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Metal-Assembled, Resorcin[4]arene-Based Molecular Trimer for Efficient Removal of Toxic Dichromate Pollutants and Knoevenagel Condensation Reaction Xue Han,† Ya-Xin Xu,† Jin Yang,*,† Xianxiu Xu,‡ Cheng-Peng Li,*,§ and Jian-Fang Ma*,† †

Key Lab for Polyoxometalate Science, Department of Chemistry, Northeast Normal University, Changchun 130024, China College of Chemistry, Chemical Engineering and Materials Science, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong Normal University, Jinan 250014, China § College of Chemistry, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, MOE Key Laboratory of Inorganic−Organic Hybrid Functional Material Chemistry, Tianjin Normal University Tianjin 300387, China

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ABSTRACT: Self-assembly of resorcin[4]arene-based coordination cages involving more than two resorcin[4]arenes poses significant challenges for the requirements of suitable functionalized resorcin[4]arene ligands and metals. Here, we report an unusual example of a metal-coordinated, resorcin[4]arene-based molecular trimer (1NO3), composed of three resorcin[4]arenes and three Cd(II) cations. In particular, 1NO3 features efficient and selective removal of environmentally toxic dichromate (Cr2O72−) anions. Moreover, the Knoevenagel condensation reaction was also explored by using 1-NO3 as an efficient heterogeneous catalyst.

KEYWORDS: molecular trimer, resorcin[4]arene, Knoevenagel condensation reaction, anion exchange, dichromate pollutant

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far.47,48 To the best of our knowledge, such supramolecular trimers with environmentally toxic oxoanion capture capability have not been explored thus far.35,49 Nevertheless, it still remains a big challenge to assemble the resorcin[4]arene-based molecular trimers, as a result of requirements for the suitable functionalized resorcin[4]arene ligands and metals.50,51 In this context, the use of a resorcin[4]arene-based multitopic donor ligand was largely neglected owing to the possibility of generation of the supramolecular trimers upon diverse donors around the metal centers.52 Along this line, self-assembly of the four triazole-functionalized resorcin[4]arene ligand (TTR4A) with Cd(II) cations affords a nanosized molecular trimer, [Cd3(TTR4A)3(H2O)6]· 6NO3·3DMF·3H2O (1-NO3), made of three TTR4A ligands and three Cd(II) cations (Scheme 1). Significantly, 1-NO3 exhibits fast and selective capture of environmentally toxic dichromate (Cr2O72−) anions.53−55 The Knoevenagel condensation reaction was also studied using 1-NO3 as an efficient heterogeneous catalyst.56,57 1-NO3 represents a unique example of a metal-assembled, resorcin[4]arene-based molecular trimer which absorbs the Cr2O72− pollutant.

INTRODUCTION Development of functional self-assembled supramolecular arrays has attracted considerable attention owing to their intriguing structural features and unique properties.1−7 In this facet, metal−ligand coordination-directed self-assembly has evolved to be a powerful technique for constructing functional discrete nanosized molecular architectures.8−15 For this purpose, judicious choice of polydentate ligand components plays a vital role in self-assembly of the resulting supramolecular architectures.16−21 Resorcin[4]arenes, as one fascinating and versatile class of bowl-shaped molecules, have been extensively utilized as building blocks for supramolecular self-assembly. 22−28 Resorcin[4]arene functionalization by inserting appropriate ligating moieties has been proven as a promising and powerful approach for the ligand design and served as an excellent platform for coordination-driven self-assembly.29−34 To date, the use of functionalized resorcin[4]arenes in combination with metals has produced an extensive series of self-assembled supramolecular arrays.35−41 It must be noted, however, that examples of these metal-coordinated resorcin[4]arene-based systems are restricted to dimeric polymetallic species.42−44 The ones in particular based on more than two resorcin[4]arenes are exceedingly less observed in the self-assembly processes upon metal coordination.45,46 In contrast to the most often exploited dimers, only limited examples of the resorcin[4]arene-based trimeric molecular loops have been reported thus © XXXX American Chemical Society

