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Article

Synthesis of Telmisartan Organotin(IV) Complexes and their use as Carbon Dioxide Capture Media

by
Angham G. Hadi
1,
Khudheyer Jawad
1,
Emad Yousif
2,*,
Gamal A. El-Hiti
3,*,
Mohammad Hayal Alotaibi
4 and
Dina S. Ahmed
5
1
Department of Chemistry, College of Science, Babylon University, Babil 51002, Iraq
2
Department of Chemistry, College of Science, Al-Nahrain University, Baghdad 64021, Iraq
3
Department of Optometry, College of Applied Medical Sciences, King Saud University, P.O. Box 10219, Riyadh 11433, Saudi Arabia
4
National Center for Petrochemicals Technology, King Abdulaziz City for Science and Technology, P.O. Box 6086, Riyadh 11442, Saudi Arabia
5
Department of Medical Instrumentation Engineering, Al-Mansour University College, Baghdad 64021, Iraq
*
Authors to whom correspondence should be addressed.
Molecules 2019, 24(8), 1631; https://doi.org/10.3390/molecules24081631
Submission received: 10 April 2019 / Revised: 22 April 2019 / Accepted: 24 April 2019 / Published: 25 April 2019
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Abstract

:
Novel, porous, highly aromatic organotin(IV) frameworks were successfully synthesized by the condensation of telmisartan and an appropriate tin(IV) chloride. The structures of the synthesized organotin(IV) complexes were elucidated by elemental analysis, 1H-, 13C-, and 119Sn-NMR, and FTIR spectroscopy. The surface morphologies of the complexes were inspected by field emission scanning electron microscopy. The synthesized mesoporous organotin(IV) complexes have a Brunauer–Emmett–Teller (BET) surface area of 32.3–130.4 m2·g−1, pore volume of 0.046–0.162 cm3·g−1, and pore size of around 2.4 nm. The tin complexes containing a butyl substituent were more efficient as carbon dioxide storage media than the complexes containing a phenyl substituent. The dibutyltin(IV) complex had the highest BET surface area (SBET = 130.357 m2·g−1), the largest volume (0.162 cm3·g−1), and was the most efficient for carbon dioxide storage (7.1 wt%) at a controlled temperature (323 K) and pressure (50 bars).

Graphical Abstract

1. Introduction

The emission of greenhouse gases, for example, carbon dioxide (CO2), from the increased use of fossil fuels is responsible for the increasing temperatures on the earth. A high level of CO2 in the atmosphere leads to global warming [1,2,3], which causes a disturbance in nature’s equilibrium. High CO2 levels are responsible for drastic climate changes such as melting of the ice at both the north and south poles, an increase in sea level, floods, droughts, and drastic changes in the weather. In addition, a high level of CO2 in natural gas can lead to a significant reduction of the natural gas capacity and quality [4], and can damage gas pipes through corrosion [4]. Therefore, CO2 capture is vital for both the environment and industry, and has attracted the attention of researchers in both industry and academia [5]. The scientific community is under pressure to find alternative renewable sources of energy which do not contribute to increased levels of CO2 in the environment, or to develop new processes and materials that can reduce such harmful emissions from burning fossil fuels.
Some progress has been made in the development of new materials for the capture of greenhouse gases such as CO2 [6,7,8,9,10,11,12,13,14,15,16]. Recent technology has concentrated on the selective removal of CO2 from natural gas through absorption by chemicals [17]. For example, amines such as ammonia and ethanolamine can be used to absorb CO2 from natural gas [18,19]. However, amines are hazardous and have high volatility. Unlike amines, ionic liquids can be used to absorb CO2 at high temperatures [20]; however, such an approach suffers from high energy cost for the regeneration of the ionic liquids for reuse, corrosion of containers, and the use of a large volume of water [17]. A CO2 capture approach that involves the use of membrane separation using porous materials such as polymers, metal-organic frameworks, mixed matrixes, and inorganics has been developed [21,22]. Such materials are chemically stable, have polar surfaces, large pore sizes, and large surface areas [23,24,25,26]. In addition, the adsorption process is effective, simple, and environmentally friendly. However, it is very challenging and complex because it requires high pressure, multiple stages, and extensive recycling steps. Therefore, efforts have been made to develop novel adsorbents to selectively capture CO2 from natural gas. Many chemically stable porous organic polymers have been synthesized using simple procedures and used for the capture of CO2 [6,27]. The chemical-looping combustion technique can be used to selectively remove both CO2 and H2O from the gas stream in the presence of an oxygen carrier (e.g., metal oxides) [28]. Such a process is energy cost-effective, but requires a high pressure to operate. CO2 in air could also be removed through a direct air capture technique [29]. This process involves the use of a similar concept to that used in the adsorption technique. Various resins, amine-metal oxides, metal-supported carbonates, and aqueous hydroxides have been tested for the direct capture of CO2 [30]. Clearly, progress has been made in the selective removal of CO2 from natural gas, but there is still room for further improvement.
Recently, we have shown that polyphosphates can act as an efficient CO2 capture media [31]. In addition, we have investigated the synthesis and successful use of several organotin(IV) complexes as efficient photostabilizers for polymeric films [32,33] as part of our research on polymers [34,35,36,37,38,39,40,41]. In the current work, we report the synthesis of several mesoporous organotin(IV) complexes that contain both aliphatic (butyl) and aromatic (phenyl) substituents using simple and efficient procedures, and their successful use as CO2 capture media at 323 K and 50 bars. In addition, telmisartan is highly aromatic, containing both heterocycles and aryl rings and different aliphatic substituents (methyl and propyl groups) which are essential to increase the surface area and storage capacity. To the best of our knowledge, this is the first report for the use of organotin(IV) complexes as carbon dioxide capture media which turned to be efficient as for metal-organic frameworks.

