Tuning Connectivity and Flexibility of Two Metal-Triazolate

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Tuning Connectivity and Flexibility of Two MetalTriazolate-Carboxylate Type Porous Coordination Polymers Zong-Wen Mo, Hao-Long Zhou, Jia-Wen Ye, Dong-Dong Zhou, Pei-Qin Liao, Wei-Xiong Zhang, and Jie-Peng Zhang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b00196 • Publication Date (Web): 23 Mar 2018 Downloaded from http://pubs.acs.org on March 23, 2018

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Crystal Growth & Design

Tuning Connectivity and Flexibility of Two ZincTriazolate-Carboxylate Type Porous Coordination Polymers Zong-Wen Mo, Hao-Long Zhou, Jia-Wen Ye, Dong-Dong Zhou, Pei-Qin Liao, Wei-Xiong Zhang, and Jie-Peng Zhang* MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun YatSen University, Guangzhou 510275, China

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KEYWORDS. Metal-organic framework, Flexibility, topology, adsorption.

ABSTRACT. Solvothermal reactions of Zn(II) salts and 4-(1H-pyrazol-4-yl) pyridine (Hpypz) in the presence of monocarboxylate or dicarboxylate ligands produce two metal-organic frameworks,

namely

[Zn(pypz)(OAc)]·guest

(1·g,

HOAc

=

acetic

acid)

and

[Zn2(pypz)2(oba)]·guest (2·g, H2oba = 4,4'-oxobisbenzoic acid). Single-crystal X-ray diffraction analyses showed that both 1 and 2 contain 2-fold interpenetrated 3-dimensional nbo-a {Zn(pypz)}+ networks consisting of 3-connected Zn(II) ions and 3-connected pypz– ligands. After considering the carboxylate ligands, 1 retains the nbo-a network structure and contains 1dimensional channels with very narrow apertures. On the other hand, 2 becomes a new uninodal 6-connected topology (point symbol 33.42.56.64) and contains discrete pores. Powder X-ray diffraction showed that, after solvent removal, 1 undergoes obvious framework shrinkage, while 2 retains the original unit cell. Activated 1 and 2 both exclude N2 at 77 K, but readily adsorb CO2 at 195 K with unconventional isotherm shapes, indicating the different types of framework flexibilities.


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Porous coordination polymers (PCPs) or metal–organic frameworks (MOFs) have attracted great interest because of their highly designable framework and pore structures, as well as their interesting flexibility under external stimuli.1-3 Flexible PCPs have been demostrated to facilitate in storage, seperation, sensing etc.4-10 Many types of framework flexibility have been reported, most of which exhibit multiple thermodynamic metastable states and show structural transformation between these states, such as shrinkage, expansion, distortion, sliding, ligand exchange, and even catenation rearragement.11-13 Flexible PCPs with thermodynamic multistability usually exhibit multi-step adsorption isotherms. In a few cases which called kinetically controlled flexibility, flexible PCPs show only one structure at the thermodynamic equilibrium state, because their structural transformations occur transiently in the nonequilibrium state.14-15 It should be noted that, compared with the composition, topology, and pore characteristics of PCPs, framework flexiblity/dynamism is more difficult to design or control.3 With simple and predictable coordination geometries, 1,2,4-trizolate derivatives have been widely used to construct PCPs.16-20 Numerous Zn(II)-triazolate-carboxylate type frameworks have been reported, in which Zn(II) and triazolate usually behave as 3-connected nodes to form a two-dimensional (2D) cationic {Zn(tz)}+ (Htz = 1,2,4-trizole) layer with the sql-a topology.21-24 The residual coordination site of Zn(II) can be terminated by monocarboxylate ligands or simple inorganic anions to form neutral 2D structures, or by dicarboxylate ligands, such as oxalate, succinate, terephthalate, isophthalate, aliphatic dicarboxylate and their derivatives, to form 3D pillared-layer PCPs.25 The framework structure, pore size/shape, and flexibility of these 3D PCPs can be tuned by changing the length, geometry, and side group of dicarboxylate ligands.23-28 For example, the 2D {Zn(atz)}+ (Hatz = 3-amino-1,2,4-triazole) layer can distort in different manners to fit the increasing length of flexible aliphatic dicarboxylate ligands.29 While



