Sulfonylcalixaren-Based ortho-Dicarboxylate-Bridged Coordination

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Sulfonylcalixaren-Based ortho-Dicarboxylate-Bridged Coordination Containers for Guest Encapsulation and Separation Cheng-Zhe Sun, Tian-Pu Sheng, Feng-Rong Dai, and Zhong-Ning Chen Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01633 • Publication Date (Web): 08 Jan 2019 Downloaded from http://pubs.acs.org on January 13, 2019

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Crystal Growth & Design

Sulfonylcalixaren-Based ortho-DicarboxylateBridged Coordination Containers for Guest Encapsulation and Separation Cheng-Zhe Sun, Tian-Pu Sheng, Feng-Rong Dai*, Zhong-Ning Chen* State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China KEYWORDS calixarenes • container molecules • guest encapsulation • guest separation

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Four new sulfonylcalix[4]arene-supported coordination containers have been designed and synthesized through the self-assembly of Co(II)/Ni(II), p-tert-Butylsulfonylcalix[4]arene, and ortho-dicarboxylate linkers, i.e. 1,2-benzenedicarboxylate or 2,3-naphthalenedicarboxylate. Due to the combined effects of rigid directionality of sulfonylcalixarene-capped tetranuclear subunits and the steric repellent between two ortho carboxylate groups, these synthetic coordination containers suffer from a distorted bonding between the tetranuclear units and dicarboxylate linkers. With the extension of aromatic system from benzene to naphthalene, significant multiple intermolecular hydrogen bonding and π-π stacking interactions were enhanced, leading to maintain solid state porosities for small gas molecule. Moreover, they exhibit similar guest binding behaviors towards bulkier dye guests, showing selectively cationic dye adsorption from an aqueous solution of either methylene blue or methylene blue-eosin Y mixture at solid-liquid interface. The results not only provide a new designing approach for construction of calixarenebased coordination containers, but also indicate a promising oppotunity of these new materials for the application of guest recognition and separation.


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INTRODUCTION Coordination containers, a currently attractive class of synthetic receptors, have attracted considerable interest due to their elegant supramolecular architectures and versatile applications.1-11 Recently, there has been growing interest in a new class of coordination containers, termed metal-organic supercontainers (MOSCs),12-16 which were constructed via modular assembly of divalent metal ions, carboxylate linkers, and most importantly, thia- or sulfonylcalix[4]arenes, a well-known class of macrocyclic containers on their own right.17 To date, various applications, including guest recognition16,

18-20,

nanoparticle encapsulation21-23,

catalysis24-27, and LB film fabrication,28 have been well demonstrated. Depending on the diverse carboxylate linkers employed during the assemble process, a variety of polyhedral topologies of thia- or sulfonylcalix[4]arenes-based coordination containers were developed, owing to the highly directionality of the sulfonylcalixarene-capped tetranuclear subunits.12 For example, an octahedra architecture14-16,29 was expected when triangular or linear carboxylate ligand was employed as the linkers. And the angular ditopic carboxlyate ligands bearing a flexible bridging units produced the cylinder-shaped coordination containers19-20,24. Meanwhile, the rigid and angular dicarboxlyate linkers with a bending angle of around 120° gave rise to square-barrel18,

30,

whereas, a trigonal prismatic23 topologies were obtained when the

bending angle increases to ca. 140°. Interestingly, the lowering of the symmetry of tritopic linkers furnished the Johnson-type (J17) hexadecahedral31 or merohedral icosahedral32 architectures. However, the carboxlyate linkers bearing a even smaller bending angle between the binding ends of multitopic bridging ligands has not yet been investigated in the construction of this new generation of coordination containers. For example, the ortho-substituted aromatic dicarboxylate ligands generally bear a bend angle of ca. 60° between the two ends of carboxylate


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units and adopt a non-planar conformation because of the steric hindance effect between the two carboxylate groups in the close proximity, which could be a potential linker for the assembly of sulfonylcalix[4]arenes-based coordination containers

Scheme 1. The self-assembly of coordination containers.

