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Halogen•••Halogen Interactions in the Supramolecular Assembly of 2D Coordination Polymers and the CO2 Sorption Behavior Faruk Ahmed, Syamantak Roy, Kaushik Naskar, Chittaranjan Sinha, Seikh Mafiz Alam, Suman Kundu, Jagadese J Vittal, and MOHAMMAD HEDAYETULLAH MIR Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b00983 • Publication Date (Web): 16 Aug 2016 Downloaded from http://pubs.acs.org on August 22, 2016

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Crystal Growth & Design

Halogen···Halogen Interactions in the Supramolecular Assembly of 2D Coordination Polymers and the CO2 Sorption Behavior Faruk Ahmed,† Syamantak Roy,§ Kaushik Naskar, ║ Chittaranjan Sinha, ║ Seikh Mafiz Alam, † Suman Kundu, # Jagadese J. Vittal*‡ and Mohammad Hedayetullah Mir*†. †

Department of Chemistry, Aliah University, New Town, Kolkata 700 156, India.

§

Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific

Research, Jakkur, Bangalore 560 064, India. ║

Department of Chemistry, Jadavpur University, Jadavpur, Kolkata 700 032, India.

#

Department of Chemistry, R. K. M. Residential College, Narendrapur, Kolkata 700 103, India.

‡

Department of Chemistry, 3 Science Drive 3, National University of Singapore, Singapore 117

543, Singapore. To

whom

correspondence

should

be

addressed.

E-mails:

[email protected]

and

[email protected] ABSTRACT: Four new mixed-ligand divalent coordination polymers (CPs) [Cu2(muco)2(4clpy)2] (1), [Cu2(muco)2(4-brpy)2] (2), [Zn2(bdc)2(4-clpy)2] (3) and [Zn2(bdc)2(4-brpy)2] (4)

ACS Paragon Plus Environment

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(H2muco = trans, trans-muconic acid or 1,3- butadiene-1,4-dicarboxylic acid; H2bdc = 1,4benzene dicarboxylic acid; 4-clpy = 4-chloro pyridine and 4-brpy = 4-bromo pyridine) have been synthesized and well characterized by elemental analysis, infrared spectra, single crystal X-ray diﬀraction techniques, powder X-ray diffraction (PXRD) patterns and thermogravimetric analysis (TGA). All the compounds 1 ̶ 4 have two-dimensional (2D) coordination polymeric sheet structure. Of these 1 and 2 are isotypical and form 3D supramolecular aggregation based on type I halogen-halogen interactions (Cl···Cl or Br···Br) and have impact on CO2 sorption properties. For the first time, halogen-halogen interactions have been used as tool in the construction of high dimensional CPs for sorption studies. However, analogous compounds 3 and 4 are expanded to 3D supramolecular structures based on π···π interactions. These compounds have no halogen-halogen interactions and hence become non-porous towards CO2 sorption. It appears that the halogen-halogen interactions between the 2D sheets are desirable for the uptake of CO2 gas. Introduction Porous coordination polymers (PCPs) or metal–organic frameworks (MOFs) have been extensively studied due to a great deal of interest as a new class of porous materials.1-5 The synthesis of PCPs has been particularly important due to its ability to systematically fine-tune the size and shape of the pore by choosing appropriate metal ions or metal clusters and suitable organic spacer ligands.6-8 PCPs are promising materials in gas storage and separation, ion exchange, trapping or sensing of target molecules, catalysis, magnetism, nonlinear optics, recognition and sensing by enzymes in solution.9-10 Among these applications, the separation and purification of gases or vapours are of special interest.11-12 For example, selective adsorption of CO2 gas is an important problem with respect to the greenhouse gas emission.13 Hence,


