Competitive Inclusion of Disubstituted Benzene Regioisomers with

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Competitive Inclusion of Disubstituted Benzenes Regioisomers with Crystals of p-tert-Butylcalix[4]arene Naoya Morohashi, Ayano Tonosaki, Taro Kitagawa, Takuro Sasaki, Kohei Ebata, and Tetsutaro Hattori Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b01007 • Publication Date (Web): 11 Sep 2017 Downloaded from http://pubs.acs.org on September 13, 2017

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Crystal Growth & Design

Competitive Inclusion of Disubstituted Benzenes Regioisomers with Crystals of p-tertButylcalix[4]arene Naoya Morohashi,* Ayano Tonosaki, Taro Kitagawa, Takuro Sasaki, Kohei Ebata, and Tetsutaro Hattori* Department of Biomolecular Engineering, Graduate School of Engineering, Tohoku University, 6-6-11 Aramaki-Aoba, Aoba-ku, Sendai 980-8579, Japan Keyword: Calixarene, Inclusion, Disubstituted benzenes, Molecular crystal

ABSTRACT

A crystal of p-tert-butylcalix[4]arene (1) has selectively included regioisomers of eight different disubstituted benzenes, giving inclusion crystals classified into four types: 2:1 (host/guest) with p-isomer and 1:1 with o-, m-, and p-isomers. X-ray crystallographic analysis of 12·p-xylene, 1·ocresol, 1·m-dichlorobenzene, and 1·p-chlorotoluene, which were chosen as representatives for the individual types of inclusion crystals, revealed that the electrostatic properties and steric bulk of the substituents in the rigid guest molecules are efficiently reflected in the interaction with the

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host molecules, which construct flexible bilayer-based packing structures in the inclusion crystals. This is considered as a principal origin for the high selectivity and wide applicability achieved in the inclusion of aromatic regioisomers with crystals of compound 1.

There has been growing interest in the development of solid porous materials for the collection of organic compounds, with the intention of establishing green and low-cost separation processes. Many studies have been reported on the separation and/or collection of organic molecules using zeolite,1–3 metal–organic frameworks (MOFs),4–7 covalent organic network polymers (COFs),8–10 and nanoporous molecular crystals (NMCs)11–15. Calixarenes (e.g., 1 and 2) are representative host molecules to construct NMCs, which have “porosity without pores”16 (Chart 1).17–27 In a guest-free crystal of thiacalixarene 2, a pair of calixarene molecules with a cone conformation include each other’s tert-butyl groups into their cavities to form a selfinclusion complex, the accumulation of which constructs tight packing with neither channel nor void structures to accommodate guest molecules. However, this crystal includes inorganic gasses and small organic molecules into the cavity of compound 2, accompanied by a structural change in the crystal packing; compound 2 usually forms a 1:1 (host/guest) complex, which piles up in a head to tail manner to form a columnar structure (Figure 1a). Recently, we succeeded in the selective inclusion of organic molecules of similar sizes and structures with the crystal of compound 2 by taking advantage of the kinetic and thermodynamic aspects of this structural change.28–32 Methylene-bridged calixarene 1 also forms a self-inclusion crystal with essentially the same crystal packing as that of compound 2 and the crystal includes inorganic gasses and small organic molecules accompanied by a structural change of the crystal packing. However, the guest selectivity of compound 1 is poor. Compound 1 constructs a stable bilayer structure in


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inclusion crystals with the aid of a network of intermolecular CH–π interaction between a methylene group of a host molecule and a benzene ring of an adjacent host molecule (Figure 1d). The bilayers are laminated in two different manners to form 1:1 (Figure 1b) and 2:1 (host/guest) inclusion complexes (Figure 1c); in the latter complex, a guest molecule is included in a molecular capsule constructed by two host molecules.17,24,30 The inclusion crystals with the same packing structure have almost the same spaces to accommodate guest molecules regardless of the guest size, which seems to be a principal reason for the poor selectivity of compound 1 to guest molecules. To the best of our knowledge, selective inclusion of organic molecules with crystals of methylene-bridged calixarenes has yet to be reported, although p-tert-butylcalix[8]arene and p-isopropylcalix[4]arene are known to include C60 and p-xylene selectively by crystalizing the host molecules from solutions of fullerene homologues33,34 and xylene isomers,35 respectively. Separation of aromatic regioisomers with similar physical properties often requires a multistage process. Therefore, the development of an efficient method for their separation is highly desired. We expected that the crystal of compound 1 would include aromatic regioisomers at different rates and with different stabilities, because the rigid structures of aromatics should bring about different interactions between the host and guest molecules and different strains to the resulting inclusion crystals. In this study, we have found that the crystal of compound 1 selectively includes various disubstituted benzenes from mixtures of their regioisomers (Chart 1).

