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. 2019 Nov 15;141(48):18949–18953. doi: 10.1021/jacs.9b10741

Selective Separation of Polyaromatic Hydrocarbons by Phase Transfer of Coordination Cages

Dawei Zhang 1, Tanya K Ronson 1, Roy Lavendomme 1, Jonathan R Nitschke 1,*
PMCID: PMC6900757  PMID: 31729877

Abstract

graphic file with name ja9b10741_0006.jpg

Here we report a new supramolecular strategy for the selective separation of specific polycyclic aromatic hydrocarbons (PAHs) from mixtures. The use of a triethylene glycol-functionalized formylpyridine subcomponent allowed the construction of an FeII4L4 tetrahedron 1 that was capable of transferring between water and nitromethane layers, driven by anion metathesis. Cage 1 selectively encapsulated coronene from among a mixture of eight different types of PAHs in nitromethane, bringing it into a new nitromethane phase by transiting through an intermediate water phase. The bound coronene was released from 1 upon addition of benzene, and both the cage and the purified coronene could be separated via further phase separation.

Polycyclic aromatic hydrocarbons (PAHs), also known as polyaromatic hydrocarbons,1 are found naturally in oil, coal, and tar, and they are produced as byproducts in the combustion processes of fuels. They are widespread pollutants, with many known to be carcinogenic, mutagenic, and teratogenic.2 Their rigid, planar, conjugated structures render them useful in the fabrication of optical and electronic devices.3,4 Both the value of PAHs in pure form, and the problems they cause as pollutants, thus motivate the development of new host molecules5−15 for selective PAH sequestration.16−22

New supramolecular strategies for the separation of target molecules, based on host–guest chemistry, are of current interest.23,24 For instance, nonporous adaptive crystals of pillararenes have been successfully employed for the separation of various aromatic and aliphatic hydrocarbons.25,26 Porous organic cages have also been developed for the selective separation of xylene isomers,27 noble gases,28 and chiral molecules.28 Our group has recently focused on the use of phase transfer29−35 of coordination cages36−48 and their molecular cargoes as a new strategy aiming to address practical separation problems.49

We have demonstrated that anion metathesis could be used to drive cages and their cargoes between phases.50 In addition, cages that incorporate hydrophobic ligands, and which thus cannot be prepared directly in water, may in certain cases be rendered water-soluble by adding hydrophilic anions.51 Cages constructed from large, hydrophobic aromatic panels, however, tend to decompose in water, as the equilibria of their formation are driven backward by ligand insolubility.51

This work describes a new method to enable the use in water of coordination cages that contain large, hydrophobic subcomponents. Coordination cage 1 (Scheme 1), constructed from a water-insoluble triazatruxene panel, is water-stable as a result of the incorporation of triethylene glycol moieties in its formylpyridine subcomponents. Cage 1 thus undergoes anion-metathesis-driven phase transfer, which in turn allows the selective separation and recovery of coronene from a mixture of similar PAHs. We also developed a means to recycle 1 by separating it from its purified coronene cargo.

Scheme 1. Subcomponent Self-Assembly of Cage 1.

Scheme 1

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The reaction of tritopic subcomponent A (4 equiv) with iron(II) bis(trifluoromethanesulfonyl)imide (triflimide, Tf2N–) (4 equiv) and triethylene glycol-functionalized formylpyridine B (12 equiv) in acetonitrile afforded tetrahedron 1 (Scheme 1). The FeII4L4 composition of the assembly was confirmed by electrospray ionization mass spectrometry (ESI-MS) (Figure S17). The 1H NMR spectrum of 1 displayed only one set of ligand signals (Figure S14), consistent with the exclusive formation of a pair of T-symmetric tetrahedral enantiomers, with faces and vertices of a single stereochemical orientation. We infer these enantiomers to be A4Δ4-1 and C4Λ4-1, with anticlockwise (A) triazatruxene panels paired with iron(II) stereocenters of Δ handedness, and clockwise (C) triazatruxene with Λ-iron(II) (Figure S18a), based upon the configuration of the parent FeII4L4 cage (Figure S18b), without triethylene glycol groups.52