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researchers are interested in designing highly selective host frameworks to capture CO2 and then release it more efficiently. Two-dimensional coordination polymers (2D CPs) have been employed not only to accommodate various guest molecules in the inter-layer spaces14-16 but also for selective gas adsorption. It is possible fine-tune the layer–layer interface by introducing weaker interactions, including H-bonds, π-electron stacking and van der Waals interactions.17-19 Among the PCPs synthesized to date, only a few flexible structural motifs have been constructed by assembling the 2D layers via π-π stacking.20-22 The halogen-halogen interactions have been rarely used for this purpose.23-25 Halogen-halogen interactions have become an increasingly popular field of research over the past decades for the construction of intriguing structures and prominent applications from catalysis to medicinal chemsitry.26-32 Desiraju and coworkers have used this type of interaction for the design and crystal engineering of organic polymers.33-34 However, the utility of halogenhalogen interactions in the construction of high dimensional PCPs for the sorption studies is still rare. Early reports have shown that halogen-halogen interactions play a major role in the assembly of high-dimensional supramolecular coordination polymers,23-25 but these interactions have not been used for the accommodation of guest species. Herein, we report four 2D CPs [Cu2(muco)2(4-clpy)2] (1), [Cu2(muco)2(4-brpy)2] (2), [Zn2(bdc)2(4-clpy)2] (3) and [Zn2(bdc)2(4brpy)2], (4) (H2muco = trans, trans-muconic acid or 1,3- butadiene-1,4-dicarboxylic acid; H2bdc = 1,4-benzene dicarboxylic acid; 4-clpy = 4-chloro pyridine and 4-brpy = 4-bromo pyridine) assembled through weak interactions to form three-dimensional (3D) aggregates. Interestingly, compounds 1 and 2 exhibit the formation of 2D PCPs which further undergo 3D supramolecular structures based on type I halogen-halogen interactions (Cl···Cl or Br···Br) and these materials show CO2 sorption properties. However, analogous compounds 3 and 4 do not have any halogen-


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halogen interactions and become non-porous towards CO2 sorption. Therefore, it appears that the halogen-halogen interactions sustain the porosity of the coordination polymers and hence their sorption behavior. Experimental Section Materials and general method All chemicals purchased were reagent grade and were used without further purification. Elemental analysis (carbon, hydrogen and nitrogen) was performed on a Perkin–Elmer 240C elemental analyzer. Infrared spectrum in KBr (4500–500 cm-1) was recorded using a Perkin– Elmer FT-IR spectrum RX1 spectrometer. Thermogravimetric analyses were recorded on a Perkin–Elmer Pyris Diamond TG/DTA in the temperature range between 30 °C and 600 °C under nitrogen atmosphere at a heating rate of 12 °C min–1. The powder XRD data was collected on a Bruker D8 Advance X-ray diffractometer using Cu Kα radiation (λ = 1.548 Å) generated at 40 kV and 40 mA. The PXRD spectrum was recorded in a 2θ range of 5–50. Synthesis of compounds 1 ̶ 4 Synthesis of compound 1: A solution of 4-clpy (0.030 g, 0.2 mmol) in MeOH (2 mL) was slowly and carefully layered to a solution of Cu(ClO4)2·6H2O (0.074 g, 0.2 mmol), in H2O (2 mL) using 2 mL 1:1 (= v/v) buffer solution of MeOH and H2O followed by layering of H2muco (0.028 g, 0.2 mmol) neutralized with Et3N (0.021 g, 0.2 mmol) in 2 mL EtOH. The blue colored block crystals of [Cu2(muco)2(4-clpy)2], 1 were obtained after three days (0.047 g, Yield 70%). Elemental analysis (%) calcd for C22H20Cl2Cu2N2O10: C 39.38, H 2.98, N 4.18; found: C 38.94, H 2.67, N 4.54. IR (KBr pellet, cm-1): 1634 νas(COO¯), 1386 νsys(COO¯).


4

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Compound 2: It was synthesized by a similar procedure as adopted for 1 using 4-brpy (0.039 g, 0.2 mmol) as auxiliary ligand instead of 4-clpy. Blue block shaped crystals [Cu2(muco)2(4brpy)2], 2 were obtained after few days. (0.057 g, Yield 75%). Elemental analysis (%) calcd for C22H20Br2Cu2N2O10: 34.76, H 2.63, N 3.68; found: C 34.57, H 2.35, N 3.96. IR (KBr pellet, cm1

): 1634 νas(COO¯), 1385 νsys(COO¯)