Chart 1


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Figure 1. Packing structures of host molecules in 2·ethanol (a), 1·ethanol (b), and 12·pentanol (c) and CH–π interactions between adjacent host molecules in 12·pentanol (d).30 Selected hydrogen atoms, disordered atoms, and guest molecules are omitted for clarity. Red dotted lines represent intermolecular CH–π interactions. The volumes of cavities (V0) to accommodate guest molecules were calculated to be 90 Å3 (2·ethanol), 165 Å3 (1·ethanol), and 253 Å3 (12·pentanol) by PLATON36 after removing the alcohol molecules.

Competitive inclusion among three regioisomers of disubstituted benzenes with the crystal of compound 1 was examined as follows. Powdery crystals of compound 137 were suspended in an equimolar mixture of three regioisomers of a disubstituted benzene and the suspension was


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stirred at a fixed temperature until inclusion reached equilibrium (1–2 d). The resulting crystals were collected by filtration, dried in vacuo (0.5–1.0 kPa) at room temperature for 2 h, and analyzed by 1H NMR spectroscopy to determine the inclusion ratio (݊തi), which was defined as the mean number of guest molecules (i) included into the crystals per host molecule. The selectivity for guest i (Si%) was calculated according to equation 1. Si% = ݊തi / (݊തo + ݊തm + ݊തp) × 100 (i = o, m, and p)

(1)

The results are listed in Table 1. Notably, the crystal of compound 1 selectivity included ocresol (entry 5), m-dichlorobenzene (entry 8), and the p-isomers of the other guest compounds tested (entries 1–4, 6, and 7); it should be noted that no interaction was observed between compound 1 and guest molecules in solution by 1H NMR titration analysis (Figure S1 as an example). A difference was observed in the inclusion ratios: ~0.5 for p-xylene and p-toluidine (entries 1 and 3) and ~1.0 for the other compounds (entries 2 and 4–8). In contrast, none of these guest molecules were included in the crystal of compound 2 (Table S1). This is apparently due to the packing structure of its inclusion crystals (Figure 1a), which does not provide enough space to accommodate aromatic compounds.


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Table 1. Competitive inclusion of regioisomers of disubstituted benzenes with crystals of compound 1.a Entry

Guest

݊ത (o- / m- / p-)b

Si %c

R1

R2

1

CH3

CH3

–e / –e / 0.50

100 (p-)

2d

CH3

CN

0.02 / 0.02 / 0.99

96 (p-)

3d

CH3

NH2

0.02 / 0.04 / 0.44

88 (p-)

4

CH3

NO2

–e / –e / 0.89

100 (p-)

5d

CH3

OH

0.85 / 0.03 / 0.02

94 (o-)

6

CH3

Cl

–e / –e / 0.93

100 (p-)

7

OH

Cl

–e / –e / 0.80

100 (p-)

8

Cl

Cl

–e / 0.84 / –e

100 (m-)

a

Conditions: powdery crystals of compound 1 (30.8 µmol), an equimolar mixture (0.5–4.0 mL) of three regioisomers, 30 °C, 24 h. b

The average value of more than two runs.

c

Calculated for the isomer indicated in parentheses.

d

Conducted for 48 h.

e

Inclusion was not observed.

For the isomers selectively included in the competitive experiments (Table 1), inclusion crystals were prepared by suspending powdery crystals of compound 1 in isomerically pure disubstituted benzenes and subjected to powder X-ray diffraction (PXRD) analysis. PXRD patterns of the inclusion crystals with two guests (p-xylene and p-toluidine) and four guests (ptolunitrile, p-nitrotoluene, p-chlorotoluene, and p-chlorophenol) are similar to those of single crystals of 12·pentanol30 and 1·ethanol30, respectively (Figure 2). The experimental inclusion


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ratios (Table 1) are in reasonable agreement with the host/guest ratios of the single crystals. On the other hand, PXRD patterns of the inclusion crystals with o-cresol and m-dichlorobenzene are different from those of the others; therefore, the inclusion crystals are classified into four types: 2:1 (host/guest) with p-isomer (xylene and toluidine) and 1:1 (host/guest) with p-isomer (tolunitrile, nitorotoluene, chlorotoluene, and chlorophenol), o-isomer (cresol), and m-isomer (dichlorobenzene).

