A Bifunctional Anionic Metal–Organic Framework: Reversible

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A Bifunctional Anionic Metal−Organic Framework: Reversible Photochromism and Selective Adsorption of Methylene Blue Yan Zhou,† Lan Qin,†,‡ Meng-Ke Wu,† and Lei Han*,† †

State Key Laboratory Base of Novel Functional Materials and Preparation Science, School of Materials Science & Chemical Engineering, Ningbo University, Ningbo, Zhejiang 315211, China ‡ School of Chemistry and Chemical Engineering, Anshun University, Anshun, Guizhou 561000, China

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S Supporting Information *

ABSTRACT: A novel anionic Cd(II)-organic framework, {[(CH3)2NH2]2[Cd(H2BIPA-TC)2]·5(DMF)}n, has been solvothermally synthesized from a naphthalenediimide-based ligand 5,5′-(1,3,6,8tetraoxobenzo[Imn][3,8]phenanthroline-2-7-diyl)bis-1,3-benzenedicarboxylic acid (H4BIPA-TC). In the crystal structure, Cd (II) cations link H2BIPA-TC2− ligands into a 3-fold interpenetrated 3D network with dia topology. Interestingly, the title compound exhibits a reversible photochromic property and excellent adsorption capacity of Methylene Blue (MB) (149 mg/g) as compared with Rhodamine (RhB), Methyl Orange (MO), and Solvent Yellow 2 (SY2) due to electrostatic interaction in aqueous solution.

interactions, π−π stacking, electrostatic interactions, and Lewis acid−base interactions. Herein, we report a novel anionic cadmium-organic framework based on NDI-tetra-carboxylate organic ligand 5,5′-(1,3,6,8-tetraoxobenzo[Imn][3,8]phenanthroline-2-7diyl)bis-1,3-benzenedicarboxylic acid (H4 BIPA-TC).49,50 {[(CH3)2NH2]2[Cd(H2BIPA-TC)2]·5(DMF)}n (1) is a 3fold interpenetrated network with dia topology that exhibits a reversible photochromic property and excellent adsorption capacity of Methylene Blue (MB) as compared with Rhodamine (RhB), Methyl Orange (MO), and Solvent Yellow 2 (SY2) due to electrostatic interactions in aqueous solution. This is the first NDI-based MOF materials that could be used practically for the treatment of cationic dye wastewater. In addition, this study provides sample evidence that NDI-based MOFs offer a new way to be used as multifunctional materials in practical applications. Single-crystal X-ray diffraction analysis revealed that 1 crystallizes in the centro-symmetric monoclinic space group C2/c (Table S1).51,52 The asymmetric unit contains one Cd center with half occupancy, two half of partially deprotonated H2BIPA-TC2− ligands, two counter cations (CH3)2NH2+, and five disordered DMF guest molecules. As shown in Figure S1, all Cd2+ ions are six-coordinated with six oxygen atoms from the H4BIPA-TC ligands, and each Cd2+ adopts distorted octahedral coordination geometry and linked with four neighboring Cd2+ by four different ligands, and the H4BIPA-

M

etal−organic frameworks (MOFs) are porous crystalline materials constructed from metal or metal clusters (nodes) and organic ligands (linkers) that have attracted significant attention not only due to their structural diversity but also their potential applications in the field of gas storage and separation,1−5 catalysts,6−10 sensors,11−14 magnetism,15,16 and drug delivery.17,18 Photochromic MOFs are an emerging area of current interest that could respond to photo stimuli with application in host−guest chemical storage and separation.19−22 For synthesizing the photochromic MOFs, one strategy is to introduce the photoresponsive functional groups onto the organic linkers via chemical modification. Azobenzene,23−25 dithioenylethene,26−28 π-conjugated anthracene,29−32 and pyrene33−35 are promising photoresponsive functional moieties to be introduced onto the carboxylic acid, which could be used for preparing photochromic MOFs. 1,4,5,8-Naphthalenediimide (NDI) derivatives are photoactive moieties to construct photochromic MOFs due to the features of NDIs; NDIs can act as redox-active units that undergo reversible single one-electron reduction to form NDI radical anions for photoinduced electron transfer. Several studies have been focused on NDI-based MOFs to date,36−44 but only a few of them have investigated their photochromic properties, the porosity, structural topology, and π−π stacking of NDI-based MOFs, which may influence the charge transfer. Furthermore, MOFs could be used as absorbent materials45−48 for the treatment of dye wastewater due to their tunable pore sizes, shape, functional active sites, and the interactions between MOFs and adsorbates, and these interactions between host−guest frameworks could enhance the selective adsorption property of organic dyes, such as hydrogen bonding © XXXX American Chemical Society