2. Results and Discussion

2.1. Synthesis of Organotin(IV) Complexes 1–4

Four organotin(IV) complexes, 1–4, were synthesized from the reaction of telmisartan and the appropriate tin(IV) chloride salts. The reaction of an equimolar mixture of telmisartan and triphenyl(IV) chloride or tributyltin(IV) chloride in methanol under reflux for 8 h gave the corresponding (telmisartan)triorganotin(IV) complex 1 or 2 in 86% and 83% yield, respectively (Figure 1). Similarly, the reaction of telmisartan (two mole equivalents) and diphenyltin(IV) chloride or dibutyltin(IV) chloride in methanol under reflux for 8 h gave the corresponding bis(telmisartan)diorganotin(IV) complex 3 or 4 in 90% and 89% yield, respectively (Figure 2). Some of the physical data for organotin(IV) complexes 1–4, along with their elemental analyses, are shown in Table 1.
Table 1 shows that the melting point for triorganotin(IV) complex 2 was noticeably higher than that for complex 2. The variation in melting could be due the high stability of complex 2 compared with that for complex 1, since it contains the flexible butyl groups compared with the bulky phenyl groups in complex 1. In contrast, diorganotin(IV) complex 3, which contains two phenyl groups, has a higher melting point compared with that for complex 4, which contains two butyl groups. For the diorganotin(IV) complexes 3 and 4, only two substituents present and the steric hindrance becomes less important compared with that for triorganotin(IV) complexes 1 and 2.

2.2. FTIR Spectroscopy of Organotin(IV) Complexes 1–4

The FTIR spectra of complexes 1–4 show characteristic peaks within the 526–536 and 445–447 cm−1 region that correspond to the vibrations of Sn–C and Sn–O groups, respectively [42]. They also show strong absorption peaks (1685–1697 cm−1) corresponding to the vibrations of the carbonyl groups. The key FTIR spectral data of complexes 1–4 are shown in Table 2 (see Supplementary Materials for details).

2.3. NMR Spectroscopy of Organotin(IV) Complexes 1–4

The structures of organotin(IV) complexes 1–4 were confirmed by NMR spectroscopy (see Supplementary Materials for details). The NMR spectra show all the expected signals at the expected chemical shifts (Table 3). However, the 13C-NMR spectra of 1–4 show the overlap of various signals within the aromatic region (Table 4). The 119Sn-NMR spectra of 1–4 show the presence of singlet signals at the –185.0 to –276.0 ppm region (Table 3), which is significantly lower than that for the corresponding organotin(IV) salts. However, the chemical shift is dependent on the geometry of the complex [43,44], and these chemical shifts are consistent with the hypothesis of an increase in the tin atom coordination number within the complexes (i.e., tin nuclear shielding) [45].