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[Zn2(tz)2(atp)] (H2atp = 2-aminoterephthalic acid) is rigid because of the intramoleculear hydrogen bonding interactions, the isostructural frameworks [Zn2(tz)2(R-tp)] (R-tpH2 = 2H/Br/OH-terephthalic acid) are flexible.25 As an elongated trizole ligand, 4-(1H-pyrazol-4yl)pyridine (Hpypz) can deprotonate and coordinate with Zn(II) to form similar 2D cationic {Zn(pypz)}+ layers with the 3-connected sql-a topology.30-31 For example, reaction of Zn(NO3)2, Hpypz and 1,3,5-benzenetricarboxylic acid (H3btc) yielded two kinds of ternary PCPs, [Zn5(pypz)4(btc)2] and [Zn3(pypz)3(btc)], with unique structures and high methane storage capacities.32-33 Notably, [Zn5(pypz)4(btc)2] is a novel 3D pillared-layer PCP consisting of a the 2D sql-a {Zn(pypz)}+ layer and 8-legged {Zn2(btc)4(H2O)}8– metalloligands.32 As an extension of our continuous investigation on metal-triazolate frameworks, we further studied the Zn-pypz-carboxylate system and successfully synthesized two new PCPs, namely [Zn(pypz)(OAc)]·guest (1·g, HOAc = acetic acid) and [Zn2(pypz)2(oba)]·guest (2·g, H2oba = 4,4'-oxobisbenzoic acid, Figure S1), in which the {Zn(pypz)}+ network adopt the 3D 3connnected nbo-a topology rather than the common 2D 3-connected sql-a topology. With different terminating carboxylate ligands, 1 and 2 show different framework connectivities, flexibilities, and adsorption behaviors. Solvothermal reaction of Zn(OAc)2 and Hpypz in DMA yields crystals of [Zn(pypz)(OAc)] (1·g). Single-crystal X-ray analysis revealed that 1·g crystallizes in the trigonal space group R-3. The Zn2+ ion adopts the tetrahedral geometry with three nitrogen atoms from three pypz– ligands and one oxygen atom from OAc– (Zn–O = 1.947(7)/2.587(7) Å). Each pypz– coordinates with three zinc atoms. The OAc– ligand was coordinated to one Zn2+ ion in a mono-dentate mode. Regarding both Zn2+ and pypz– as 3-connected nodes, the {Zn(pypz)}+ network can be simplified as a 3-connected nbo-a topology, which can be further simplified as the 4-connected nbo


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topology considering the pyrazolate-bridged binuclear unit Zn2(Rpz)2(Rpy)2 (Rpz– = pyrazolate group; Rpy = pyridine group) as 4-connected nodes (Figure 1a).34-35 While the topology of {Zn(pypz)}+ is the same as [Cu(detz)] (MAF-2, Hdetz = 3,5-diethyl-1,2,4-triazole), the length of pypz– is much longer than detz–.14 Therefore, {Zn(pypz)}+ networks in 1·g are 2-fold interpenetrated (Class Ia, related by a single translation) (Figure 1b).36-38 Even taking account of the acetate ligands, there are still 1D channels along the c-axis (41%), in which large windmilllike cavities with diameter of 6.8 Å are interconnected through narrow necks with diameter of 3.2 Å), deducting the van der Waals radii (Figure 1c).

Figure 1. (a) An nbo cage fragment, (b) the simplified topological structure (two-fold interpenetrated 4-connected nbo nets considering Zn2(Rpz)2(Rpy)2 units as 4-connected nodes



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and pypz– as 2-connected linkers, with terminal acetate ligands as dangling sticks), and (c) the pore surface structure of 1·g.