Compound 3: It was synthesized by a similar procedure as adopted for 1 except using Zn(NO3)2.6H2O (0.059g, 0.2 mmol) instead of Cu(ClO4)2·6H2O and H2bdc (0.016 g, 0.2 mmol) instead of H2muco. Colourless block shaped crystals of [Zn2(bdc)2(4-clpy)2], 3 were obtained after few days. (0.055 g, Yield 80%). Elemental analysis (%) calcd for C26H16Cl2Zn2N2O8: C 45.50, H 2.33, N 4.08; found: C 45.52, H 2.35, N 4.20. IR (KBr pellet, cm-1): 1638 νas(COO¯), 1393 νsys(COO¯). Compound 4: It was synthesized by a similar procedure as adopted for 3 except using 4-brpy (0.039 g, 0.2 mmol) as auxiliary ligand instead of 4-clpy. Colourless block shaped crystals of [Zn2(bdc)2(4-brpy)2], 4 were obtained after few days. (0.062 g, Yield 80%). Elemental analysis (%) calcd for C26H16Br2Zn2N2O8: C 40.28, H 2.06, N 3.62; found: C 40.20, H 2.16, N 3.38. IR (KBr pellet, cm-1): 1645 νas(COO¯), 1387 νsys(COO¯). Gas adsorption measurements The adsorption isotherms of N2 (77 K) and CO2 (195 K) were measured using the dehydrated sample of 1 and 2 in a QUANTACHROME QUADRASORB-SI analyzer. In a sample tube, adsorbent samples 1 and 2 (~100–150 mg) were placed which had been prepared at 120 °C, respectively, under 1 × 10-1 Pa vacuum for about 6 h prior to measurement of the isotherms. Helium gas (99.999% purity) at a certain pressure was introduced in the gas chamber and


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allowed to diffuse into the sample chamber by opening the valve. The amount of gas adsorbed was calculated from the pressure difference (Pcal- Pe), where Pcal is the calculated pressure with no gas adsorption and Pe is the observed pressure at equilibrium. All operations were computercontrolled and automatic. Water vapor adsorption was also measured at 298 K in the de-solvated samples of 1 and 2 by using a BELSORP Aqua-3 analyzer. Around 80 mg of samples were activated under similar conditions as mentioned earlier. Water molecules used to generate the vapor were fully degassed by repeated evacuation. The dead volume was measured with helium gas. The adsorbate was placed into the sample tube, then the change in the pressure was monitored and the degree of adsorption was determined by the decrease in pressure at the equilibrium state. All operations were computer controlled and automatic General X-ray Crystallography Single crystal of the compound 1 ̶ 4 having suitable dimensions, was used for data collection using a Bruker SMART APEX II diffractometer equipped with graphite-monochromated MoKα radiation (λ = 0.71073 Å). The molecular structure was solved using the SHELX-97 package.35 Non-hydrogen atoms were refined with anisotropic thermal parameters. Hydrogen atoms were placed in their geometrically idealized positions and constrained to ride on their parent atoms. The crystallographic data for 1 ̶ 4 are summarized in Table 1 and selected bond lengths and bond angles are given in Table S1 and S2.


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Table 1. Formula

Crystal data and refinement parameters for compounds 1 ̶ 4 C22H20Cl2Cu2N2O10

C22H20Br2Cu2N2O10

C26H16Cl2Zn2N2O8

C26H16Br2Zn2N2O8

(1)

(2)

(3)

(4)

fw

670.38

759.30

686.05

774.97

cryst syst

Monoclinic

Monoclinic

Triclinic

Triclinic

space

C2/c

C2/c

Pī

Pī

a (Å)

21.046(4)

21.2857(13)

7.7201(2)

7.7138(4)

b (Å)

11.1739(17)

11.1539(6)

9.5991(3)

9.6730(5)

c (Å)

12.1686(19)

12.4229(8)

10.8117(3)

10.8188(5)

α (deg)

90

90

115.579(2)

115.805(2)

β (deg)

101.017(10)

102.565(4)

95.223(2)

94.506(2)

γ (deg)

90

90

102.942(2)

103.448(2)

V (Å3)

2808.8(8)

2878.8(3)

688.08(4)

691.76(6)

Z

4

4

1

1

1.585

1.752

1.656

1.860

µ (mm-1)