2.4. Field Emission Scanning Electron Microscopy (FESEM) of Organotin(IV) Complexes 1–4

The morphology of the synthesized organotin(IV) complexes 1–4 was inspected by FESEM. The images (Figure 3) reveal that complexes 1–4 have homogeneous and porous structures. In addition, the images show the presence of tiny particle agglomerates, and the organotin(IV) complexes have different shapes and particles sizes. The particle sizes were calculated to be 24.56–34.13, 28.66–49.66, 23.50–32.94, and 19.68–51.47 nm for complexes 1, 2, 3, and 4, respectively. Organotin(IV) complex 3 has a lower porosity and more surface smoothness than the other organotin(IV) complexes.

2.5. Pure Gas Adsorption of Organotin(IV) Complexes 1–4

The physisorption isotherms of a gas can be determined either from the amount of gas removed in the gas phase or directly from the amount of gas uptake. The latter process is based on the gravimetric measurement of the adsorbent mass change [46]. The pore textural properties of complexes 1–4 were measured from the N2 adsorption–desorption graphs recorded at 77 K. In addition, the pore size of mesoporous complexes 1–4 were calculated from the adsorption–desorption isotherms using the Barrett–Joyner–Halenda (BJH) method. Organotin(IV) complex networks 1–4 show the formation of mesoporous structures and type III nitrogen sorption isotherms. Such isotherms have no identifiable monolayer formation [31]. The N2 isotherms and pore sizes of complexes 1–4 are shown in Figure 4, Figure 5, Figure 6 and Figure 7.
The mesopore size distribution can be calculated either from the desorption or adsorption branch of the isotherm. Organotin(IV) complexes 1–4 have small mesopores with consistent pore sizes (2.428–2.433 nm). Organotin(IV) complex 4 has the highest Brunauer–Emmett–Teller surface area (SBET = 130.357 m2·g−1) and the largest volume (0.162 cm3·g−1) of the organotin(IV) complexes. The porosity properties of complexes 1–4 are listed in Table 5.
The sorption of complexes 1–4 was investigated at a constant temperature (323 K) and pressure (50 bars). The sorption isotherms of CO2 and H2 in the presence of complexes 1–4 are shown in Figure 8, Figure 9, Figure 10 and Figure 11 and the gas uptakes are listed in Table 6. Complexes 1–4 showed a high CO2 uptake, possibly as a result of the strong van der Waals interaction between such complexes and CO2. The quantity of adsorbed CO2 was 18.2, 20.5, 16.5, and 35.0 cm3·g−1 for complexes 1, 2, 3, and 4, respectively. Clearly, complex 4 has the highest CO2 uptake capacity (7.1 wt%) of the organotin(IV) complexes, possibility because it has the largest BET surface area (SBET = 130.357 m2·g−1). In addition, strong hydrogen bonding and/or dipole-quadrupole interactions between CO2 and heteroatoms within the organotin(IV) complexes could take place [47]. Indeed, porous organic polymers containing oxygen, nitrogen, or sulfur atoms are efficient for the selective capture of CO2 over other gases such methane and nitrogen [48,49,50]. However, complexes 1–4 show very low adsorption for H2 (0.5–1.1 cm3·g−1) under identical conditions to those used for the CO2 uptake. Such behavior could be due to the weak interaction between the complexes and H2.
Complexes 1–4 have different geometries and substitution groups (phenyl and butyl), and therefore showed varied gas capture efficiency. It is clear that the butyl-substituted complexes (2 and 4) have better storage capacities than the phenyl-substituted complexes (1 and 3). The butyl group is flexible and leads to a larger surface area in complexes 2 and 4 (SBET = 68.357–130.357 m2·g−1) compared with that of phenyl-substituted complexes 1 and 3 (SBET = 32.374–46.338 m2·g−1). In complex 4, the flexible substitution unit (butyl group) points into the channels and leads to the formation of a molecular gate for gas adsorption [51]. It has been reported that the inclusion of alkyl chain substituents within the metal-organic frameworks can be used to tune the pores size to allow a better accommodation of gas molecules within the pores [12,52].