Figure 2. PXRD patterns of inclusion crystals of compound 1 with p-xylene (a), p-toluidine (b), p-tolunitrile (c), p-nitorotoluene (d), p-chlorotoluene (e), p-chlorophenol (f), o-cresol (g), and mdichlorobenzene (h) as compared with those of powdery crystals of 1 (i), 1·ethanol (j),30 and 12·pentanol (k).30


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To explore the origin of isomer selectivity, single crystals of inclusion complexes were prepared by crystallizing compound 1 from neat p-xylene, p-chlorotoluene, o-cresol, and mdichlorobenzene and subjected to single-crystal X-ray diffraction (XRD) analysis. These disubstituted benzenes were chosen as representative guests for the four types of inclusion crystals. The formulae of the inclusion crystals were revealed as 12·p-xylene, 1·p-chlorotoluene, 1·o-cresol, and 1·m-dichlorobenzene; their XRD data nicely simulated the PXRD patterns of the respective inclusion crystals prepared by the suspension method (vide supra; Figures S2–S5). Inclusion crystal 12·p-xylene belongs to the tetragonal system with the P4/nnc space group. In the crystal (Figures 3a and 4a, b), compound 1 constructs molecular capsules similar to those in reported 2:1 (host/guest) inclusion crystals such as 12·pentanol (Figure 1c); each capsule is densely filled with a p-xylene molecule. The inner volume of the capsule (Vo) was calculated to be 263 Å3 by PLATON36 as a void after removing the guest molecule from the X-ray structure; the volume is close to that in 12·pentanol (253 Å3). The guest molecule is well adapted in the capsule with the two methyl groups directed inside the cavities of different host molecules to form a highly symmetrical inclusion complex. Cooperative CH–π interactions are observed between each methyl group of the guest molecule and the four benzene rings of the host molecule including it. Apparently, the CH–π interactions are most effective for the p-isomer among the three isomers because of its symmetric molecular structure. Therefore, out of the three isomers, the p-isomer should form the most stable inclusion crystal, which is probably responsible for the inclusion selectivity toward the p-isomer.


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Figure 3. X-ray structures of inclusion complexes in 12·p-xylene (a), 1·p-chlorotoluene (b), 1·ocresol (c) and 1·m-dichlorobenzene (d). Hydrogen atoms and disordered atoms are omitted for clarity. Red dotted lines represent CH–π, OH–π and CH–halogen interactions. An independent structure of 1·o-cresol (c) is shown. Selected distances: (a) C14···ring A (3.869 Å), (b) C12···ring B (3.678 Å), (c) C38···ring C (3.693 Å), O5···ring C (3.832 Å), (d) C3···C46 (3.730 Å), C19···Cl2 (3.856 Å).


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Figure 4. Packing structures of compound 1 in 12·p-xylene (a and b), 1·p-clorotoluene (c and d), 1·o-cresol (e and f), and 1·m-dichlorobenzene (g and h). Molecules are color-coded and guest molecules, hydrogen atoms, and disordered atoms are omitted for clarity.

Inclusion crystal 1·p-chlorotoluene belongs to the tetragonal system with the P4/n space group. As in the case of reported 1:1 (host/guest) inclusion crystals such as 1·EtOH (Figure 1b), a guest molecule is accommodated in a space between two host molecules oriented in the same direction along the c-axis, directing the methyl group inside the cavity of a host molecule (Figures 3b and 4c, d). V0 was calculated to be av. 186 Å3; this volume is smaller than that of the capsule in 12·p-xylene. CH–π interactions are observed between the methyl group of the guest molecule and the four benzene rings of the host molecule including it. No interactions are observed between the chloro group and host molecules. It is easily conceivable that it is difficult for the chloro group to take a suitable position in a capsule for making effective interactions with the host molecules. Therefore, the formation of a 1:1 (host/guest) inclusion complex is advantageous over that of a capsule-type complex. Furthermore, p-chlorotoluene having a highly symmetric structure is advantageous for the formation of such a 1:1 complex compared to the oand m-isomers, unless the chloro group has attractive interactions with host molecule(s) around it. Inclusion crystals 1·o-cresol and 1·m-dichlorobenzene belong to the tetragonal system with the P4 space group and the orthorhombic system with the Pna21 space group, respectively. Although these crystals are constructed by 1:1 inclusion complexes similar to those in usual 1:1 inclusion crystals such as 1·p-chlorotoluene, their crystal structures are less symmetric and have larger cavities than the usual ones [Figure 4e and g (4f and h) as compared with 4c (4d)]; V0 values


