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CO2 and iodine uptake properties of Co(II)-coordination polymer constructed from tetracarboxylic acid and flexible bis(imidazole) linker Mürsel Ar#c#, Okan Zafer Yesilel, Murat Ta#, and Hakan Demiral Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b00171 • Publication Date (Web): 03 Apr 2017 Downloaded from http://pubs.acs.org on April 4, 2017

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Crystal Growth & Design

CO2 and iodine uptake properties of Co(II)-coordination polymer constructed from tetracarboxylic acid and flexible bis(imidazole) linker Mürsel Aricia,*, Okan Zafer Yeşilela, Murat Taşb and Hakan Demiralc a

Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University,

26480 Eskişehir, Turkey b

Department of Science Education, Education Faculty, Ondokuz Mayıs University, 55139,

Samsun, Turkey c

Department of Chemical Engineering, Faculty of Engineering and Architecture, Eskişehir

Osmangazi University, 26480 Eskişehir, Turkey

ABSTRACT: New coordination polymer, formulated as {[Co2(µ8-abtc)(betib)]·DMF}n (1) (abtc= 3,3′,5,5′-azobenzenetetracarboxylate, betib: 1,4-bis(2-ethylimidazol-1-yl)butane), was synthesized with 3,3′,5,5′-azobenzenetetracarboxylic acid and flexible betib ligand. Complex 1 was immersed in methanol to obtain {[Co2(µ8-abtc)(betib)]·H2O}n (2). The complexes were characterized by IR spectra, elemental analyses, single-crystal and powder X-ray diffractions and thermal analyses. X-ray results demonstrated that complexes 1 and 2 were porous 3D framework with sqc5381 net. Complex 2 was activated at 105 oC (2a) and CO2 and iodine adsorption properties of 2a were studied. The CO2 uptake capacity of 2a was 52.94 cm3/g (10.40 %). Moreover, complex 2a encapsulated the 30.34 % and 21.98 % iodine in the vapor phase and solution, respectively, which corresponded to 1.975 and 1.42 molecules of iodine per formula units, respectively. Keywords: Azobenzenetetracarboxylate; coordination polymer; CO2 adsorption; iodine encapsulation.

1 ACS Paragon Plus Environment


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1. INTRODUCTION Porous coordination polymers with the permanent porosity have attracted interest not only their potential applications in especially gas storage/separations, iodine adsorption, sensor, catalysis, luminescence and drug delivery, so on, but also because of their intriguing structural topologies1-13. Especially, the adsorption of CO2 which gives rise to global warming with porous coordination polymers has attracted great attention for the cleaner environment 14, 15

. Moreover, iodine uptake with porous coordination polymers has been widely examined

due to fact that iodine and its isotopes are not only used for beneficial applications but also some iodine isotopes are dangerous for health. Hence, iodine and its isotopes need to be safely storage

5,

15,

16

. In the design and construction of porous coordination polymers,

polycarboxylate and/or N-donor ligands and have been widely employed17,

18

. Though

appropriate ligands and metal ions to obtain porous coordination polymers, it is still great challenge to expect the final structure depending on reaction conditions in the self-assembly19, 20

. The secondary building units (SBUs) are highlighted to obtain porous and robust structures

and play important role to estimate final structures20, 21. Recently, the mixed-ligand coordination polymers based on multi-carboxylate and Ndonor ligands have been drawn attention to tune the structural frameworks. In this study, as a multi-carboxylate ligand, 3,3′,5,5′-azobenzenetetracarboxylic acid, a symmetric rigid ligand, and binding to metal ions with four carboxylate groups in diverse coordination modes, was used22-24. In the mixed-ligand approach, flexible 1,4-bis(2-ethylimidazol-1-yl)butane was employed as a N-donor secondary ligand. Flexible bis(imidazole) linkers can offer variable configurations to supply the coordination requirements of metal ions20. Taking inspiration from the above considerations, the mixed-ligand Co(II) coordination polymer, namely {[Co2(µ8-abtc)(betib)]·DMF}n (1) was synthesized with 3,3′,5,5′-azobenzenetetracarboxylic acid (H4abtc) and 1,4-bis(2-ethylimidazol-1-yl)butane (betib). {[Co2(µ8-abtc)(betib)]·H2O}n


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(2) was prepared from complex 1 which was immersed in methanol for one week. They were characterized by elemental analysis, IR spectra, single crystal X-ray diffraction and powder X-ray diffraction (PXRD) as well as thermal analysis techniques. Moreover, BET surface area, CO2 and I2 adsorption properties were examined.

