 K, respectively, which approaches the values of NJU-Bai7 (Table S4). The moderate selectivity for CO2 of NJU-Bai33 might be mainly resulted from the open metal site exposed in pore channels of the framework. To evaluate the adsorbent-adsorbate interaction, the adsorption enthalpy for CO2 of NJU-Bai33 at zero-loading calculated by the virial method using the experimental isotherm data at 273 and 298 K is 25.7 kJ mol-1 (Fig. S13), which is in the usual range of the porous MOFs.1 The isosteric heats (Qst) for CH4 adsorption of NJU-Bai33 is also estimated to be 20.8 kJ mol-1, which is close to the corresponding values found for most promising MOFs for methane storage.39-41 In summary, based on the organic ligand of 5-(pyridin-3yl)isophthalic acid (H2L), a new distorted [Mn2(COO)4N2] cluster based MOF with (3,3,6) topology, NJU-Bai33, has been synthesized. Very interestingly, it exhibits a new point (Schläfli) symbol of (4·62)2(42·68·85) and further enriches the library of (3,6)connected MOFs. Moreover, it shows selective adsorption of CO2 over N2 and CH4 with the CO2 uptake amounts high up to 7.9 and 4.2 wt% at 0.15 bar and at 273 and 298 K, respectively and may be an excellently potential candidate for CO2 capture, such as the post-combustion CO2 capture and the purification of natural gases.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.


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Synthesis of ligands and MOFs, X-ray single crystal structure determination, low pressure gas sorption measurements, estimation of the isosteric heats of gas adsorption, prediction of the gases adsorption selectivity by IAST, PXRD patterns, TGA plots, IR spectra, and H-NMR spectrum (PDF) Accession Codes CCDC 1447021 contains 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 * E-mail: [email protected].

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (21371091).

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A distorted [Mn2(COO)4N2] cluster based MOF with (3,3,6) Topology and Selective Adsorption of CO2 Jingjing Jiang,1 Qian Wang,2 Mingxing Zhang1 and Junfeng Bai*,2,1 1

State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering,

Nanjing University, Nanjing 210023, China 2

School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119, China

E-mail: [email protected]. Tel: +86-25-89683384.

(1.375 inches high × 3.5 inches wide, 600 dpi)

A new distorted [Mn2(COO)4N2] cluster based MOF with (3,3,6) topology was synthesized, which exhibits a new point (Schläfli) symbol of (4·62)2(42·68·85), contains open metal sites after removal of ligated solvent, and shows selective adsorption of CO2 over N2 and CH4 with the CO2 uptake amounts high up to 7.9 and 4.2 wt% at 0.15 bar and at 273 and 298 K, respectively.


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Fig. 1 (a) The ball and stick model of the distorted [Mn2(COO)4N2] cluster with coordinated DMF molecule. The gray, red, rose and blue spheres represent carbon, oxygen, manganese and nitrogen atoms, respectively. (b) The coordination environment of the distorted [Mn2(COO)4N2] cluster; (c) The coordination modes of the organic ligand, H2L. 75x69mm (300 x 300 DPI)



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Fig. 2 (a) The metal cluster is linked by the ligand of L2 leading to the formation of 2D hcb topological layer, which is further pillared by the ligand of L1 giving the formation of 3D NJU-Bai33 (top and middle); (middle) In NJU-Bai33, the 2D hcb topological layer adopts the packing way of AB stacking model; (bottom) The topological network of NJU-Bai33 with the point symbol of (4•62)2(42•68•85), in which two different kinds of organic ligands, L1 (lime) and L2 (gold), can both be simplified as 3-connected nodes; (b) In NJU-Bai33, two similar 1D channels along the directions of (a+b) and (a-b) are formed, respectively, and both of their pore sizes are 4.0 × 4.8 Å2. H atom and the coordinated DMF molecule are omitted for clarity. 199x519mm (300 x 300 DPI)


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Fig. 3 CO2, N2 and CH4 adsorption isotherms of NJU-Bai33 at 273 (a) and 298 K (b) (filled symbols, adsorption; open symbols, desorption). 124x188mm (300 x 300 DPI)



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Fig. 4 IAST predicted selectivity for CO2/N2 (0.15:0.85) and CO2/CH4 (1:1) mixture of NJU-Bai33 at 273 and 298 K. 64x50mm (300 x 300 DPI)


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A Distorted [Mn2(COO)4N2] Cluster Based MetalâOrganic Framework

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A Distorted [Mn2(COO)4N2] Cluster Based MetalâOrganic Framework