Herein, we describe the self-assembly of a series of new coordination containers constructed from divalent metal ions, sulfonylcalix[4]arene, and ortho-dicarboxylate ligands (Scheme 1). As demonstrated by X-ray crystallogarphy, the coordination containers adopt a cylinder-shaped topology with two sulfonylcalixarene-supported tetranuclear units bridged by four orthodicarboxylate linkers. It is noticeworthy that a distorted bonding mode is adopted between the


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highly directional sulfonylcalixarene-capped tetranuclear subunits and rigid ortho-dicarboxylate bridging ligands. They exhibit distinct guest binding behaviors towards small guest molecules, such as N2, attributed to the different degree of multiple hydrogen bonding and π-π stacking interactions in solid-state. However, they behave similar guest binding properties to bulkier guests such as dye molecules. Remarkably, efficent guest separation is achieved by the selectively encapsulting cation guests at the solid-liquid interface. EXPERIMENTAL SECTION General Methods. Unless otherwise noted, starting materials and solvents were purchased from commercial suppliers and used without further purification. p-tert-Butylsulfonylcalix[4]arene (H4TBSC)33 was prepared according to the reported procedures. UV-vis absorption spectra were recorded on a Perkin-Elmer Lambda 35 UV-Vis spectrophotometer. Infrared spectra (IR) were collected on a Magna 750 FT-IR spectrophotometer using KBr pellets as internal standard. Powder X-ray diffraction results were measured on Rigaku Miniflex with Cu Kα radiation of λ = 1.5405 Å operated at 30 kV at the scan rate of 2 degree/min. Thermogravimetric analysis (TGA) was obtained from a Netzsch thermal analyzer (model-STA449C) at a heating rate of 5 °C/min under a constant nitrogen flow. General procedure for the synthesis of the coordination containers. H4TBSC (42.50 mg, 0.05 mmol), M(NO3)2∙6H2O (M = Ni or Co, 0.25 mmol), and ortho-dicarboxylic acid (1,2benzenedicarboxylic acid, L1 or 2,3-naphthalenedicarboxylic acid, L2, 0.15 mmol) were dissolved in mixture solvents of DMF (3 mL) and methanol (3 mL) in a scintillation vial (10-mL capacity). The vial was placed in a sand bath and then heated to 100 °C at a rate of 0.5 °C/min in


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a programmable oven. The temperature was held at 100 °C for 1 d before the oven was cooled at a rate of 0.2 °C/min to room temperature. The crystals were collected by washing with DMF and methanol, and then dried in vacuum at 100 °C to give the desired activated samples. X-Ray Crystallography: X-ray single-crystal diffraction data were collected using graphitemonochromated Mo-K radiation ( = 0.71073 Å) on a Rigaku Mercury CCD diffractometer. The CrystalClear software package was used for data reduction and empirical absorption correction. The structures were solved by the Direct methods (SHELX 97)34 in conjunction with standard difference Fourier techniques and subsequently refined by full-matrix least-squares analyses on F2. Hydrogen atoms were generated in their idealized positions and all non-hydrogen atoms were refined anisotropically. The electron count due to disordering solvents in the void space was calculated using the program SQUEEZE in PLATON software package. Crystallographic data and structure refinement parameters are summarized in Tables S1 and S2. CCDC numbers 1875736-1875739 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

RESULTS AND DISCUSSION As shown in Scheme 1, the new sulfonylcalix[4]arenes-based coordination containers 1-Co, 1Ni, 2-Co, and 2-Ni were obtained as single crystals from the typical self-assembly reactions of Co(II)/Ni(II)

and

H4TBSC

with

1,2-benzenedicarboxylic

acid

(L1)

or

2,3-

naphthalenedicarboxylic acid (L2). The crystallinity and phase purity of the as-synthesis materials were confirmed by the PXRD patterns (Figure S5). The TGA data revealed that all the