1.758

4.306

1.989

4.673

λ (Å)

0.71073

0.71073

0.71073

0.71073

data [I >

3488/194

2701/182

2667/182

1.001

group

Dcalcd 3

(g/cm )

2549/194

2σ(I)]/par ams GOF

on

1.098

1.049

1.067

R1 = 0.0386

R1 = 0.0313

R1 = 0.0230

R1 = 0.0412

wR2 = 0.1137

wR2 = 0.0820

wR2 = 0.0593

wR2 = 0.1078

F2 final

R

indices [I > 2σ(I)]a,b a

R1 = Σ||Fo| ̶ |Fc||/ Σ|Fo|, b wR2 = [Σw(Fo2 ̶ Fc2)2/Σw(Fo2)2]1/2 on w = 1/[σ2Fo2 + (aP)2 + bP],

and P = (Fo2 + 2Fc2)/3.


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Results and Discussion Structural descriptions of [Cu2(muco)2(4-clpy)2], (1) and [Cu2(muco)2(4-brpy)2], (2) X-ray crystallography revealed that both 1 and 2 are isotypical and crystallize in the monoclinic space group C2/c with Z = 4. The asymmetric unit contains half of the formula unit. The paddle wheel [Cu2(O2C-C)4] repeating unit has a crystallographic inversion center. Each Cu(II) with distortional pentagonal pyramid geometry is bridged by four carboxylate groups of the muconate dianions. The axial positions of the Cu(II) atoms are coordinated by a 4-clpy/4brpy terminal ligand as shown in Figure 1a. The connectivity of the paddle wheel units bridged by dicarboxylate spacer ligands generates a 2D sheet structure with (4,4) square-grids as shown in Figure 1b. The lengths of the squares are 11.174 Å and 11.103 Å in 1 and 11.154 Å and 11.095 Å in 2. The axial 4-clpy/4-brpy ligands are projecting on both sides of the layer. The empty voids in the square-grids are interdigitated by the 4-clpy/4-brpy ligands from the adjacent layers. Furthermore, the halogen atoms of the terminal pyridine ligands between the first and the fourth layers form type I halogen-halogen bonds as shown in Figure 2a. The Cl···Cl distance, 3.465 Å (∠C ̶ Cl···Cl = 131.6°) in 1 (Figure 2b) and Br···Br distance of 3.529 Å in 2 (∠C ̶ Br···Br = 134.4°) are comparable to the reported distances in the literatures.36-38 The halogen-halogen interactions data of these compounds are summarized in Table S3.


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(a)

(b) Figure 1. (a) X-ray crystal structure of 1 showing a paddle-wheel building unit and (b) a portion the (4,4) net structure. If this interaction is considered as a pillar joining the layers, then the overall structure of 1 and 2 can be described as triply interpenetrated halogen-halogen pillared layer structure (Figure S1). A constricted 1D channel runs along the c-axis and the solvent-accessible void volume of the channel was estimated to be 13.3% (373.3 Å3) and 13.9% (399 Å3) of the total unit cell volume for 1 and 2 respectively calculated using the PLATON program.39-40


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(a)

(b) Figure 2. (a) A view of the 3D supramolecular aggregate of 1 by Cl···Cl interaction and (b) illustration of Cl···Cl interaction of 1st and 4th layers. Other layers are omitted for the clarity. Structural descriptions of [Zn2(bdc)2(4-clpy)2], (3) and [Zn2(bdc)2(4-brpy)2], (4) X-ray crystallography revealed that both 3 and 4 are isotypical and crystallize in the triclinic space group Pī with Z = 1. The asymmetric unit contains half of the formula unit and the paddle wheel [Zn2(O2C-C)4] repeating unit has a crystallographic inversion center. Each Zn(II) with distortional square pyramid geometry is bridged by four carboxylate groups of the benzene dicarboxylate dianions. The axial positions of the Zn(II) atoms are coordinated by a 4-clpy/4brpy terminal ligand as shown in Figure 3a.