The gradual addition of coronene (Figure 1) to a solution of 1 (0.13 mM, 500 μL) in CD3NO2 led to the formation of the host–guest complex coronene⊂1. Encapsulation was signaled by the disappearance of the 1H NMR peaks of free 1 and the concurrent appearance of a new set of host peaks and a single peak for bound coronene, which was shifted upfield (Δδ = −1.89 ppm), consistent with a slow-exchange binding process (Figures 2 and S19). When excess coronene (3.4 equiv) was added to 1, 85% conversion to coronene⊂1 was observed. The degree of host–guest complexation was limited by the poor solubility (ca. 0.44 mM) of coronene in this solvent. The bound coronene was released from the cavity of 1 upon addition of excess C6D6 (100 μL) (Figure 2). We infer that the coronene guest is better solvated by a solvent mixture that contains benzene, thus favoring guest release upon benzene addition.

Figure 1.

Figure 1

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PAH guests for 1.

Figure 2.

Figure 2

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Partial 1H NMR spectra (CD3NO2, 500 MHz, 25 °C) of 1 (0.13 mM) after the addition of increasing amounts of coronene and then following further addition of deuterated benzene (100 μL to a 500 μL sample) to the mixture.

A binding constant Ka1 = (1.9 ± 0.3) × 104 M–1 of 1 for coronene was determined by 1H NMR integration at 25 °C. The binding affinity was observed to decrease as the temperature increased (Table S1 and Figure S20). A van’t Hoff analysis (Figure S21) revealed that the binding is driven by enthalpy (ΔH = −27 kJ mol–1; ΔS = −1.7 × 10–3 kJ K–1 mol–1).

Decreasing the concentration of 1 to 0.040 mM allowed us to add 10 equiv of coronene without precipitation. In this experiment a new singlet peak, corresponding to the bound coronene of a 1:2 host–guest complex, was also observed (Figure S22), as assigned using NOESY and HSQC spectra (Figures S24 and S25). A binding constant of Ka2 = (1.1 ± 0.2) × 103 M–1 was determined from integration. The affinity of 1 for a second coronene is thus more than an order of magnitude less than for the first (1.9 × 104 M–1). PM3 models (Figure S23) indicate room for two molecules of coronene within 1 without distortion.

Addition of other PAH guests, such as anthracene, phenanthrene, pyrene, chrysene, triphenylene, and perylene, resulted in gradual shifts of the peaks of 1 as well as the guests, consistent with fast-exchange binding on the NMR chemical shift time scale (Figures S26–S31). Binding constants were not determined in these cases due to the low solubilities of the guests and host–guest peak overlaps. Similarly to coronene, corannulene was observed to bind in slow exchange (Figures S32–S34), but the binding strength ((2.8 ± 0.4) × 103 M–1) was 7 times weaker than for coronene. We infer the high selectivity of the cage toward coronene to result from a better size match with the inner cavity, as compared to the other, smaller, guests.17

We tested the phase transfer of free 1 between two liquid phases, namely, D2O and CD3NO2, triggered by anion exchange.50 The assembled cage with triflimide counteranions was initially soluble in the lower nitromethane layer, transferring to the upper water layer after addition of tetrabutylammonium sulfate (8 equiv) as anion exchange took place (Figures 3 and S35–S37). Removal and replacement of the nitromethane layer with fresh nitromethane, followed by addition of lithium triflimide (16 equiv), led 1 to transfer back into the new nitromethane layer, as signaled by the deep red color of 1.

Figure 3.

Figure 3

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Sequential phase transfer of 1 (0.13 mM) by addition of sulfate and triflimide anions, from CD3NO2 (lower layers) to D2O (upper layers) and back again.

The 1H NMR spectra of 1 in the initial and final CD3NO2 phases presented well-defined cage peaks, the integrations of which suggested that more than 95% of 1 transferred through water and back into nitromethane (Figure S35). The proton signals of 1 in the intermediate D2O phase were broad but became sharper after the addition of acetone-d6 (Figure S36), consistent with T point symmetry. This tetrahedron paired with sulfate was also detected by ESI-MS (Figure S37). We infer that the cage molecules tend to aggregate in water, giving rise to broad 1H NMR signals, while dispersion occurs after addition of a water-miscible organic solvent.53

Notably, an analogue of 1 having no peripheral triethylene glycol groups (Figure S18b) was not observed to transfer into water, even following the addition of a large excess (>100 equiv) of sulfate. Instead it decomposed to produce insoluble solids, demonstrating the necessity of incorporating hydrophilic triethylene glycol groups into subcomponent B.