2. MATERIALS AND PHYSICAL MEASUREMENTS All materials and solvents were commercially available and were used without further purification. H4abtc25 and betib8,

20

ligands were synthesized according to literatures. IR

spectra were recorded with a Bruker Tensor 27 FT−IR spectrometer by KBr pellets in the range

4000−400

cm−1. UV-vis

spectra

were

recorded

by

Shimadzu

UV-2600

spectrophotometer in the wavelength range 200–800 nm. Elemental analyses (CHN) were performed on a Perkin-Elmer 2400C Elemental Analyzer. Powder X-ray diffraction (PXRD) patterns were collected by a Rikagu Smartlab X-ray diffractometer with Cu-Kα radiation (λ= 1.5406 nm) operating at 40 kV and 30 mA in the range 5-50o 2θ at a rate of 5°/min. Thermogravimetric analyses were carried on a Perkin Elmer Diamond TG/DTA Thermal Analyzer with a heating rate of 10 °C/min in the static air atmosphere. Topological analyses were performed using ToposPro software26. N2 and CO2 adsorption measurements were carried out with Quantachrome Autosorb 1-C device at 77 K and 273 K, respectively. Diffraction data of 1 and 2 were collected on a Bruker Smart Apex II CCD equipped with Mo-Kα (0.71073 Å). The structures were solved by SHELXS and refined by full-matrix leastsquares on all F2 data using SHELXL in conjunction with the OLEX2 graphical user interface 27, 28

. For all complexes, the anisotropic thermal parameters were refined for non-hydrogen

atoms and hydrogen atoms were calculated and refined with a riding model. The aliphatic parts of compounds showed positional disorder, the disordered atoms were divided two parts



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by dealt with the peaks of diffraction maps. Molecule drawings were carried out with Mercury program 29. 2.1 Syntheses of the complexes {[Co2(µ8-abtc)(betib)]·DMF}n (1) A mixture of Co(NO3)2·6H2O (0.162 g, 0.558 mmol), H4abtc (0.10 g, 0.279 mmol) and betib (0.068 g, 0.279 mmol) was stirred at room temperature in the mixture of DMF:H2O (10:2, v:v, mL) for 30 min. Then, HNO3 (6.0 M, 3 drops) was added into the mixture to obtain a clear solution. The clear solution was sealed in a glass bottle (25 mL) and heated at 95 oC for 3 days to obtain blue crystals. Yield: 0.135 g, 61 % (based on H4abtc). Anal. Calcd. for C33H35Co2N7O9: C, 50.07; H, 4.46; N, 12.39 %. Found: C, 50.48; H, 4.75; N, 11.89 %. IR (KBr, cm–1): 3134 w, 3072 w, 2974 w, 1637 vs, 1521 w, 1452 s, 1385 vs, 14257 m, 1346 vs, 785 m, 717 m, cm-1. {[Co2(µ8-abtc)(betib)]·H2O}n (2) Complex 2 was obtained from complex 1 which was immersed in methanol for one week. After one week, crystals were filtered and dried in open atmosphere. Anal. Calcd. for C15H16CoN3O5: C, 47.76; H, 4.28; N, 11.14 %. Found: C, 47.98; H, 4.48; N, 11.12 %. IR (KBr, cm–1): 3427 m, 3138 w, 3074 w, 2976 w, 2937 w, 1637 vs, 1574 m, 1498 m, 1454 s, 1385 vs, 1261w, 785 m, 719 m, cm-1. 3. RESULTS AND DISCUSSION 3.1 Synhesis and Characterization Complex 1 was synthesized by the reaction of Co(NO3)2·6H2O, H4abtc and betib ligands. Complex 1 was immersed in methanol for one week to change DMF molecule to methanol for activation. After removal of methanol, 1 was dried in room temperature. Again, crystal data of 1 was collected to obtain complex 2. Interestingly, water molecule was found in the pore of complex. This situation may be due to 95 % methanol or moisture of room.