10

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(a)

(b) Figure 3. (a) The repeating unit of 3 and (b) a portion of the (4,4) net in 3. The connectivity of the paddle wheel units bridged by dicarboxylate spacer ligands generates a 2D sheet structure with (4,4) square-grids as shown in Figure 3b. The lengths of the squares are 10.928 Å and 10.888 Å in 3 and 10.932 Å and 10.880 Å in 4. The axial 4-clpy/4-brpy ligands are projecting on both sides of the layer. The empty voids in the square-grids are interdigitated by the 4-clpy/4-brpy ligands from the adjacent layers (Figure S2). As a result, there is no solventaccessible void volume in 3. However, compound 4 has also very little void space of the channel


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estimated to be 2.1% of the total unit cell volume. Unlike 1 and 2, compounds 3 and 4 do not have any halogen-halogen interactions despite of having analogous structures. The Cl···Cl distance, 4.641 Å in 3 (Figure S3) and Br···Br distance, 4.715 Å in 4 indicate nonbonding. The layers are inter-connected through π···π interactions. The adjacent layers are stacked by π···π interactions between pyridyl ring of 4-clpy/4-brpy and phenyl ring of bdc. The shortest distance between the centroids of pyridyl and phenyl ring is 3.77 Å. TGA and PXRD analysis To check the thermal stability of the compounds, thermogravimetric analyses (TGA) were carried out in the temperature range 30 ̶ 600 °C. TGA indicate that the compounds 1 and 2 are thermally stable up to approx. 200 °C (Figure S4). However, little weight loss for PCP 1 and 2 is due to guest molecule as shown in the crystal structure. Whereas 4 and 5 do not have any guest molecule and hence, there is no weight loss upto 200 °C (Figure S5). Powder X-ray diffraction (PXRD) patterns have been carried out at room temperature. As shown in Figure S6 ̶ S7, some intensity of peaks in as-synthesized phase of 1 and 2 do not match with the simulated peaks, may be due to disordered guest molecules.41 However, PXRD patterns of as-synthesized 3 and 4 exactly match with those simulated from single crystal data indicating phase purity of the bulk (Figure S8 ̶ S9). To investigate the framework stability of PCP 1 and 2, we have done the PXRD of the desolvated compounds. However, there is no change in their diffraction patterns before and after guest removal, which suggests the framework stability. These results prompted us to investigate their sorption properties.


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Adsorption studies To reveal the porous properties of compounds 1 and 2, samples were subjected to gas (N2 and CO2) and solvent vapor (H2O) adsorption experiments. Both 1 and 2 were found to be nonporous for N2 at 77 K because of the slow diffusion rate of N2 into the micropores. But surprisingly, at 195 K both the frameworks of 1 and 2 exhibit a typical type-I profile for CO2, suggesting a microporous nature of the frameworks (Figure 4) with respect to CO2. The CO2 adsorption capacities of 1 and 2 are about 34.9 cm3g-1 and 28.7 cm3g-1, respectively. This difference between the isotherms may be attributed to deference in the pore surface, size and the shape of the frameworks. Compound 1 shows little high adsorption capacity may be due to better interactions in the confined space of pillared layer structure generated by strong chlorinechlorine interaction. Interestingly, both the compounds showed little hysteresis loops. Such hysteresis loops are often observed in PCPs upon guest accommodation due to interaction with the pore surface.42

Figure 4. CO2 sorption isotherms of PCP 1 (left) and PCP 2 (right) at 195 K: adsorption (filled circle), desorption (open circle).


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In order to check the nature of the pore surface of 1 and 2, water vapor adsorption experiments have been carried out. We observed lower adsorption of H2O in both cases of 1 and 2 (61.3cm3g1

and 56.6cm3g-1 respectively), suggesting more or less hydrophobic nature of the frameworks

(Figure 5). PCP 1 exhibits little high water adsorption capacity which is at par with the CO2 uptake profile.