Solvothermal

reaction

of

Zn(NO3)2,

Hpypz

and

H2oba

in

DMF

yields

[Zn2(pypz)2(oba)]·guest (2·g), possessing a crystal symmetry and framework structure highly related with 1·g (Table S1). The coordination geometries of Zn2+ and pypz– in 2·g are virtually identical with those in 1·g. The {Zn(pypz)}+ networks in 2·g also adopt the two-fold interpenetrated nbo-a topology, but the two networks are related a 2-fold axis (Class IIa), as indicated by its space group of R-3c (Figure 2a). The carboxylate coordination mode of oba2– (Zn–O 2.081(6)/2.902(7) Å) is similar with OAc–. However, since oba2– is a 2-connnected linker rather than a terminal ligand, the Zn2(Rpz)2(Rpy)2(RCOO)2 units can be considered as sixconnected nodes and the whole network form a new uninodal 6-connected topology with point symbol of 33.42.56.64 (Figure 2b). Due to the bulkier oba2– ligand, 2·g contains a small solvent accessible pore ratio of 23%, and the channels running along the c-axis are cut into discrete propeller-like cavities (Figure 2c).


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Figure 2. (a) A cage fragment and (b) the simplified topological structure (two-fold interpenetrated uninodal 6-connected net with a point symbol of 33.42.56.64 considering Zn2(Rpz)2(Rpy)2(RCOO)2 units as 6-connected nodes and pypz–/oba2– ligands as 2-connected linkers), and (c) the pore surface structure of 2·g.

Thermogravimetry and PXRD showed that 1·g and 2·g can completely release all guest molecules at ca. 150 and 200 oC, respectively (Figure S2). The relatively high temperature for removing the guests of 2·g can be assigned to its discrete cavities. Variable-temperature PXRD measurements showed that, after guest removal, [Zn(pypz)(OAc)] adopts a new phase (hereafter denoted as 1'). On the other hand, [Zn2(pypz)2(oba)] (2) retains the original phase of 2·g. Further, 1' and 2 can be stable up to 300 and 400 oC, respectively (Figure S3). 1' can convert back to 1·g upon adsorption of DMA vapors, meaning that the structural transformation is reversible and guest-induced (Figure S4). We also examined the chemical stabilities of the activated samples (Figure S5), which showed that 1' and 2 can retain their PXRD patterns in saturated water vapour for 3 days and in liquid water for 1 year, respectively. The higher stabilities and rigidity of 2 can be explained by its higher connectivity and smaller porosity (Figure 2a). We successfully determined the crystal structure of 1', which retains the original space group of R-3, but the unit-cell volume shrinks 10% (Table S1, Figure 3), mainly because of the 7 ACS Paragon Plus Environment


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large change of the conformation of pypz–. Specifically, the dihedral angle between the two aromatic rings of pypz– changed from 2.7º in 1·g to 27.3º in 1' (Figure S6). Concomitantly, the solvent accessible void ratio decreased to 31%, and diameters of the cavities and apertures decreased to 6.0 Å and 3.0 Å, respectively (Figure S7). Interestingly, the coordination mode of OAc– ligand in 1' became bidentate (Zn-O 2.191(9)/2.167(4) Å).

Figure 3. An nbo cage fragment of 1'.