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Elemental analysis results of complexes 1 and 2 are consistent with the single crystal X-ray results. IR spectra of the complexes are similar. In the IR spectrum of complex 2, the broad pick observed at 3427 cm-1 is assigned to ν(O-H) stretching vibration of water molecule. The bands observed at 1710 and 1278 cm-1 are attributed to asymmetric and symmetric stretching vibrations of carboxylate groups of H4abtc ligand, respectively. The asymmetric stretching vibration of H4abtc is shifted to lower frequency after converting to complex 1, demonstrating the full deprotonation of carboxylate groups of H4abtc. The asymmetric and symmetric stretching vibrations corresponding to carboxylate groups of 1 and 2 are observed at 1637 cm1

and 1385 cm-1, respectively. The weak peaks appearing between at 3138 and 2937 cm-1 are

due to aromatic and aliphatic ν(C–H) stretching vibrations. Description of crystal structures The crystal data and the refinement details of complexes are given in Tables 1. Selected bond distances and angles are listed in Tables S1 and S2, respectively. Crystal structures of complexes 1 and 2 are similar. They crystallize in the monoclinic system with the space group C2/c. There are one Co(II) ion, half abtc anion, half betib ligand and one DMF molecule in the asymmetric unit of complex 1 while the asymmetric unit of complex 2 contains one Co(II) ion, half abtc anion, half betib ligand and one water molecule. Each Co(II) ion adopts a distorted [CoO4N] distorted square pyramidal geometry (τ5 = 0.0077 for 1 and 0.0047 for 2) by coordinating to four carboxylate oxygen atoms from four different abtc ligands and one nitrogen atom from one betib ligand30 (Fig. 1). The Co-N1 bond lengths for 1 and 2 are 2.048 and 2.032 Å, respectively. Each abtc ligand acts an octadentate ligand to connect to eight Co(II) center in 1 and 2 and 3,3′,5,5′-carboxyl groups exhibit bidentate bridging modes. A pair of Co(II) ions is connected by four carboxylate oxygen atoms to form paddle-wheel {Co2(CO2)4} SBUs with the Co···Co distances of 2.963 Å for 1 and 3.066 Å for 2, respectively. Each {Co2(CO2)4} is connected by four different abtc ligands to form 3D



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framework. In the complexes, betib ligand and 3,3′-carboxylate oxygen atoms bridge two Co(II) ions to generate 1D hexagonal channels with size of 10.102 × 8.389 Å2 for 1 and 10.139 × 9.105 Å2 for 2, respectively (Fig. 2a). Topologically, complexes 1 and 2 have 3,6connected sqc5381 net with the point symbol of {42.6}2{44.66.85} (Fig. 2b)

3.2 Powder X-ray Diffraction and Thermal analysis Results PXRD patterns were recorded to check the phase purities of bulk materials (Fig. S1). Experimental PXRD patterns of complexes 1 and 2 are matched well with the simulated XRD patterns obtained from their single-crystal structures, indicating the phase purities of the complexes. Thermal analyses were carried out in order to determine divergence temperatures of solvent molecules in pores for gas and iodine sorption properties and thermal stabilities of the complexes (Fig. 3). For complexes 1 and 2, first steps are related to removal of solvent molecules with the weight losses of 9.80 % and 2.98 %, respectively (calc.: 9.24 % for 1; 2.98 % for 2). After removal of solvents in the pores, on further heating, the frameworks were decomposed with the exothermic peaks. The final products of 1 and 2 with the weights of 18.89 % and 19.45 % are CoO (calcd.: 18.93 % for 1 and 19.86 % for 2), respectively. 3.3 Gas sorption property Before the gas adsorption measurements, complex 1 was immersed in methanol to obtain complex 2 for one week and then heated at 105 oC for 12 h under vacuum to obtain fully activated complex 2a (Fig. 4a). PXRD pattern of 2a showed the robustness of framework because most of peaks were similar to PXRD pattern of complex 2. N2 adsorption measurement was performed at 1.0 bar and 77 K to determine the porosity of framework. BET surface area of 2a is 30.19 m2/g. Complex 2a seems to be nonporous. However, CO2 adsorption measurement obtained volumetrically at 1.0 bar and 273 K exhibits typical type-I