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were calculated to be 203 Å3 on average for 1·o-cresol and 216 Å3 for 1·m-dichlorobenzene. In 1·o-cresol, there are three kinds of independent inclusion complexes (Figure S6); one of them is shown in Figure 3c. In each independent inclusion complex, the guest molecule included in the cavity of a host molecule directs the methyl group toward the cavity. CH–π interactions are observed between the methyl group and the four benzene rings. Furthermore, an OH–π interaction is observed between the hydroxy group of the guest molecule and one benzene ring of the host molecule. These cooperative interactions are assumed to favorably affect the selective formation of the 1:1 inclusion crystal with the o-isomer. In 1·m-dichlorobenzene, a guest molecule is included in the cavity of a host molecule, directing two chloro groups outside the cavity (Figure 3d). This is attributed to the difficulty in the formation of effective interactions between the chloro groups and the benzene rings of the host molecule because of the geometry of the guest molecule. Lamination of the bilayer structure along the a axis is slightly misaligned compared to that of 1·p-chlorotoluene, resulting in a lowsymmetry structure [Figure 4g (4h) as compared with 4c (4d)]. A CH–halogen interaction is observed between a methyl group of the host molecule and a chloro group of the guest molecule in addition to CH–π interactions between a benzene ring of the host and a hydrogen atom of the guest molecule (Figure 3d). These interactions are assumed to be partly responsible for the inclusion selectivity toward the m-isomer; although the same interactions are expected for the oisomer, the less symmetric structure of its inclusion complex could increase the lattice strain. In summary, we have shown here that crystals of compound 1 selectively include one isomer from a mixture of three isomers (o-, m-, p-) for eight different disubstituted benzenes by forming four types of inclusion crystals with different regioisomers and/or host/guest ratios. In the development of porous separation materials, host materials have been tailored for individual


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guest compounds to achieve high guest selectivity. Therefore, the simultaneous achievement of both high selectivity and wide applicability is a remarkable success. X-ray crystallographic analysis of four inclusion complexes, as representatives for the individual types of inclusion crystals, revealed that the electrostatic properties and steric bulk of the substituents in the rigid guest molecules are efficiently reflected in the host–guest interactions by virtue of the flexible bilayer-based packing structures of the host compound in the inclusion crystals. Detailed mechanisms for the guest selectivity are under current investigation.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publication website at DOI: Experimental details, 1H NMR spectra of compound 1 in the absence or presence of 1–10 molar equivs of p-tolunitrile, competitive inclusion of regioisomers of disubstituted benzenes with crystals of compound 2, comparison of PXRD patterns of inclusion crystals between experimental data and simulations from XRD data, X-ray structures of two independent complexes in 1·o-cresol other than the complex shown in Figure 3c, crystallographic data and ORTEP drawings of 12·p-xylene, 1·p-chlorotoluene, 1·o-cresol, and 1·m-dichlorobenzene (PDF).

Accession Codes CCDC 1562875–1562878 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif or by emailing [email protected] or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.


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AUTHOR INFORMATION Corresponding Authors *E-mail: [email protected] *E-mail: [email protected]. ORCID Naoya Morohashi: 0000-0001-6589-5237 Tetsutaro Hattori: 0000-0001-8422-4674 Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS The authors wish to thank Prof. K. Asai for courteous permission to use instruments. This work was supported by JSPS KAKENHI Grant Number 25410032.

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For Table of Contents Use Only

Competitive Inclusion of Disubstituted Benzenes Regioisomers with Crystals of p-tertButylcalix[4]arene Naoya Morohashi,* Ayano Tonosaki, Taro Kitagawa, Takuro Sasaki, Kohei Ebata, and Tetsutaro Hattori*

A molecular crystal of p-tert-butylcalix[4]arene (1) selectively includes one isomer from a mixture of three isomers (o-, m-, p-) for eight different disubstituted benzenes by forming four types of inclusion crystals with different regioisomers and/or host/guest ratios.


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Chart 1 75x34mm (300 x 300 DPI)


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Figure 1 111x97mm (300 x 300 DPI)



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Figure 2 103x130mm (300 x 300 DPI)


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Figure 3 75x71mm (300 x 300 DPI)



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Figure 4 225x359mm (300 x 300 DPI)


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