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compounds are stable without obvious degradation at 350 °C under the nitrogen atmosphere (Figures S7-8). The ca. 20% weight loss before 200 °C is attributed to the release of solvent molecules entrapped within the coordination capsule. According to the crystallographic analysis, SQUEEZE results, and TGA analysis, the empirical formula is estimated to be [M4(μ4H2O)TBSC]2(L)4∙8DMF (L = L1: M = Co, 1-Co; M = Ni, 1-Ni; L = L2: M = Co, 2-Co; M = Ni, 2-Ni). The single crystal X-ray diffraction analysis revealed that the structures of 1-Co and 1-Ni are isomorphic and adopt a cylinder-shaped configuration with C2h symmetry (Figure 1a). Taking 1Co as an example, it consists of two TBSC-capped tetranuclear Co4 cluster fragments bridging by four dicarboxylate linkers. Each CoII ion adopts a distorted octahedral coordination geometry composed of two μ-phenoxo and one sulfonyl O atoms from TBSC, two oxygen atoms from two carboxylate units, and one µ4-oxygen species from a presumably neutral water molecule. The TBSC4- ligand displays a cone conformation providing an exo cavity suitable for guest encapsulation. A significant short distances between the two tetranuclear Co4 clusters with the O⋯O distances of 4.73 Å between the two opposing μ4-H2O molecules was observed, thus providing a rather small endo cavity compared to the reported MOSCs19. Two square planes of Co4 cores exhibit a parallel displaced configuration with the centroid-to-centroid distance of 6.06 Å and an offsetting angle of 5.6° between the Co4 planes and the line of Co4 centers. The μ4-H2O molecule is located above the Co4 plane with a distance of 0.67 Å. The L1 ligand orientates in a nearly C2 symmetry, wherein the two ortho- carboxylate units with a dihedra angle of 69.4° between them distort from the phenyl plane to form a dihedra angle of ca. 72.3°, respectively. It is noticeable that the two ortho- carboxylate planes possess quite different dihedral angles with the Co4 plane, in which one (41.4°) is within the normal range (40-45°) as observed in the


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reported MOSCs13-15, 19 whereas the other is significant smaller (29.9°). This provides a distorted bonding pattern between carboxylates and sulfonylcalixarene-capped tetranuclear cluster, implying the excellent flexibility and tolerability of the connecting mode of calixarene-based tetranuclear fragment during the coordinate self-assembly. Therefore, it opens up a new approach to design appropriate carboxylate linkers for constructing novel sulfonylcalixarene-based coordination containers with new topology and functionality. As depicted in Figure 1b, a close packing mode of 1-Co in solid state is stabilized through multiple intermolecular CH∙∙∙O=S hydrogen bonds between the sulfonyl oxygen atoms and methyl or phenyl with the H∙∙∙O distances of 2.422.55 Å and the CH∙∙∙O angles of ca. 170°. A total potential solvent-accessible volume was then estimated to be 27.2% using the PLATON program.

Figure 1. (a) A view of the Co8 cluster structure of 1-Co. (b) The CH∙∙∙O=S hydrogen bonding interactions between the adjacent molecules of 1-Co. The hydrogen atoms uninvolved in the hydrogen bonds and solvent molecules are not included.


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With the extension of aromatic system, L2 linker gave rise to two isomorphic coordination containers 2-Co and 2-Ni, which have a similar cylinder-shaped architecture with the same C2h symmetry (Figure 1, right). Compared with 1-Co, two parallel Co4 squares in 2-Co show a similar centroid-to-centroid distance of 6.08 Å but a significantly larger offsetting angle of 14.21°. Compared with those in L1, the two ortho- carboxylates in L2, which have a dihedral angle of 64.16° between them, deviate less from the aromatic plane to produce the smaller dihedral angles of 54.08 and 51.04°, respectively. The two ortho- carboxylates in L2 afford 46.18 and 21.47° dihedral angles with the Co4 plane, respectively. Noticeably, the extended aromatic system in L2 promotes additional parallel-displaced π-π stacking and CH∙∙∙π hydrogen bonding interactions between the adjacent 2-Co molecules, giving rise to a more robust packing in solid state (vide infra).

Figure 2. (a) A view of the Co8 cluster structure of 2-Co; (b) the parallel-displaced π-π stacking interactions (purple), CH∙∙∙π (pink) and CH∙∙∙O=S (blue) hydrogen bonding interactions between the adjacent molecules of 2-Co. The hydrogen atoms uninvolved in the hydrogen bonds and solvent molecules are not included.