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isotherms, indicating the microporosity of the complex (Fig. 5). The CO2 uptake capacity of 2a is 52.94 cm3/g (10.40 %) despite the low BET surface area. The CO2 uptake result is higher than some MOFs, like MOF-5 (6.2 %), MOF-602 (5.0 %), SNU-15 (7.0 %) and CuTUH (7.3 %) at 1 bar and 273 K15, 31-35. 3.4 Iodine uptake and release Complex 2a was used for iodine uptake and release experiments both in vapor phase and in solvent. In vapor phase, 25 mg of complex 2a was exposed to I2 vapor at 75 oC for 3 days in close caped tube to obtain 2a@I2 (vapor). Three days later, 2a@I2 (vapor) was washed with cyclohexane to remove I2 residing on sample surface. The amount of iodine uptake of 2a@I2 (vapor) was calculated by thermal analysis which showed 30.62 wt % loss. (Fig. 6) Moreover, TG result was supported by elemental analysis (30.34 wt % iodine uptake) (Table 2). These can be attributed to 1.975 molecules of I2 per formula unit of 2a.This result is higher than some reported coordination polymers related to I2 uptake in vapor phase5, 36-39. Moreover, 25 mg of complex 2a was immersed in 3.0 mL (0.01 M) I2 cyclohexane solution for 48h to obtain 2a@I2 (solvent). The dark brown solution of I2 fade slowly to red after 48 h (Fig. S2). I2 encapsulated 2a@I2 (solvent) was filtered and washed with cyclohexane to remove I2 residing on crystal surfaces. In solvent, the amount of iodine uptake calculated by thermal analysis was 21.98 wt % which corresponded to 1.42 molecules of iodine per formula unit of 2a (Fig. 6). This result was also supported by elemental analysis (21.69 wt % iodine uptake) (Table 2). PXRD patterns and IR spectra of 2a@I2 (vapor) and 2a@I2 (solvent) were recorded to investigate the interaction between 2a and I2 (Fig. 4). The stability of iodine molecules within the framework pores can be assigned to weak interactions (π···I interaction between iodine and imidazole rings and C-H···I interaction between iodine and 2-ethyl substitute



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group of imidazole ring) 36. PXRD patterns and IR spectra of complexes 2a, 2a@I2 (vapor) and 2a@I2 (solvent) are in good agreements which indicate the host-guest (weak) interaction.

The iodine release from 2a@I2 (in both vapor and solution) immersed in EtOH was followed by naked-eye and UV-Vis spectra at room temperature (Fig. 7). UV-Vis spectra of iodine release show the absorption bands at 230, 290, 360 and 442 nm in ethanol. The intensity of absorption band at 230 nm is related to concentration of iodine and the others are due to polyiodide40,

41

. UV-Vis spectra of iodine in ethanol show that the delivery of I2

increases with time (Fig. S3). The recyclability of 2a for the iodine adsorption and release was studied up to five cycles (Fig. S4). For this purpose, 25 mg of 2a was immersed in I2 cyclohexane solution for one day (2a@I2) then iodine release from 2a@I2 immersed in EtOH was followed by UV-Vis spectra. After five cycles, UV-Vis spectra of iodine in ethanol showed that I2 release did not change significantly. I2 adsorption-desorption process is reversible and conducted by the host-quest interaction. 4. CONCLUSIONS In this study, Co(II)-coordination polymer (1) with 3,3′,5,5′-azobenzenetetracarboxlate and flexible betib ligands was synthesized and structurally characterized. DMF molecule in the pore of complex 1 was changed to H2O molecule (complex 2) after immersed in methanol for one week at room temperature. Complex 2 was activated at 105oC and the CO2 and I2 adsorption properties were also studied. Activated complex 2 showed the CO2 adsorption (10.40 %) at 1.0 bar 273 K despite the low surface area. Moreover, activated complex 2 displayed high iodine uptake in the vapor phase and solution and encapsulated iodine can be released in ethanol solution. The results showed that Co(II)-coordination polymer could be utilized for CO2 adsorption and iodine uptake.