Received: January 31, 2019 Accepted: April 4, 2019

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DOI: 10.1021/acsami.9b02068 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

Research Article

ACS Applied Materials & Interfaces Scheme 1. Self-Assembly of Cadmium(II)-Coordinated Resorcin[4]arene-Based Molecular Trimer (1-NO3)

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nm (characteristic peak of the N3−) in 1-N3 and 2071 nm (characteristic peak of the SCN−) in 1-SCN occurred (Figure 2).60 The result indicates that the NO3− anions in 1-NO3 were partly exchanged by the incursive anions. The powder X-ray diffraction (PXRD) patterns indicate that the structural integrity was well retained after the anion exchanges (Figure S4). Considering such structural features, the capture capability of environmentally toxic Cr2O72− was studied using 1-NO3 as an adsorbent. As shown in Figures 3a, S5, and S6, the typical Cr2O72− exchange was conducted by simply immersing the crystalline samples of 1-NO3 (30 mg) in an aqueous solution of Cr2O72− (3 mM, 5 mL) at room temperature. The concentration of Cr2O72− in the aqueous solution was monitored by UV−vis spectroscopy. The intensity of the characteristic adsorption peak of Cr2O72− (λmax = 352 nm) decreases by 44% within 90 min. After 210 min, the corresponding Cr2O72− concentration in aqueous solution decreased by 60.8%. Accordingly, the capture capacity of Cr2O72− reached to 66 mg/g. After 1440 min, the Cr2O72− exchange was accomplished with an overall Cr2O72− capture capacity of 94.5 mg/g. When the Cr2O72− concentrations changed from 3 to 5 mM, ca. 29.7 and 51% of the Cr2O72− anions were exchanged after 90 and 210 min, respectively. The corresponding Cr2O72− trapping capacities are up to 53.8 and 92.4 mg/g, respectively. The maximum capture capacity after 1440 min reaches 120.5 mg/g. Further, a similar Cr2O72− exchange experiment was also carried out in 7 mM solution of Cr2O72−. The concentrations of Cr2O72− decreased by ca. 22 and 40.7% after 90 and 210 min, respectively. After 1440 min, the total Cr2O72− exchange capacity is up to 139 mg/g. At the same time, the color of the crystals varied from colorless to yellow (Figure 3b), and the color change of the solution well corresponds to the UV−vis absorption spectra of time dependence (Figure S6). Clearly, the Cr2O72− trapping capacities were gradually enhanced with the increased Cr2O72− concentrations varying from 3 to 7 mM. The result implies that the Cr2O72− exchange capacity by using 1-NO3 as an adsorbent is highly dependent on the concentrations of Cr2O72− in water. The PXRD pattern demonstrates that the structural integrity still remained after the Cr2O72− exchange (Figure S7). The energy-dispersive Xray (EDX) spectrum further confirmed the inclusion of loaded Cr2O72− after the anion exchange (Figures 3c and S8). In contrast to conventional anion exchange, anion selectivity is also critical and challenging in the adsorption process.61−63 Thus, the selective adsorption toward the mixed anions was