1' and 2 both showed no N2 adsorption at 77 K, which can be attributed to the presences of extremely narrow channel apertures and discrete pores. On the other hand, they can both adsorb large amounts of CO2 at 195 K. Although similar phenomena have been widely reported and can be ascribed to the smaller kinetic diameter of CO2,39-41 the aperture sizes of 1' (3.0 Å) and 2 (1.3 Å) are obviously too small (the smallest cross section diameter of CO2 is 3.4 Å). This means the barriers of their channels have to be opened for CO2 diffusion at 195 K, being similar with the case of MAF-2.14 The CO2 adsorption isotherm of 1' contained two steps. The first step adsorption saturates at P/P0 = 0.33 with an uptake 133 cm3 g–1, corresponding to a pore volume 8 ACS Paragon Plus Environment

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of 0.24 cm3 g–1, which is close to the value of 0.25 cm3 g–1 calculated from its crystal structure. The CO2 uptake of the second step reached 180 cm3 g–1, corresponding to the pore volume of 0.32 cm3 g–1, which is somewhat lower than the value of 0.36 cm3 g–1 calculated from the crystal structure of 1 (Figure 4a). It is ordinary that the measured pore volume is a little lower than the value calculated from the crystal structure, because the large and irregular CO2 molecules can utilize the small channel less efficiently, compared with the probe used for accessible void calculation.37 GCMC simulations showed that 1 and 1' can adsorb 39 and 27 CO2 molecules per unit cell, corresponding to uptakes of 181 and 134 cm3 g-1, or pore volumes of 0.32 and 0.24 cm3 g–1, respectively, which are consistent well with the experimental values (Figure S8 and Table S2). The CO2 isotherm of 2 exhibits a quasi-type-I character, in which the CO2 uptake gradually increases from 88 cm3 g–1 at P/P0 = 0.1 to 116 cm3 g–1 at P/P0 = 0.90, corresponding to the pore volumes from 0.16 cm3 g–1 to 0.21 cm3 g–1, respectively (Figure 4b). For comparison, the pore volume calculated from the crystal structure is 0.19 cm3 g–1, indicating that after saturation adsorption at low relative pressure, the host framework can further expand to accommodate additional CO2 molecules.

-1

(a) 200 180 160 140 120 100 80 60 40 20 0 Uptakes / cm (STP) g

77K N2 195 K CO2

3

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


0.0

0.2

0.4

0.6 P/P0

0.8

1.0



-1

(b) 120

Uptakes / cm (STP) g

100

3

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

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77 K N2 195 K CO2

80 60 40 20 0 0.0

0.2

0.4

0.6 P/P0

0.8

1.0

Figure 4. 77 K N2 and 195 K CO2 adsorption and desorption isotherms of (a) 1' and (b) 2.

Based on Zn(II), an elongated trizolate ligand and monocarboxylate/dicarboxylate ligands, we synthesized two ternary PCPs, in which the cationic Zn(II) triazolate networks possesses the 3D 3-connected nbo-a topology instead of the usually observed 2D 3-connected sql-a topology. After considering the terminal carboxylate ligands, the whole coordination network retains the nbo-a network structure for the monocarboxylate ligand, but transforms to a new uninodal 6connected topology for the dicarboxylate ligand. With increased connectivity and decreased porosity, the PCP consisting of dicarboxylate ligands exhibits reduced framework flexibility toward guest adsorption/desorption. These results may enlighten design and synthesis of new PCPs with desired framework structures and flexibility.

Supporting information The supporting information is available free of charge on the ACS Publications website at DOI: xxx Experimental details and additional figures/tables.


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Corresponding Author *E-mail: [email protected] Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes The authors declare no competing financial interest. ACKNOWLEDGMENT This work was supported by the “973 Project” (2014CB845602) and NSFC (21290173 and 21473260). REFERENCES 1.

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Tuning Connectivity and Flexibility of Two ZincTriazolate-Carboxylate Type Porous Coordination Polymers Zong-Wen Mo, Hao-Long Zhou, Jia-Wen Ye, Dong-Dong Zhou, Pei-Qin Liao, Wei-Xiong Zhang, and Jie-Peng Zhang*

Combination of Zn(II) and an elongated trizolate ligand as well as monocarboxylate or dicarboxylate ligands produce two metal-organic frameworks with highly similar structures but different topologies and flexibilities.


Tuning Connectivity and Flexibility of Two Metal-Triazolate

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