3. Materials and Methods

3.1. General

Chemicals were purchased from Merck (Schnelldorf, Germany). FTIR spectra (400–4000 cm−1) were recorded on an FTIR 8300 Shimadzu spectrophotometer (Tokyo, Japan) using KBr discs. An EM-017mth instrument was used to perform the elemental analyses. An MPD Mitamura Riken Kogyo apparatus (Tokushima, Japan) was used to determine melting points. 1H-(300 MHz), 13C-(75 MHz), and 119Sn-(107 MHz) NMR spectra were recorded on a Bruker DRX300 NMR spectrometer (Zurich, Switzerland). The FESEM images were recorded on a TESCAN MIRA3 FESEM system (Kohoutovice, Czech Republic) at an accelerating voltage of 26 kV. A Quantchrome chemisorption analyzer was used to record the nitrogen adsorption–desorption isotherms (77 K). The samples were dried at a vacuum oven 70 °C for 6 h under a flow of nitrogen. The pore volumes were determined at a relative pressure (P/P°) of 0.98. The BJH method was used to verify the pore size distributions. Gas uptakes were performed on an H-sorb 2600 high pressure volumetric adsorption analyzer (Beijing, China) at 50 bars and 323 K.

3.2. Synthesis of Triorganotin(IV) Complexes 1 and 2

A solution of telmisartan (0.51 g, 1.0 mmol) in chloroform (20 mL) was added slowly to a stirred solution of triphenyl or tributyltin chloride (1.0 mmol) in ethanol (10 mL) and the mixture was refluxed for 8 h. The solid obtained upon cooling was collected and recrystallized from methanol to give triorganotin(IV) 1 or 2.

3.3. Synthesis of Diorganotin(IV) Complexes 3 and 4

A solution of telmisartan (1.03 g, 2.0 mmol) in chloroform (30 mL) was added slowly to a stirred solution of diphenyl or dibutyltin chloride (1.0 mmol) and the mixture was refluxed for 8 h. The solid obtained upon cooling was collected and recrystallized from methanol to give diorganotin(IV) 3 or 4.

4. Conclusions

Four new organotin(IV) complexes containing telmisartan were synthesized and their structures were confirmed. The organotin(IV) complexes have predominantly mesoporous and heteroatom-rich structures. The performance and affinity of the tin complexes for carbon dioxide gas uptake were highly efficient compared with the performance and affinity for hydrogen gas uptake under the conditions used. The dibutyl organotin(IV) complex was the most efficient carbon dioxide storage medium, having a CO2 gas uptake up to 7.1 wt% at 323 K and 50 bar. However, the toxicity and degradability of such a complex, as well as the environmental accumulation of telmisartan, should be tested.

Supplementary Materials

The following are available online.

Author Contributions

Conceptualization and experimental design, A.G.H., K.J., E.Y., G.A.E.-H., and M.H.A.; Experimental work and data analysis, D.S.A; Writing, E.Y., G.A.E.-H., and D.S.A. All authors discussed the results and improved the final text of the paper.

Funding

The authors would like to extend their appreciation to the College of Applied Medical Sciences Research Centre and the Deanship of Scientific Research at King Saud University for their funding of this research, and to Al-Nahrain and Babylon Universities for the continued support.

Conflicts of Interest

The authors declare no conflicts of interest.