RESULTS AND DISCUSSION Structural Description of [Cd3(TTR4A)3(H2O)6]·6NO3· 3DMF·3H2O (1-NO3). The metal-coordinated, resorcin[4]arene-based molecular trimer (1-NO3) was achieved by selfassembly of TTR4A and Cd(NO3)2·4H2O under solvothermal conditions. The SQUEEZE function of PLATON was applied to remove the disordered solvents, and the formula was established by the elemental analysis,58 thermogravimetric data, and the residual electron density (Figure S1). Crystallographic analysis demonstrated that 1-NO3 crystallizes in the hexagonal space group P63/mmc. As shown in Figure 1a, each Cd(II) cation is six-coordinated with four nitrogen atoms (N3, N3#1, N3#2, and N3#3) from two different TTR4A ligands and two water oxygen atoms (O1W and O2W) in an octahedral coordination sphere. Each TTR4A ligand bridges two Cd(II) cations via two pairs of 1,2,4-triazole groups. In this fashion, three Cd(II) cations were interlinked by three TTR4A cavitands to give a nanosized Cd(II) resorcin[4]arene trimer [Cd3(TTR4A)3(H2O)6]6+ (Figure 1b). Three bowl-shaped resorcin[4]arene ligands afford three corners of an equilateral molecular triangle. The anions were not located from the difference Fourier maps because of their high disorders. The strong peak associated with NO3− appeared at 1384 nm in the infrared (IR) spectrum, demonstrating that the positive charge of the triangle [Cd3(TTR4A)3(H2O)6]6+ is balanced by the NO3− anions (Figure 2). Interestingly, each TTR4A cavitand is further interacted with six nearest neighbors through aromatic π−π interactions with centroid-to-centroid and centroid-toplane distances of ca. 3.95 and 3.86 Å, respectively, and a dihedral angle of 14.168° (Figure S2), producing an elegant supramolecular layer with a channel diameter of about 9.4 Å regardless of the van der Waals radius of the two related C atoms (C10 and its symmetry-related C10#4, #4 1 + x − y, 2 − y, 1 − z) (Figures 1c and S3). The solvents and nitrates probably reside in the channels of the supramolecular layers, based on an elucidation of crystallographic data of 1-NO3. The free volume after removal of the disordered solvents is about 36.3% in one unit cell by PLATON calculation.62 During anion exchange, as mentioned above, the NO3− anions are probably encapsulated in the supramolecular channels of 1-NO3. Therefore, we wonder if the NO3− anion could be exchanged by other anions. The crystalline samples of 1-NO3 were simply soaked in an aqueous solution of KN3 and KSCN (20 mM). After 6 h, the IR spectra of the N3− and SCN− exchanged samples show that the strong bands associated with NO3− at 1384 nm were weakened drastically, as illustrated in Figure 2.59 In contrast, the new peaks at 2039 B

DOI: 10.1021/acsami.9b02068 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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ACS Applied Materials & Interfaces

Figure 3. (a) Adsorption kinetics of aqueous Cr2O72− with different concentrations (3, 5, and 7 mM). (b) Photographs showing the color changes of the samples after Cr2O72− exchange. (c) EDX mapping profiles for 1-Cr2O7.

performed for 1-NO3. The crystalline sample of 1-NO3 (10 mg) was immersed into a 3 mL aqueous solution of the mixed NO3−, H2PO3−, and Cr2O72− anions (5 mM of each anion) for 24 h, and the crystals gradually turned yellow. Accordingly, the overall adsorption capacity of Cr2O72− reached up to 113 mg/ g, demonstrating that the capture behavior of Cr2O72− was not disturbed by other anions (Figure 4). When a mixture of 40-

Figure 1. (a) Coordination environments of the Cd(II) cations in 1NO3. (b) View of the Cd(II) resorcin[4]arene trimer of 1-NO3. (c) View of the 2D supramolecular layer formed by aromatic π−π interactions of each trimer with six nearest neighbors (dotted lines: the centroid-to-centroid distances of the aromatic π−π interactions). The yellow ball and blue ball represent the inner cavities of the resorcin[4]arenes and the channels formed by six resorcin[4]arenebased trimers, respectively. Symmetry codes: #1−y + 1, −x + 1, −z + 1/2; z; #2x, y, −z + 1/2; #3−x + y + 1, y, z.

Figure 4. Trapping capability of Cr2O72− by 1-NO3 in the absence or presence of disturbing anions.

fold disturbing anions was employed (200 mM of each disturbing anion), the Cr2O72− sorption capability still retains high efficiency (115 mg/g), as shown in Figure 4. The result suggests good selectivity for Cr2O72− over NO3− and H2PO3− anions. The selective adsorption for Cr2O72−probably arises from the stronger interaction of Cr2O72− with a cationic trimer network than NO3− and H2PO3− anions.64 Knoevenagel Condensation Reaction. The crystalline sample of 1-NO3 was soaked in acetone for 2 days and then was activated at 90 °C to remove the coordinated water molecules. Given the exposed Lewis acid Cd(II) sites and Lewis base N sites, the catalytic performance of 1-NO3 toward Knoevenagel condensation reaction was conducted under solvent-free conditions. Gas-chromatography (GC) was used to calculate the conversion yields, which are further conformed

Figure 2. IR spectra of 1-NO3, 1-N3, and 1-SCN.