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Supporting Information PXRD patterns and UV-Vis spectra and tables for bond distances and angles of complexes 1 and 2. Crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic Data Centre, CCDC No 1486587 and 1486588 for 1 and 2, respectively. Copies of this information may be obtained free of charge from the Director, CCDC, 12 Union

Road,

Cambridge

CB2

1EZ,

UK

(fax:

+44-1223-336033;

[email protected] or www: http://www.ccdc.cam.ac.uk) This material is available free of charge via the Internet at http://pubs.acs.org. *Corresponding Author: E–mail: [email protected] Tel: +902222393750, Fax: +902222393578


e-mail:


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Table and Figure Captions Table 1. Crystal data and structure refinement parameters for complexes 1 and 2

Table 2. Elemental analysis results after iodine uptake in vapor and solvent Fig. 1. The molecular structures of 1 (a) and 2 (b) showing the atom numbering scheme Fig. 2. (a) Space-filling mode of 3D structure in 1 and 2 (b) a view of 3D (3,6)-connected sqc5381 net Fig. 3. TG analyses of complexes 1, 2 and 2a Fig. 4. (a) PXRD patterns of complexes 2, 2a and I2 capsulated complex 2a (in vapor and solvent) (b) IR spectra of complexes 2a and I2 capsulated complex 2a (in vapor and solvent) Fig. 5. CO2 adsorption-desorption isotherms for complex 2a at 273 K Fig. 6. TG curves of 2a, 2a@I2 (vapor) and 2a@I2 (solvent) Fig. 7. Photographs of I2 release from 2a@I2 in ethanol solution



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Table 1. Crystal data and structure refinement parameters for complexes 1 and 2 Crystal data

1

2

C33H35Co2N7O9

C15H16CoN3O5

Formula weight

791.54

377.24

Crystal system

Monoclinic

Monoclinic

C2/c

C2/c

a (Å)

27.625 (2)

27.574

b (Å)

9.9064 (8)

9.776

c (Å)

15.5403 (12)

15.557

α (º)

90.00

90.00

β (º)

119.742 (3)

119.48

90.00

90.00

3692.6 (5)

3650.9

4

8

1.424

1.373

0.96

0.97

3.0-28.3

3.0-28.3

Measured refls.

16972

54164

Independent refls.

3572

4546

Rint

0.026

0.044

S

1.09

1.08

0.089/0.255

0.070/0.200

3.13/-2.02

2.14/-2.02

Empirical formula

Space group

γ (º) 3

V (Å ) Z -3

Dc (g cm ) -1

µ (mm ) θ range (º)

R1/wR2 ∆ρmax/∆ρmin (eÅ-3)


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Table 2. Elemental analysis results after iodine uptake in vapor and solvent Complexes

C%

H%

N%

2a@I2 (vapor)

1.975 I2

20.58 (20.91)

1.84 (1.75)

4.66 (4.88)

2a@I2 (solvent)

1.42 I2

24.69 (25.00)

2.26 (2.10)

5.57 (5.83)

Theoretical results were given in brackets.



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(a) (b) Fig. 1. The molecular structures of 1 (a) and 2 (b) showing the atom numbering scheme


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(a) (b) Fig. 2. (a) Space-filling mode of 3D structure in 1 and 2 along the c*-axis (b) a view of 3D (3,6)-connected sqc5381 net along the a-axis



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Fig. 3. TG analyses of complexes 1, 2 and 2a


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(a) (b) Fig. 4. (a) PXRD patterns of complexes 2, 2a and I2 capsulated complex 2a (in vapor and solvent) (b) IR spectra of complexes 2a and I2 capsulated complex 2a (in vapor and solvent)



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Fig. 5. CO2 adsorption-desorption isotherms for complex 2a at 273 K


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Fig. 6. TG curves of 2a, 2a@I2 (vapor) and 2a@I2 (solvent)



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Fig. 7. Photographs of I2 release from 2a@I2 in ethanol solution


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For Table of Contents Use Only

CO2 and iodine uptake properties of Co(II)-coordination polymer constructed from tetracarboxylic acid and flexible bis(imidazole) linker Mürsel Aricia,*, Okan Zafer Yeşilela and Murat Taşb, Hakan Demiralc

In this study, Co(II)-coordination polymer (1) with 3,3′,5,5′-azobenzenetetracarboxlate and flexible 1,4-bis(2-ethylimidazol-1-yl)butane ligands was synthesized. Complex 1 was immersed in methanol to obtain complex 2. They were structurally characterized. Complexes 1 and 2 possessed 3D structures with sqc5381 net. Complex 2 was activated at 105 oC (2a) and the CO2 uptake capacity of 2a was 52.94 cm3/g (10.40 %). Complex 2a displayed 30.34 % and 21.98 % iodine uptake in the vapor phase and solution, respectively, and reversibly released iodine in ethanol solution.


CO2 and Iodine Uptake Properties of Co(II ... - ACS Publications

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