Received: June 12, 2018 Revised: September 8, 2018 Published: September 11, 2018 A

DOI: 10.1021/acs.cgd.8b00895 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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network with a total point symbol of {66}. The simplified structure is shown in Figure 1b and Figure S3b. The phase purity of 1 was demonstrated by PXRD analysis on the crystalline samples at room temperature (Figure 2a). The experimental peak positions match well with the simulated PXRD patterns, which confirms that compound 1 is phase pure. As shown in Figure 2b, thermogravimetric analyses (TGA) under air atmosphere revealed that 1 could stable up to 140 °C with weight loss of 21.5% from 140 to 311 °C corresponding to the removal of five free DMF guest molecules (calcd 20.8%). Then, the whole framework collapsed with the loss of organic species quickly from 355 °C, and the line became flat after 721 °C. This reveals that 1 exhibits less thermal stability after loss of DMF guest molecules. Interestingly, title compound 1 shows photochromic transformation upon irradiation by sunlight or UV light; the color changes from yellow brown (1a) to dark green (1b) after irradiation. The FT-IR spectroscopy of both nonradiated (1a) and radiated (1b) conditions are shown in Figure 2c; similar absorbance peaks of 1a and 1b indicate that the crystal structure was retained after irradiation. The main characteristic absorption peaks of 1713, 1675, 1611, and 1558 cm−1 could be ascribed to C=O imide stretching and asymmetric stretching of COO− functional groups, which are in good agreement with many NDI-based MOFs.36−38 Furthermore, single X-ray crystallography shows that 1b possesses the same unit cell as 1a; however, their UV/vis spectra are different. This phenomenon indicates that an electron-transfer process rather than structure transformation may be occuring under photoresponse, and their photochromic behaviors have been proven by both UV−vis diffuse-reflectance spectroscopy and electron spin resonance (ESR) spectra. As depicted in Figure 2d, the UV−vis diffuse-reflectance spectrum of the as-synthesized crystalline sample of 1a exhibits two intense electronic absorption bands at 225 and 370 nm. They turned weak upon irradiation in the region of 200−400 nm in 1b, and the absorption band was at 370 nm, which is attribute to naphthalene diimides. Furthermore, the UV−vis spectra of radiated sample 1b displays enhanced absorption in the region of 450−800 nm, and an obvious new band at ∼630 nm appeared, which may be caused by the photoinduced electron transfer process.36,54,55 As is shown in Figure 2e, semiquantitative ESR experiments of 1a and 1b were also carried out to compare the amount of photogenerated radicals of NDI before and after irradiation under the same conditions. The generation of NDI radicals of as-synthesized 1a may be induced by indoor light, and the ESR signal with enhanced intensity could be observed after irradiation in 1b. Furthermore, the ESR spectroscopy further indicates its photochromic behavior, which gives a sharp signal at g = 2.0023. The larger amount of radicals generated upon irradiation in 1b, which led to the crystal color change and this double confirmed its photosensitive property. The abovementioned UV−vis and ESR spectra reveals that the color change of 1 may arise from photoinduced electron transfer and generation of NDI radicals (NDI•) because NDI could undergo a redox reaction to generate NDI radical anions upon light irradiation.36−38 The photoluminescent properties of 1 have also been investigated in the solid state at room temperature in Figure 2f: the maximum emission peak occurs at 580 nm under excitation at 285 nm, and the fluorescence emission intensities decrease with the increase in irradiation time. This luminescence phenomenon might be due to LLCT

TC ligands possess mono- or bidentate coordination modes between Cd2+ ions, whereas the uncoordinated COOH groups have strong O−H···O hydrogen bonds with the O···O distances equal to 2.488(3) Å. The Cd−O bond lengths and the O−Cd−O bond angles of 1 are listed in Tables S2 and S3 with the range of 2.245−2.393 Å and 54.42−140.70°, respectively. The SBU units are composed of [Cd6(H2BIPATC)6] in Figure S2, which are further extended to a 3D packing structure and its 3-fold interpenetrating structure in Figure 1a and Figure S3a. The total solvent accessible volume