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DOI: 10.1021/acsami.9b02068 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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ACS Applied Materials & Interfaces by 1H NMR (Figures S9−S11). The optimum reaction condition was investigated by using the typical benzaldehyde and malononitrile as substrates (Scheme 2). Almost no

Table 1. Knoevenagel Condensation Reaction of Malononitrile with Various Benzaldehyde Derivatives Catalyzed by 1-NO3a

Scheme 2. Schematic Representation of Knoevenagel Condensation Reaction by Using Benzaldehyde and Malononitrile as Substrates

catalytic product was achieved without catalyst 1-NO3 at 60 °C after catalytic reaction of 1 h (Table S1). In contrast, when catalyst 1-NO3 (0.001 mmol) was used, the conversion of benzaldehyde is up to 44% under the same condition. Noticeably, with the increased catalyst amounts from 0.001 to 0.003 mmol, the conversions of the substrates were enhanced from 44 to 98% after 1 h (Figure S12). Moreover, only 17% conversion was achieved in the presence of 1-NO3 (0.003 mmol) at 30 °C after 1 h. By elevating temperatures from 30 to 60 °C, the conversions increased from 17 to 98% (Figure S13, entry 1). As a result, the following catalytic experiments were conducted with catalyst 1-NO3 (0.003 mmol) at 60 °C. It should be noted that the TTR4A as the homogeneous catalyst also was used in Knoevenagel condensation reaction with the conversion of 79% under the same condition (Figure S9j). However, there exists a great difficulty in separating the TTR4A from the homogeneous reaction system relative to heterogeneous catalyst 1-NO3. To explore the generality of 1-NO3, a series of benzaldehyde derivatives with various moieties were chosen as substrates. As illustrated in Table 1, the benzaldehyde derivatives with electron-withdrawing moieties, such as −CN, −Cl, and −NO2, were converted to the products within 1 h with a high turnover frequency of 330.0 h−1 (entries 2−4). However, the electrondonating benzaldehyde derivatives with −CH3, −C2H5, and −OCH3 gave the relatively low conversion yields (entries 5− 7). The result demonstrates that the benzaldehyde derivatives possessing electron-withdrawing moieties are greatly reactive with respect to the ones with electron-donating groups in Knoevenagel condensation reaction.65,66 For the large substrate cinnamaldehyde, only 68% conversion yield was achieved at the optimum reaction condition (entry 8), which may be ascribed to the increased steric hindrance of the substrate.67 In order to check the heterogeneity of the catalytic reaction, the filtration experiment of catalyst 1-NO3 was studied. The catalyst was removed after 30 min, and the resulting filtrate was further stirred for 30 min. As depicted in Figure 5, the conversion yield of the benzaldehyde still remains unchanged for the filtrate, suggesting that the catalytic process is heterogeneous. Moreover, the recyclability of catalyst 1-NO3 was further studied by using 2-chlorobenzaldehyde and malononitrile as substrates. After 1 h of the catalytic reaction, the sample of 1NO3 was filtrated and washed with dichloromethane. Then, the resulting catalyst 1-NO3 was reused for the next cycle of catalytic reaction. Noticeably, the catalytic activity of 1-NO3 almost remains unchanged after four cycles (Figure 6). Further, the PXRD pattern of 1-NO3 after catalysis still well corresponds to the simulated one (Figure S14). The result

a

Reaction condition: catalyst 1-NO3 (0.003 mmol), benzaldehyde derivative (1 mmol), malononitrile (2 mmol), 1 h, 60 °C. b Conversion was calculated by GC and 1H NMR. cMoles of the catalytic product per mole of 1-NO3 per hour.