Figure 5. H2O sorption isotherms of PCP 1 (left) and PCP 2 (right) at 298 K: adsorption (filled square), desorption (open square). We have carried out N2 and CO2 sorption studies of compounds 3 and 4 under similar experimental condition. However, preliminary experiments indicated that they do not show any sorption property. Conclusion In summary, 2D coordination polymers composed of paddle wheel dimeric Cu(II) units have been synthesized. The 2D layers herein stack together by the combination of a layer–layer interface via halogen-halogen interaction to form 3D structures. To the best of our knowledge, for the first time, halogen-halogen interactions have been used as tool in the construction of high


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dimensional PCPs for CO2 sorption studies. Thus, we have investigated gas sorption properties of 1 and 2 with respect to CO2 capture. This work affords an efficient method for sorption of greenhouse gas CO2 from industrial emission. Further, analogous compounds 3 and 4 with bdc linker show no halogen-halogen interactions in the frameworks and hence become non-porous towards guest molecular sorption. It appears that the retention of 3D structure by halogen…halogen interaction is related to the sorption behavior. Furthermore, this work provides us further insights for the construction of a series of 2D PCPs involving supramolecular interactions by the replacement of pyridine based ligands. SUPPORTING INFORMATION AVAILABLE Table S1 ̶ S3, Figure S1 ̶ S3, TGA, PXRD and X-ray crystallographic data in CIF format for compounds 1 ̶ 4. CCDC 1440072 (1), 1440073 (2), 1486891 (3) and 1486890 (4). This material is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author To

whom

correspondence

should

be

addressed.

E-mails:

[email protected]

and

[email protected] ACKNOWLEDGMENT This work was supported by SERB, India (Grant No. SB/FT/CS-185/2012, dated 30/07/2014) and F. A. thanks the UGC for MANF. We also acknowledge Dr. Tapas Kumar Maji, Associate Professor, Chemistry and Physics of Materials Unit & New Chemistry Unit, Jawaharlal Nehru


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37) Awwadi, F. F.; Willett, R. D.; Peterson, K. A.; Twamley, B. Chem. Eur. J. 2006, 12, 8952–8960. 38) Bui, T. T. T.; Dahaoui, S.; Lecomte, C.; Desiraju, G. R.; Espinosa, E. Angew. Chem. Int. Ed. 2009, 48, 3838 –3841. 39) Sluis, P. v. d.; Spek, A. L. Acta Crystallogr., Sect. A 1990, 46, 194–201. 40) Speck, A. L. Acta Crystallogr., Sect. D 2009, 65, 148–155. 41) Hijikata, Y.; Horike S.; Sugimoto, M.; Sato, H.; Matsuda, R.; Kitagawa, S. Chem. Eur. J. 2011, 17, 5138–5144. 42) Matsuda, R.; Kitagawa, S. Coord. Chem. Rev. 2007, 251, 2490–2509.


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For Table of Contents Use Only

Halogen···Halogen Interactions in the Supramolecular Assembly of 2D Coordination Polymers and the CO2 Sorption Behavior Faruk Ahmed,† Syamantak Roy,§ Kaushik Naskar, ║ Chittaranjan Sinha, ║ Seikh Mafiz Alam, † Suman Kundu, # Jagadese J. Vittal*‡ and Mohammad Hedayetullah Mir*†. †

Department of Chemistry, Aliah University, New Town, Kolkata 700 156, India.

§

Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific

Research, Jakkur, Bangalore 560 064, India. ║

Department of Chemistry, Jadavpur University, Jadavpur, Kolkata 700 032, India.

#

Department of Chemistry, R. K. M. Residential College, Narendrapur, Kolkata 700 103, India.

‡

Department of Chemistry, 3 Science Drive 3, National University of Singapore, Singapore 117

543, Singapore. To

whom

correspondence

should

be

addressed.

E-mails:

[email protected]

and

[email protected]


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Two 2D porous coordination polymeric sheets assembled through halogen-halogen interactions (Cl···Cl & Br···Br) generate 3D supramolecular frameworks which have suitable pore shape and surface for the uptake of CO2 gas. On the other hand, analogous compounds devoid of halogenhalogen interactions become non-porous towards CO2 sorption.


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Two 2D porous coordination polymeric sheets assembled through halogen-halogen interactions (Cl•••Cl & Br•••Br) generate 3D supramolecular frameworks which have suitable pore shape and surface for the uptake of CO2 gas. On the other hand, analogous compounds devoid of halogen-halogen interactions become non-porous towards CO2 sorption. 88x33mm (300 x 300 DPI)


HalogenÂ·Â·Â·Halogen Interactions in the ... - ACS Publications

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