Figure 1. (a) Perspective view of 3D structure in 1; (b) simplified single dia 3D topological network in 1.

of 1 is ∼3892.3 Å3 (46.5%) per unit cell. Moreover, strong π−π stacking interactions (Cg-Cg 2.7969 and 2.7971 Å) exist between the 3-fold interpenetrating frameworks calculated by PLATON,53 and these strong π−π stacking interactions favor electron transfer between the interpenetrating networks, which may cause the behavior of photoinduced electron transfer. The counter cations and DMF molecules residing in the channel interspace regions act as structure-directing or templated agents and could balance the charge of the whole frameworks. These counterions and guest DMF molecules could stabilize as well as strengthen the 3D framework. For understanding the 3D frameworks of 1 better, a topological analysis was performed. By linking the neighboring Cd2+ and viewing the ligand as a linear linker, the Cd2+ center is thus regarded as a four-connected node and the 3D framework of 1 can be deconstructed into a 4-connected underlying uninodal net that possesses a dia topological B

DOI: 10.1021/acs.cgd.8b00895 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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Figure 2. (a) Synthesized and simulated PXRD patterns in 1; (b) TGA curve of 1; (c) FTIR spectra of nonradiated 1a and radiated 1b; (d) UV/vis spectra of 1a and 1b with the inset photographic images showing photochromic transformation; (e) ESR spectra of 1a and 1b; (f) emission spectra of 1 in the solid state at room temperature upon different radiation times.

Figure 3. UV−vis spectra and related photographs of the adsorbate MB (20 mg/L) in aqueous solution for 1 with different (a) quantities and (b) times.

and/or LMCT related to π···π stacking interactions between the 3-fold interpenetrated frameworks because the free ligand

H4BIPA-TC is a nonluminescent compound.36,56 The strong O−H···O hydrogen bond and π···π stacking interactions of this C

DOI: 10.1021/acs.cgd.8b00895 Cryst. Growth Des. XXXX, XXX, XXX−XXX

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Figure 4. (a) UV−vis spectra of three desorption and resorption cycles of 1 toward MB; (b) desorption and adsorption rate of 1 toward MB and related photographs.

and photo images show that this material still displays relative high effective removal capability toward MB molecules within the first three cycles. The desorption and readsorption rates gradually decreased from 94.7 to 81% as compared with the initial concentration of MB0 in Figure 4b. In addition, we have also demonstrated the stability of this material by FTIR spectra and PXRD patterns after several cycles in Figures S10 and S11. The results of FTIR spectra showed similar absorbance peaks of all conditions, indicating the structure of the adsorbent was maintained well. Figure S11 shows the comparison PXRD patterns of 1, and after the third cycle, adsorption and desorption of MB. The result indicates that the structural framework was retained but that some peaks disappeared due to the removal of guest molecules. Thus, this material could be recyclable and reusable for practical applications in the treatment of MB dye wastewater. For confirming whether this adsorption property is related to the structural porosity of 1, N2 adsorption and desorption isotherms were performed on a Micromeritics 3Flex analyzer at 77 K, as shown in Figure S12, with N2 uptake of 4.44 cm3/g at relative pressure (P/P0 = 1.0), which is significantly small and negligible. Even though the solvent accessible volume of 1 is nearly 3892 Å3 (46.5%) per unit cell, the 3-fold interpenetrating structural framework reduces the porosity of the whole framework. On the basis of these data results, we give a proposed adsorption mechanism that electrostatic interaction affects the dye uptake capacity for 1.46,57,58 Even though the particle sizes of these three dye molecules (MB, SY2, and MO) are similar, the anionic framework prefers to adsorb more cationic organic dye molecules (MB) than anionic MO and neutral SY2 molecules. Because the framework of 1 is negatively charged and would have an electrostatic interaction with positively charged organic dye MB molecules, it thus significantly enhances MB adsorption. Compared with another cationic dye molecules (RhB), it is hard to diffuse the pores of the adsorbent due to its large size, which decreases the uptake capacity. Taking the interpenetration structural feature into consideration, the 3-fold interpenetrated frameworks reduce its porosity and prevent large molecules from entering the pores; thus, electrostatic interactions play a prominent role in dye adsorption. In summary, a 3-fold interpenetrated anionic MOF based on naphthadiimide tetracarboxylate ligands has been successfully synthesized under solvothermal conditions, ands this interpenetrated network possesses dia topology. Furthermore, title compound 1 showed bifunctional properties including reversible photochromic and cationic organic dye adsorption property, and the photochromism of 1 may arise from photoinduced electron transfer and the generation of NDI