Figure 5. Conversion of the benzaldehyde in Knoevenagel condensation reaction by using catalyst 1-NO3 (red) and the filtrate (black).

indicates that 1-NO3 as the catalyst exhibits good recyclability and stability. The Knoevenagel condensation reaction is usually catalyzed by Lewis base or acid−base bifunctional catalysts. As shown in Figure S15, the Cd(II) and N sites act as Lewis acid and Lewis base, respectively. 68,69 The carbonylate group of the benzaldehyde interacts with Cd(II) ions during catalysis. Simultaneously, malononitrile interacts with weak Lewis basic D

DOI: 10.1021/acsami.9b02068 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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ACS Applied Materials & Interfaces

(2) Fang, Y.; Xiao, Z.; Li, J.; Lollar, C.; Liu, L.; Lian, X.; Yuan, S.; Banerjee, S.; Zhang, P.; Zhou, H.-C. Formation of A Highly Reactive Cobalt Nanocluster Crystal within a Highly Negatively Charged Porous Coordination Cage. Angew. Chem., Int. Ed. 2018, 57, 5283− 5287. (3) Gan, M.-M.; Liu, J.-Q.; Zhang, L.; Wang, Y.-Y.; Hahn, F. E.; Han, Y.-F. Preparation and Post-Assembly Modification of Metallosupramolecular Assemblies from Poly(N-Heterocyclic Carbene) Ligands. Chem. Rev. 2018, 118, 9587−9641. (4) Bi, Y.; Li, Y.; Liao, W.; Zhang, H.; Li, D. A Unique Mn2Gd2 Tetranuclear Compound of p-tert-Butylthiacalix[4]arene. Inorg. Chem. 2008, 47, 9733−9735. (5) Carné-Sánchez, A.; Craig, G. A.; Larpent, P.; Hirose, T.; Higuchi, M.; Kitagawa, S.; Matsuda, K.; Urayama, K.; Furukawa, S. Self-assembly of Metal−Organic Polyhedra into Supramolecular Polymers with Intrinsic Microporosity. Nat. Chem. 2018, 9, 2506− 2514. (6) Smith, J. N.; Lucas, N. T. Rigid tetraarylene-bridged cavitands from reduced-symmetry resorcin[4]arene derivatives. Chem. Commun. 2018, 54, 4716−4719. (7) Choi, Y.; Jeon, D.; Choi, Y.; Ryu, J.; Kim, B.-S. Self-Assembled Supramolecular Hybrid of Carbon Nanodots and Polyoxometalates for Visible-Light-Driven Water Oxidation. ACS Appl. Mater. Interfaces 2018, 10, 13434−13441. (8) Kashapov, R. R.; Kharlamov, S. V.; Sultanova, E. D.; Mukhitova, R. K.; Kudryashova, Y. R.; Zakharova, L. Y.; Ziganshina, A. Y.; Konovalov, A. I. Controlling the Size and Morphology of Supramolecular Assemblies of Viologen-Resorcin[4]arene Cavitands. Chem.Eur. J. 2014, 20, 14018−14025. (9) Wang, S.; Gao, X.; Hang, X.; Zhu, X.; Han, H.; Liao, W.; Chen, W. Ultrafine Pt Nanoclusters Confined in a Calixarene-Based {Ni24} Coordination Cage for High-Efficient Hydrogen Evolution Reaction. J. Am. Chem. Soc. 2016, 138, 16236−16239. (10) Rathnayake, A. S.; Fraser, H. W. L.; Brechin, E. K.; Dalgarno, S. J.; Baumeister, J. E.; White, J.; Rungthanaphatsophon, P.; Walensky, J. R.; Barnes, C. L.; Teat, S. J.; Atwood, J. L. In Situ Redox Reactions Facilitate the Assembly of A Mixed-Valence Metal-Organic Nanocapsule. Nat. Commun. 2018, 9, 2119. (11) Kumari, H.; Mossine, A. V.; Kline, S. R.; Dennis, C. L.; Fowler, D. A.; Teat, S. J.; Barnes, C. L.; Deakyne, C. A.; Atwood, J. L. Controlling the Self-Assembly of Metal-Seamed Organic Nanocapsules. Angew. Chem., Int. Ed. 2012, 51, 1452−1454. (12) Park, J.; Jiang, Q.; Feng, D.; Mao, L.; Zhou, H.-C. SizeControlled Synthesis of Porphyrinic Metal-Organic Framework and Functionalization for Targeted Photodynamic Therapy. J. Am. Chem. Soc. 2016, 138, 3518−3525. (13) Shivayuk, A. Nanoencapsulation of Calix[4]arene Inclusion Complexes. J. Am. Chem. Soc. 2007, 129, 14196−14199. (14) Wang, C.-X.; Xia, Y.-P.; Yao, Z.-Q.; Xu, J.; Chang, Z.; Bu, X.-H. Two Luminescent Coordination Polymers as Highly Selective and Sensitive Chemosensors for CrVI-Anions in Aqueous Medium. Dalton Trans. 2019, 48, 387−394. (15) Chen, C.-X.; Wei, Z.; Jiang, J.-J.; Fan, Y.-Z.; Zheng, S.-P.; Cao, C.-C.; Li, Y.-H.; Fenske, D.; Su, C.-Y. Precise Modulation of the Breathing Behavior and Pore Surface in Zr-MOFs by Reversible PostSynthetic Variable-Spacer Installation to Fine-Tune the Expansion Magnitude and Sorption Properties. Angew. Chem., Int. Ed. 2016, 55, 9932−9936. (16) Ye, Y.; Guo, W.; Wang, L.; Li, Z.; Song, Z.; Chen, J.; Zhang, Z.; Xiang, S.; Chen, B. Straightforward Loading of Imidazole Molecules into Metal-Organic Framework for High Proton Conduction. J. Am. Chem. Soc. 2017, 139, 15604−15607. (17) Hang, X.; Liu, B.; Zhu, X.; Wang, S.; Han, H.; Liao, W.; Liu, Y.; Hu, C. Discrete {Ni40} Coordination Cage: A Calixarene-Based Johnson-Type (J17) Hexadecahedron. J. Am. Chem. Soc. 2016, 138, 2969−2972. (18) Zhang, L.; Han, Y.-F. A Macrocyclic Silver Polycarbene Complex Based on 1,2,4-Triazole Units: Synthesis and Postsynthetic Modification. Dalton Trans. 2018, 47, 4267−4272.