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Sample Availability: Samples of the telmisartan organotin (IV) complexes are available from the authors.
Molecules 24 01631 g001 550
Figure 1. Synthesis of triorganotin(IV) complexes 1 and 2.
Figure 1. Synthesis of triorganotin(IV) complexes 1 and 2.
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Figure 2. Synthesis of diorganotin(IV) complexes 3 and 4.
Figure 2. Synthesis of diorganotin(IV) complexes 3 and 4.
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Figure 3. Field emission scanning electron microscopy (FESEM) images of 1–4.
Figure 3. Field emission scanning electron microscopy (FESEM) images of 1–4.
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Figure 4. N2 isotherms and pore diameters of 1.
Figure 4. N2 isotherms and pore diameters of 1.
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Figure 5. N2 isotherms and pore diameters of 2.
Figure 5. N2 isotherms and pore diameters of 2.
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Figure 6. N2 isotherms and pore diameters of 3.
Figure 6. N2 isotherms and pore diameters of 3.
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Figure 7. N2 isotherms and pore diameters of 4.
Figure 7. N2 isotherms and pore diameters of 4.
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Figure 8. Adsorption isotherms of CO2 and H2 for complex 1.
Figure 8. Adsorption isotherms of CO2 and H2 for complex 1.
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Figure 9. Adsorption isotherms of CO2 and H2 for complex 2.
Figure 9. Adsorption isotherms of CO2 and H2 for complex 2.
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Figure 10. Adsorption isotherms of CO2 and H2 for complex 3.
Figure 10. Adsorption isotherms of CO2 and H2 for complex 3.
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Figure 11. Adsorption isotherms of CO2 and H2 for complex 4.
Figure 11. Adsorption isotherms of CO2 and H2 for complex 4.
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Table
Table 1. Physical properties and elemental analysis of 1–4.
Table 1. Physical properties and elemental analysis of 1–4.
Sn(IV) ComplexRColorYield (%)Melting Point (°C)Calcd. (Found; %)
CHN
1Phpale yellow86163–16570.93 (71.12)5.14 (5.13)6.49 (6.36)
2Buwhite83243–24567.25 (67.46)7.02 (7.11)6.97 (7.06)
3Phoff white90237–23972.06 (71.97)5.27 (5.36)8.62 (8.63)
4Buoff white89184–18670.53 (70.41)6.08 (5.98)8.89 (9.00)
Table
Table 2. Key FTIR spectral data of complexes 1–4.
Table 2. Key FTIR spectral data of complexes 1–4.
Sn(IV) ComplexFTIR (ν, cm−1)
C=OC=NC=CSn–CSn–O
1168515411455526447
2169715401458528447
3169715431456536445
4169715361454536447
Table
Table 3. 1H- and 119Sn-NMR spectral data (ppm, DMSO-d6) of complexes 1–4.
Table 3. 1H- and 119Sn-NMR spectral data (ppm, DMSO-d6) of complexes 1–4.
Sn(IV) Complex1H-NMR119Sn-NMR
11.00 (t, J = 7.6 Hz, 3H, Me), 1.83 (quintet, J = 7.6 Hz, 2H, CH2), 2.61 (s, 3H, Me), 3.17 (m, 2H, CH2), 3.81 (s, 3H, Me), 5.62 (s, 2H, CH2), 7.26–7.86 (m, 29H, Ar)–193.0
20.90 (t, J = 7.5 Hz, 9H, 3 Me), 0.99 (t, J = 7.7 Hz, 3H, Me), 1.23 (m, 6H, 3 CH2), 1.46 (m, 6H, 3 CH2), 1.58 (m, 6H, 3 CH2), 1.86 (quintet, J = 7.7 Hz, 2H, CH2), 2.63 (s, 3H, Me), 2.92 (t, J = 7.7 Hz, 2H, CH2), 3.39 (s, 3H, Me), 5.63 (s, 2H, CH2), 7.26–7.74 (m, 14H, Ar)–185.0