3-fold interpenetrated framework lead to the change of their luminescent behaviors as compared with those of the free ligand. For systemic study of the absorption properties of 1 toward organic dyes in aqueous solution, four dye molecules were selected (Figure S4); that is, cationic Methylene Blue (MB), Rhodamine B (RhB), anionic Methyl Orange (MO), and neutral Solvent Yellow 2 (SY2) as adsorbates. The sizes of these dye molecules are similar except RhB, which is the largest. The UV−vis spectra results show that Methylene Blue (MB) could be significantly absorbed with excellent capacity and dye removal rate (Figure 3a and Figure S5), whereas RhB (Figure S6), SY2 (Figure S7), and MO (Figure S8) just show slight absorbance. In Figure 3a, the blue MB solutions fade rapidly, and the concentration of MB decreased to 5.7% of the original concentration C0, which means that MB removal % equals 94.3%. The standard adsorption curve was carried out to calculate the saturated adsorption capacity of 1 toward MB with different concentrations in which it fits well linearly as a function of absorbance verse concentration (C0, mg/L) (Figure S9). The adsorption capacity of 1 is 149.0 mg/g relative higher than those of many of the absorbent MOF materials (Table S4). Moreover, the adsorption efficiency of 1 toward MB was tested. In Figure 3b, 5.0 mg of activated sample 1 was dipped into MB (20 mg/L, 10 mL) with different given times, respectively. The results show that 82.3% of original MB could be quickly adsorbed within 5 min; then, after a slow adsorption process, even 8.6% of MB was still unabsorbed after 24 h. The above-mentioned experimental results show that 1 can be used as adsorbent material to remove MB dye molecules efficiently from aqueous solution. Comparing with the MB adsorption ability of 1, only 46% of the original SY2 adsorbed even with 13 mg of absorbents, and the adsorption capacity of 1 toward neutral SY2 is 7.1 mg/g. The adsorption capacity of the largest RhB dye molecules is equal to 8.0 mg/g, whereas MO is the least adsorbing for 1 with an adsorption capacity of 4.6 mg/g. Furthermore, for investigating the recyclability of the dye adsorption and desorption, dye release and readsorption experiments were carried out as follows: the sample of MB @ 1 after adsorption process was immersed into a solution of NaCl in 1:1 ethanol and water. The solution immediately turns blue, which indicates that MB molecules released rapidly from MB-loaded MOFs. After 3 h, the colored solution of MB released from MB @ 1 was centrifuged and monitored by UV−vis spectra. Meanwhile, the MB released MOFs solid sample was dried at 60 °C and continuously used for the second and third cycles of readsorption and desorption experiments. As shown in Figure 4a and b, the spectroscopy D

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radicals (NDI•). Furthermore, it exhibits excellent adsorption capacity of Methylene Blue (MB) (149 mg/g) as compared with Rhodamine (RhB), Methyl Orange (MO), and Solvent Yellow 2 (SY2) due to electrostatic interactions in aqueous solution. It also displays relatively high desorption and readsorption rates of MB within several cycles. In addition, this material is quite stable and reusable, which could be practically used for the treatment of cationic dye wastewater.

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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/acs.cgd.8b00895. Materials and characterization, detailed synthesis, X-ray crystallographic data, UV−vis spectra, N2 adsorption and desorption isotherms, FTIR spectra, PXRD patterns, and related figures and supplementary tables (PDF) Accession Codes

CCDC 1840948 contains 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 CB21EZ, UK; fax: + 44 1223 336033.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Lei Han: 0000-0002-2433-9290 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We are grateful for financial support from the National Natural Science Foundation of China (no. 21471086) and the K.C. Wong Magna Fund of Ningbo University.

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REFERENCES

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DOI: 10.1021/acs.cgd.8b00895 Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Communication

(58) Hou, Y. X.; Sun, J. S.; Zhang, D. P.; Qi, D. D.; Jiang, J. Z. Porphyrin−Alkaline Earth MOFs with the Highest Adsorption Capacity for Methylene Blue. Chem. - Eur. J. 2016, 22, 6345−6352.

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DOI: 10.1021/acs.cgd.8b00895 Cryst. Growth Des. XXXX, XXX, XXX−XXX