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The solid-state porosity of the synthetic coordination containers was examined by the N2 adsorption experiments carried out at 77 K. As shown in Figure 3a, Compound 2-Co displays a “pseudo” type I adsorption isotherm with a Brunauer-Emmett-Teller (BET) surface area of 247 cm2/g. In contrast, the activated sample of 1-Co is essentially nonporous to N2 as confirmed by the negligible N2 uptake (~10 cm3/g STP at 77 K and 1 atm) (Figures S9 and S10). Consequently, the results reveal that 2-Co retains its crystal packing and solid-state porosity for N2 gas even after removal of its lattice solvents, which is attributed to the substantial ππ and CH∙∙∙π interactions enhanced by the extension of aromatic system from benzene to naphthalene. However, the two types of containers exhibit very similar guest binding behaviors when bulkier guests were employed (Figure 3b-d). When the solids of evacuated 1-Co or 2-Co were soaked in an aqueous solution containing methylene blue (MB), the coordination containers were found to adsorb ca. 0.6 equiv. of the dye molecules monitoring by the UV-vis spectra (Figure 3b), which shows the disappearance of the characteristic absorption maximum of MB centered at 665 nm after treated MB with 1-Co or 2-Co. Remarkably, they showed almost negligible uptake of the anion dye such as eosin Y (EY) or methyl orange (MO) even after period of one week (Figure 3c and Figure S11), possible due to the electrostatic repulsion effect induced by the negatively charged guests with respect to the electronegative oxygen atoms abundant sulfonylcalixarene-based coordination containers. Encourage by the selectivity of guest encapsulation, we next evaluated the ability of these containers in the separation of cation and anion dyes in a mixture. The cation-anion mixture of MB-EY (1 : 1) was prepared in an aqueous solution,. which displays two well-defined absorption bands centered at 519 nm and 665 nm attributed to EY and MB, respectively. After the addition of the solids of 1-Co into the MB-EY mixture solution, the absorption band centered at 665 nm (MB) decreased significantly whereas


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the absorption maximum centered at 519 nm (EY) remained unchanged (Figure 3d). Efficient separation of MB from the MB-EY mixture was achieved in the same way when 2-Co was used instead of 1-Co. The phenomenon thus confirmed unambiguously that the MB was successfully and selectively adsorbed by 1-Co or 2-Co from the MB-EY mixture. Additionally, efficient separation of MB from the MB-MO mixture was also successfully achieved in a similar manner (Figure S12). These results together reveal the potential applications of this type of sulfonylcalixarene-based coordination containers for guest separation.

Figure 3. The N2 sorption isotherms of 1-Co and 2-Co at 77 K (a) and the UV-Vis spectra of MB (b), EY (c), and MB-EY mixture (d) in aqueous solutions before and after treated with 1-Co or 2-Co.


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CONCLUSIONS We have demonstrated the design of a new family of cylinder-shaped sulfonylcalixarenebased coordination containers using ortho-dicarboxylate bridging ligands, which features a quite small bend angle of 60° with two carboxylate groups twisted obviously away from the aromatic ring. The N2 adsorption experiments indicate that the solid state porosities were well maintained through the multiple intermolecular hydrogen bonding and π-π stacking interactions after the extension of aromatic system in carboxylate linkers. Most interestingly, they exhibit promising molecular recognition towards the cation dye molecules, thus suggesting the potential applications of these new materials for guest recognition and separation. ASSOCIATED CONTENT Supporting Information. The following files are available free of charge. additional characterization data (PDF) crystallographic data (CIF) AUTHOR INFORMATION Corresponding Author * [email protected] * [email protected] ORCID Feng-Rong Dai: 0000-0003-0850-6906 Zhong-Ning Chen: 0000-0003-3589-3745 Notes


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The authors declare no competing ﬁnancial interest. ACKNOWLEDGMENT C.Z.S., Z.N.C. and F.R.D. thank the support of National Natural Science Foundation of China (21673239, 21501179, 21390392 and 21531008) and Natural Science Foundation of Fujian Province (2017J06008), the 973 Project from MSTC (Grant 2014CB845603), the CAS/SAFEA International Partnership Program for Creative Research Teams, and the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant XDB20000000). We thank the staffs from BL17B at Shanghai Synchrotron Radiation Facility for assistance during data collection. REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9.

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For Table of Contents Use Only

Sulfonylcalixaren-Based

ortho-Dicarboxylate-Bridged

Coordination

Containers for Guest Encapsulation and Separation Cheng-Zhe Sun, Tian-Pu Sheng, Feng-Rong Dai*, Zhong-Ning Chen*

Four new sulfonylcalix[4]arene-supported coordination containers were prepared using aromatic ortho-dicarboxylates as bridging ligands with both carboxylate groups twisted away from the aromatic rings. They exhibit molecular recognition towards cationic dye molecules, while specific gas adsorption properties are observed with the extension of aromatic system.


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Sulfonylcalixaren-Based ortho-Dicarboxylate-Bridged Coordination

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