31.02 (t, J = 7.5 Hz, 6H, 2 Me), 1.83 (quintet, J = 7.5 Hz, 4H, 2 CH2), 2.63 (s, 6H, 2 Me), 2.93 (t, J = 7.5 Hz, 4H, 2 CH2), 3.40 (s, 6H, 2 Me), 5.63 (s, 4H, 2 CH2), 7.28–7.73 (m, 38H, Ar)–267.0
40.94–1.01 (m, 12H, 4 Me), 1.21–1.31 (m, 8H, 4 CH2), 1.79–1.83 (m, 8H, 4 CH2), 2.63 (s, 6H, 2 Me), 2.91 (t, J = 7.7 Hz, 4H, 2 CH2), 3.80 (s, 6H, 2 Me), 5.61 (s, 4H, 2 CH2), 7.21–7.86 (m, 28H, Ar)–242.5
Table
Table 4. 13C-NMR Spectral data (ppm, DMSO-d6) of complexes 1–4.
Table 4. 13C-NMR Spectral data (ppm, DMSO-d6) of complexes 1–4.
Sn(IV) Complex13C-NMR
1168.3 (C=O), 156.7, 154.4, 143.1, 142.6, 141.3, 140.6, 137.0, 136.6, 136.4, 136.3, 135.2, 130.9, 129.8, 129.4, 128.6, 127.8, 126.8, 123.7, 122.7, 122.3, 119.1, 110.8, 109.7, 46.6 (CH2), 32.2 (Me), 29.2 (CH2), 21.2 (CH2), 16.9 (Me), 14.3 (Me)
2171.0 (C=O), 156.6, 154.5, 143.2, 142.5, 137.0, 136.4, 135.2, 130.8, 129.6, 129.2, 128.7, 128.1, 127.8, 126.8, 123.7, 122.6, 119.1, 110.4, 109.8, 46.0 (CH2), 32.2 (Me), 29.2 (CH2), 28.4 (CH2), 28.2 (CH2), 26.7 (CH2), 21.2 (CH2), 16.9 (Me), 14.3 (Me), 14.1 (Me)
3170.0 (C=O), 156.7, 154.4, 142.5, 141.5, 140.9, 140.7, 136.9, 136.4, 135.2, 132.7, 131.3, 130.8, 129.6, 129.2, 128.8, 127.7, 126.9, 123.7, 122.7, 122. 5, 119.0, 111.0, 109.9, 46.6 (CH2), 32.3 (Me), 29.2 (CH2), 21.2 (CH2), 16.9 (Me), 14.3 (Me)
4169.6 (C=O), 156.6, 154.5, 143.2, 142.9, 141.0, 140.8, 137.1, 136.3, 135.2, 133.1, 130.1, 129.8, 129.4, 128.6, 127.8, 126.8, 126.8, 123.7, 122.7, 119.1, 110.8, 109.4, 46.6 (CH2), 32.2 (Me), 30.8 (CH2), 29.2 (CH2), 27.3 (CH2), 26.1 (CH2), 21.2 (CH2), 16.9 (Me), 14.3 (Me), 13.9 (Me)
Table
Table 5. Porosity properties of complexes 1–4.
Table 5. Porosity properties of complexes 1–4.
Sn(IV) ComplexSBET (m2·g−1) aVtotal (cm3·g−1) bPore Size (nm) c
146.3380.0622.433
268.4340.0972.428
332.3740.0462.432
4130.3570.1622.429
a Brunauer–Emmett–Teller (BET) surface area; b pore volume was calculated at a relative pressure (P/Po) of 0.98 from the nitrogen adsorption isotherm; c Barrett–Joyner–Halenda (BJH) average pore diameter was calculated from the desorption data.
Table
Table 6. Gas uptake capacities at 323 K and 50 bars of complexes 1–4. a
Table 6. Gas uptake capacities at 323 K and 50 bars of complexes 1–4. a
Sn(IV) ComplexCO2 Uptake (cm3·g−1)CO2 Uptake (wt%)H2 Uptake (cm3·g−1)H2 Uptake (wt%)
118.23.61.10.009
220.54.00.70.006
316.53.30.50.006
435.07.11.10.013
a Data were collected by the volumetric gas sorption method.

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Hadi, A.G.; Jawad, K.; Yousif, E.; El-Hiti, G.A.; Alotaibi, M.H.; Ahmed, D.S. Synthesis of Telmisartan Organotin(IV) Complexes and their use as Carbon Dioxide Capture Media. Molecules 2019, 24, 1631. https://doi.org/10.3390/molecules24081631

AMA Style

Hadi AG, Jawad K, Yousif E, El-Hiti GA, Alotaibi MH, Ahmed DS. Synthesis of Telmisartan Organotin(IV) Complexes and their use as Carbon Dioxide Capture Media. Molecules. 2019; 24(8):1631. https://doi.org/10.3390/molecules24081631

Chicago/Turabian Style

Hadi, Angham G., Khudheyer Jawad, Emad Yousif, Gamal A. El-Hiti, Mohammad Hayal Alotaibi, and Dina S. Ahmed. 2019. "Synthesis of Telmisartan Organotin(IV) Complexes and their use as Carbon Dioxide Capture Media" Molecules 24, no. 8: 1631. https://doi.org/10.3390/molecules24081631

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