Figure 6. Recycled experiments for Knoevenagel condensation reaction using catalyst 1-NO3.

N sites to generate carbon anion species. Finally, the carbon anion species attack the activated benzaldehyde, producing the benzylidenemalononitrile.66

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CONCLUSIONS In summary, we have described an unusual example of the metal-assembled, resorcin[4]arene-based molecular trimer (1NO3). 1-NO3 can act as an efficient adsorbent for environmental pollutant Cr2O72−. Moreover, 1-NO3 exhibits open Cd(II) sites after activation, making 1-NO3 an efficient heterogeneous catalyst for the Knoevenagel condensation reaction with high conversion and selectivity. This work provides an attractive route to achieve the resorcin[4]arenebased functional molecular trimers by the careful use of a resorcin[4]arene-based multitopic donor ligand. Our efforts to design the metal-coordinated, functional, molecular assemblies with the resorcin[4]arene-based ligands are ongoing.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.9b02068. Experimental section, GC spectra, 1H NMR spectra, thermogravimetric analysis, PXRD patterns, IR, figures, and tables (PDF) Crystallographic data for 1-NO3 (CIF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (J.Y.). *E-mail: [email protected] (C.-P.L.). *E-mail: [email protected]. Fax: +86-431-85098620 (J.F.M.). ORCID

Jian-Fang Ma: 0000-0002-4059-8348 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (grant nos. 21771034 and 21471029). REFERENCES

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DOI: 10.1021/acsami.9b02068 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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DOI: 10.1021/acsami.9b02068 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX