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. 2024 Jun 26;24(14):5883–5888. doi: 10.1021/acs.cgd.4c00125

Confinement and Separation of Benzene from an Azeotropic Mixture Using a Chlorinated B←N Adduct

Isabella J Jupiter †, Jesus Daniel Loya †, Nicholas Lutz †, Paulina M Sittinger †,‡, Eric W Reinheimer §, Gonzalo Campillo-Alvarado †,*
PMCID: PMC11261595  PMID: 39044733

Abstract

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Separations of azeotropic mixtures are typically carried out using energy-demanding processes (e.g., distillation). Here, we report the capacity of a self-assembled chlorinated boronic ester-based adduct to confine acetonitrile and benzene in channels upon crystallization. The solvent confinement occurs via a combination of hydrogen bonding and [π···π] interactions. Quantitative separation of benzene from an azeotropic 1:1 mixture of a benzene/acetonitrile (v/v), and methanol is achieved through crystallization with the chlorinated adduct by complementary [C–H···O] and [C–H···π] interactions. Inclusion behavior is rationalized by molecular modeling and crystallographic analysis. The chlorinated boronic ester adduct shows the potential of modularity via isosteric substitution for the separation of challenging chemical mixtures (e.g., azeotropes).

Short abstract

We demonstrate the use of a chlorinated boronic ester-based adduct to separate benzene from an azeotropic mixture of benzene/acetonitrile/methanol by crystallization. Chemical separations of azeotropes (i.e., mixtures that exhibit the same concentration in the vapor and liquid phases) are fundamentally challenging and require alternative methods to traditional distillation. We highlight the opportunities of highly modular boron adducts to provide control over chemical separations of mixtures via selective crystallization.

Efficient chemical separations of petrochemicals and small molecules are industrially relevant due to the need for pure chemical feedstock for plastics, drugs, and fuel.1 In the U.S., chemical separations carried out by traditional methods (e.g., distillation) account for 10–15% of the total energy consumption.2 The problem is exacerbated when chemical mixtures exhibit complex phenomena. The formation of azeotropes in mixtures (i.e., the vapor phase has the same composition as a liquid phase) is a relevant example that requires the addition of entrainers to ensure efficient azeotropic distillations.3 Consequently, explorations of sustainable, green, and less-energy-demanding alternatives for complex chemical separations (e.g., metal–organic or covalent-organic frameworks)1,4 are a critical demand for industry and academia.1,5

Our group and others have employed boronic ester coordination with pyridines (B←N)6 to generate H-shaped7 and T-shaped8 adducts. The adducts have enabled the confinement and separation of petrochemicals,9 and the design of electronic10 and dynamic materials.11 Our design has exploited the generation of electron-deficient surfaces resulting from coordinated pyridyl linkers to boronic esters and aided by additional noncovalent interactions (e.g., [C–H···F]) with 2,4-difluorophenylboronic acid (F-ba).7 To modulate properties of B←N adducts, we envisage isosteric substitution (i.e., replacement of a functional group with another of similar electronic structure)12 of boronic ester adducts (e.g., replacing -F for -Cl in the boronic acid) can result in diverse selectivities and confinement modes that could promote the separation of challenging chemical mixtures (e.g., azeotropes). Isosteric substitution has been used to modulate π-stacking modes in organic semiconductors13 to promote photoreactivity,14 and activate molecular motion15 in the solid state.

Here, we demonstrate the use of a chlorinated boronic ester adduct (Cl-1) to confine and separate acetonitrile (MeCN) and benzene (ben). The boron adduct is formed by self-assembly of 2,4-dichlorophenylboronic acid (Cl-ba), catechol (cat), and 4,4′-bipyridine (bpy) in MeCN or ben (Scheme 1a). Confinement of MeCN is supported by the generation of weak halogen bonding (i.e., [Cl···Cl]) between the adducts, which was absent in fluorinated systems, in addition to [C–H···N] contacts). Confinement of ben relies on [C–H···O] and [C–H···π] contacts. In contrast to previous studies, the guests sit on the boronic ester periphery of the B←N adduct rather than on the electron-deficient surface of bpy. The resulting solvent confinement mode results in the formation of “side” pockets instead of enclosed pockets as previously observed (Scheme 1b,c).7 Applicability of Cl-1 for the separation of ben and MeCN was demonstrated by crystallization (i.e., selective uptake of ben from an isovolumetric mixture) (Scheme 1d). Rationale for the separation is provided by a combination of crystallographic analysis with molecular calculations performed using the Hartree–Fock method (HF/3-21G basis set). To our knowledge, our study represents the first example of an azeotropic separation (i.e., acetonitrile/benzene/methanol) carried out via crystallization using a supramolecular host.

Scheme 1. Design and Application of Chlorinated Adduct Cl-1: (a) Self-Assembly of Cl-1; Confinement Modes in (b) Previous Studies7 and (c) This Study; and (d) Separation of Benzene from an Azeotropic Mixture with Adduct Cl-1 via Crystallization.

Scheme 1

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To evaluate the modularity of B←N adducts, Cl-ba (12.2 mg, 0.0639 mmol) was combined with cat (7.04 mg, 0.0639 mmol) and bpy (5.0 mg, 0.0320 mmol) in MeCN (3 mL) with dropwise addition of methanol (ca. 0.5 mL). The vial was gently heated until the solution was clear. After 3 days of slow evaporation, single crystals of Cl-1⊃MeCN formed as yellow blades. The stoichiometry of the crystals was confirmed by 1H nuclear magnetic resonance (NMR) spectroscopy (See SI).

A single crystal X-ray diffraction (SCXRD) analysis of Cl-1⊃MeCN revealed the system to crystallize in the trigonal space group R-3. The asymmetric unit consists of half a molecule of 1 and one molecule of MeCN. Linker bpy is coordinated to two phenylboronic acid catechol ester (be) units through a B←N bond (1.671 Å), forming a discrete H-shaped adduct where phenyl rings are in anti-conformation (Figure 1a). The pyridyl rings are effectively coplanar. The calculated tetrahedral character of four-coordinate boron (THC = 69.1%)16 is slightly smaller than fluorinated H-shaped B←N adducts (∼72%), indicating a weaker interaction.7 In the system, adducts Cl-1 assemble into tapes in the ac-plane sustained by face-to-face [π···π] embrace between adjacent bpy and the boronic esters (Figure 1b). Notably, MeCN is confined in hexagonal pockets through hydrogen bonds ([C–H···N] = 2.785 Å) with the chlorinated phenyl ring of Cl-1. Chlorine atoms aggregate in a regular hexagons via [Cl···Cl] contacts (3.320 Å) through the c-axis, highlighting the structure-forming ability of the interactions.17 The adduct aggregation is additionally supported by edge-to-face [C–H···π] interactions between hosts (C–H···centroid(catecholate) = 2.801 Å). The MeCN guests occupy 11.3% (contact surface analysis) of the unit cell volume and are regularly situated within the side pockets (Figure 1c,d). Numerous attempts to confine MeCN with the analogous fluorinated adduct (F-1) were unsuccessful.7

Figure 1.

Figure 1

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Single crystal X-ray structure of Cl-1⊃MeCN: (a) Molecular unit of Cl-1 interacting with MeCN via [C–H···N] contacts. (b) Face-to-face π-stacking between adjacent bpy and be molecules. (c) Edge-to-face [C–H···π] contacts between Cl-1 units. (d) Formation of side pockets in the ab-plane. (e) Hexagonal architecture of pockets via short [Cl···Cl] contacts.

We have determined that the Cl-1 adduct can be exploited to separate ben from MeCN, and methanol. Because of the similar boiling points of MeCN and ben (81.6 and 80.1 °C, 1 atm)18 and azeotrope formation, the separation of the azeotropic mixture is fundamentally challenging and relevant for industry.19 Current separation methods employ energy-demanding distillation with entrainers to increase the relative volatility of compounds and improve separation.20 When the starting materials Cl-ba, cat, and bpy (using the same for Cl-1⊃MeCN) were dissolved in a 1:1 MeCN/ben solution (3 mL, v/v) and ca. 0.5 mL of methanol (used to facilitate complete dissolution), single crystals in the form of orange blocks precipitated after a period of 1 day. While we note the role of methanol to be a solubilizing agent, azeotropes of methanol/ben and methanol/MeCN are likely present as ternary azeotropic system.19 Remarkably, filtered single crystals crystallized with ben quantitatively as the only solvent confined, as indicated by 1H NMR spectroscopy (see SI). Crystals of pure Cl-1 were not observed in the crystallization vial. The performance is comparable to existing separation methods for azeotropic separations using triple-column pressure-swing distillation19 or entrainers.20 Partial recovery of the Cl-1 host was enabled by heating the Cl-1⊃ben crystals at 100 °C for 24 h. 1H NMR spectroscopy confirmed ben desolvation of 14% after heating at 100 °C for 5 min. Additional 15 min of heating afforded 45% ben desolvation (see SI). Prolonged heating resulted in sample decomposition. We envisage the partial recovery of Cl-1 will inspire the design of methods to enable full recovery of hosts after guest uptake from azeotropic mixtures, ensuring sustainability and recyclability of separation processes.21

Structural determination by SCXRD revealed the components of Cl-1⊃ben to crystallize in the monoclinic space group C2/c (Table 1). The stoichiometry of the crystals was confirmed by 1H NMR spectroscopy (see SI). The asymmetric unit comprises two one-halves of Cl-1 (i.e., 1a and 1b) and half a molecule of ben (Figure 2a). The [B←N] bond distances of 1a and 1b (1.667 and 1.646 Å, respectively) and calculated THC (73.9 and 77.1%, respectively) are comparable to those of previously reported H-type adducts.7 It is noteworthy that the twist angles of pyridyl rings in 1a and 1b are 64.2° and 0°, respectively. We hypothesize the twisted bpy in 1a is due to the loss of efficient conjugation of the π-cloud in the molecule to favor face-to-face [π···π]-stacking of individual pyridine rings with be motifs of adjacent Cl-1 molecules, and to maximize edge-to-face [C–H···π] interactions between the pyridyl and dichlorophenyl rings.22 Intermolecular π-stacking interactions between adducts generate side pockets along the b-axis in the crystal that contain ben molecules (19.5% of unit cell volume, contact surface analysis) (Figure 2b,c). Molecules of ben are supported by [C–H···O] and [C–H···π] contacts with the catechol and phenyl ring moieties, respectively, in the be (Figure 2d). Confinement of ben with Cl-1 (Figure 2e) differs from the analogous fluorinated B–N adduct (F-1), which relies on the formation of enclosed pockets primarily by face-to-face [π···π] stacking with the bpy linker and additional edge-to-face [C–H···π] stacking, and [C–H···F] contacts.7

Table 1. Summary of Crystallographic Data for Cl-1⊃MeCN, Cl-1⊃ben, Cl-1, and F-1.

crystal dataa Cl-1⊃MeCN Cl-1⊃ben Cl-1 F-1
chemical formula 3(C34H22B2 Cl4N2O4)·2(C2H3N) 2(C17H11BCl2NO2)·0.5(C6H6) C34H22B2Cl4N2O4 C34H22B2F4 N2O4
MW (g mol–1) 2139.97 725.01 685.95 620.15
space group R-3 C2/c P21/c P21/n
a (Å) 19.5553(12) 24.8867(10) 9.4842(5) 9.3110(9)
b (Å) 19.5553(12) 10.3952(5) 12.8576(7) 13.0637(18)
c (Å) 22.4722(16) 26.6246(9) 13.1489(5) 13.1643(17)
α (deg) 90 90 90 90
β (deg) 90 98.089(4) 95.932(4) 109.440(12)
γ (deg) 120 90 90 90
V (Å3) 7442.3(11) 6819.3(5) 1594.84(14) 1510.0(3)
Z 3 8 2 2
μ (mm–1) 0.403 0.391 0.414 0.105
ρcalcd (g cm–3) 1.432 1.412 1.428 1.364
R1b,c 0.0894 0.0479 0.0478 0.0648
wR2d,e 0.2253 0.1075 0.1191 0.1683
CCDC 2327025 2327023 2327022 2327024
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a

λMoKα = 0.71073 Å.

b

F0 > 2σ(F0).

c

R1 = ∑|F0| – |Fc|/∑|F0|.

d

All data.

e

wR2= [∑w(F02 – Fc2)2/∑w(F02)2]1/2.

Figure 2.

Figure 2

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Single crystal X-ray structure of Cl-1⊃ben: (a) Molecular unit of Cl-1 interacting with ben via [C–H···O] contacts. (b) Encapsulated ben molecules in the periphery of the be motif. (c) Channel volume (highlighted in red). (d) Inclusion of ben molecules in side pockets in the ab-plane. (e) Side pockets formed along the b-axis.

During the course of our studies, single crystals of pure host Cl-1 (i.e., apohost) in the form of yellow blocks were harvested in minor amounts from the vial containing Cl-1⊃MeCN. SCXRD analysis revealed the apohost to self-assemble in the monoclinic space group P21/c (Figure 3a). The asymmetric unit contains one-half of the Cl-1 adduct with [B←N] bond distance and THC of 1.657 Å and 75.3%, respectively. The values are comparable to the solvated Cl-1⊃ben adduct. The bipyridyl rings in bpy are effectively coplanar. In the system, the Cl-1 adducts self-assemble into tapes that run along the c-axis. The tapes are sustained by a combination of [C–Cl···O], [C–H···π], and phenyl embraces generated by face-to-face [π···π] interactions (Figure 3b). Notably, the crystal structure has spherical voids that account for 2.6% of the unit cell volume (40.7 Å3). The observation supports the solvate-forming propensity of Cl-1 to decrease void space and lead to more efficient packing (Figure 3c).23 Notably, Cl-1 does not exhibit short [Cl···Cl] contacts, which are present in both solvated systems. An isoskeletal structure of F-1 was isolated during our studies with 2,4-difluorophenylboronic acid. The structure was deemed a polymorph of F-1 that exhibits an inversion center between the pyridyl rings of bpy (i.e., rings are coplanar), which is absent in the previously reported structure (see SI for structural analysis).7

Figure 3.

Figure 3

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Single crystal X-ray structure of Cl-1: (a) Molecular unit of Cl-1. (b) Tapes of adjacent Cl-1 adducts supported by [C–Cl···O], [C–H···π], and [π···π] contacts. (c) Voids formed along the c-axis.

Molecular coordinates obtained from single crystals from Cl-1 and the F-1 polymorph enabled us to perform Hirshfeld surface analysis24 and molecular modeling to provide a rationale for the solvent inclusion and selectivity of Cl-1 (Figure 4a,b). For the apohosts, F-1 showed the presence of minimal F···F interactions, while Cl-1 showed no [Cl···Cl] interactions. Upon inclusion with ben and MeCN, there was an increase in [Cl···Cl] interactions in both inclusion complexes with Cl-1. Specifically, the percentage of [Cl···Cl] interactions in Cl-1⊃ben and Cl-1⊃MeCN increased to 1.6% and 4.2%, respectively (Figure 4c). Halogen bonding aided in the aggregation of the adducts. In the case of Cl-1⊃MeCN, the adduct formed hexagonal-shaped pockets sustained by [Cl⊃Cl] interactions. For Cl-1⊃ben, while the increase of [Cl···Cl] was minimal, the combination with [C–H···π], [C–H···O], and [π···π] contacts supported ben confinement in side pockets along the crystallographic b-axis (Table S5), and enhanced selectivity over MeCN and methanol when cocrystallized in an azeotropic mixture with Cl-1. The formation of halogen bonding interactions in Cl-1⊃ben and Cl-1⊃MeCN is in agreement with the increase in the σ-hole and a larger negative belt surface area observed in electrostatic potential maps from molecular modeling, as shown in calculations performed using the Hartree–Fock method (HF/3-21G basis set) of Cl-1, which is larger than surfaces generated in F-1. Specifically, σ-holes in Cl1 and Cl2 from Cl-1 were calculated as ca. 28 and 66 kJ/mol, respectively, while both F1 and F2 from F-1 were ca. −129 kJ/mol, indicating a more effective surface for halogen bonding in Cl-1 (Figure 4d), which is in agreement with the formation of [Cl···Cl] interactions in Cl-1⊃MeCN.

Figure 4.

Figure 4

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Hirshfeld surface analysis maps of (a) Cl-1⊃MeCN and (b) Cl-1⊃ben. (c) Selected projection interaction percentages of the reported structures. (d) Electrostatic potential maps of F-1, Cl-1, ben, MeCN, and bpy.

In summary, we have highlighted the potential of confinement modularity of boronic ester-based adducts using isosteric substitution (i.e., replacing -F with -Cl). Specifically, we demonstrated that by installing -Cl atoms to adduct Cl-1, selective uptake and separation of benzene from an azeotropic mixture of benzene/acetonitrile/methanol was achieved. We envisage the highly modular nature of boron adducts can result in the separation of additional challenging mixtures,2 and serve as a proof-of-concept to engineer alternatives to energy-demanding distillation methods in industry.21

Acknowledgments

We gratefully acknowledge financial support from the M. J. Murdock Charitable Trust (NS-202222588, FSU-202118942), Reed College (start-up, Stillman Drake, and summer funds), and the National Science Foundation (CHE-2319929). I.J.J. appreciates support from the Marshall W. Cronyn Student Research Fund. J.D.L. appreciates support from the Consortium of Faculty Diversity Postdoctoral Fellowship. P.M.S. appreciates financial support from Internationale Studierendenmobilität – Team Direktaustausch via the Reed College Exchange Program fellowship. The authors would like to thank Kyle Petersen, Nicole Xu, and Deepika Shingwekar for discussions on X-ray crystallography. We are thankful to the Chemistry Department of Portland State University for access to the NMR facility and to Charlene Kupara for her assistance with sample collection.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.cgd.4c00125.

  • Experimental conditions and additional data for single crystal X-ray diffraction, powder X-ray diffraction, molecular modeling, and 1H and 19F nuclear magnetic resonance (PDF)

Author Contributions

# I.J.J. and J.D.L. contributed equally.

The authors declare no competing financial interest.

Special Issue

Published as part of Crystal Growth & Designvirtual special issue “Celebrating Mike Ward’s Contributions to Molecular Crystal Growth”.

Supplementary Material

cg4c00125_si_001.pdf (1.9MB, pdf)

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