We then set about investigating the use of cage 1 to build a system capable of chemical purification by catching and releasing a coronene cargo. As shown in Figure S38, the addition of sulfate (8 equiv) to a mixture of 1 (0.090 mM, 500 μL) and coronene (3.7 equiv) led to the transfer of the cage with its cargo into the D2O layer (Figure S38b). Subsequent addition of triflimide (16 equiv) drove the complex back to a new CD3NO2 layer (Figure S38c). The bound coronene was released from 1 following the addition of C6D6 (100 μL, Figure S38d). The 1H NMR spectrum of this solution indicated the presence of free 1 and free coronene (0.86 equiv, Figure S39), without host–guest complex peaks. Replacement of the upper D2O layer and addition of sulfate (8 equiv) resulted in transfer of the free cage to the new D2O layer. The coronene was thus isolated through evaporation of the CD3NO2 (Figure S38e). Cage 1 was recovered as the triflimide salt in fresh nitromethane after a final anion metathesis step (Figure S38f).

Intriguingly, an aqueous solution of 1 as the sulfate salt (Figure S38e) could be also used for direct extraction of coronene from CD3NO2 (Figure S40), with comparable efficiency to the procedure involving phase transfer. The combination of extraction and subsequent phase transfer thus offers an alternative route to coronene separation and recycling.

Cage 1 was able to selectively separate coronene from a mixture of other PAHs including anthracene, phenanthrene, pyrene, chrysene, triphenylene, perylene, and corannulene (Figure 4). A similar sequential phase-transfer process as described above was performed, resulting in the successful separation of the coronene target from the other PAHs. The coronene (0.75 equiv) was isolated in CD3NO2, with no other PAHs detectable by 1H NMR (Figure S42), indicating a high selectivity. The amount of coronene isolated (0.75 equiv) was slightly less than the amount obtained (0.86 equiv) when no other PAHs were present. Control experiments showed that, when the mixture of PAHs contained only these other guests without coronene, no PAH molecules were transported during phase transfer of 1 (Figure S43). This observation suggests that the weaker interactions of these other PAHs with 1 led to their ejection during phase transfer. However, their presence appeared to slightly decrease the coronene transport efficiency, which we infer to be a consequence of their blocking the cavity of 1.

Figure 4.

Figure 4

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Selective separation and recovery of coronene from a mixture of other PAHs including anthracene, phenanthrene, pyrene, chrysene, triphenylene, perylene, and corannulene. All upper layers in these schematic vials are D2O, and the lower layers are CD3NO2. (a) Cage 1 took up coronene selectively in CD3NO2 (0.090 mM 1; 0.33 mM coronene, and 0.090 mM of each of the other PAHs) and (b) transferred to the aqueous layer together with its coronene cargo after the addition of SO42–; (c) replacement of the CD3NO2 layer and addition of Tf2N– drove the complex into CD3NO2. (d) Cage 1 discharged the coronene cargo upon addition of C6D6, and the released coronene (e) was separated by transferring empty 1 to D2O upon addition of SO42–. (f) Cage 1 was recovered in fresh CD3NO2 following the addition of Tf2N–. Free 1 paired with SO42– in D2O could also directly extract coronene from a new mixture of PAHs in CD3NO2 (e→b).

The triethylene glycol functionalization strategy developed herein may well allow other cages to undergo phase transfer, in turn permitting the purification of a wider range of molecules.54 This method may thus be rendered useful in the purification of valued products from many different sources, from petroleum feedstocks to drug synthesis procedures.

Acknowledgments

This work was supported by the European Research Council (695009) and the UK Engineering and Physical Sciences Research Council (EPSRC EP/P027067/1). The authors thank the Dept. of Chemistry NMR facility, Univ. of Cambridge, for performing some NMR experiments, and the EPSRC UK National Mass Spectrometry Facility at Swansea Univ. for performing high-resolution mass spectrometry. D.Z. acknowledges a Herchel Smith Research Fellowship from the Univ. of Cambridge.

Supporting Information Available

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.9b10741.

  • Complete experimental details (PDF)

The authors declare no competing financial interest.

Supplementary Material

ja9b10741_si_001.pdf (4.2MB, pdf)

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