Multifunctional Zinc MetalâOrganic Framework ... - ACS Publications

Subscriber access provided by University of Newcastle, Australia

Article 4

A multifunctional zinc metal-organic framework based on designed HTCPP ligand with AIE effect: CO adsorption, luminescence and sensing property 2

Yangyang Jiang, Libo Sun, Jianfeng Du, Yuchuan Liu, Huaizhong Shi, Zhiqiang Liang, and Jiyang Li Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b00068 • Publication Date (Web): 15 Mar 2017 Downloaded from http://pubs.acs.org on March 18, 2017

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

Crystal Growth & Design is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 22

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Crystal Growth & Design

A multifunctional zinc metal-organic framework based on designed H4TCPP ligand with AIE effect: CO2 adsorption, luminescence and sensing property Yangyang Jiang, Libo Sun, Jianfeng Du, Yuchuan Liu, Huaizhong Shi, Zhiqiang Liang* and Jiyang Li* State Key Lab of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun, 130012, P. R. China E-mail: [email protected]; [email protected].

ABSTRACT: A

new

rigid

and

2,3,5,6-tetrakis(4-carboxyphenyl)pyrazine

symmetrical (H4TCPP)

tetracarboxylic with

ligand

aggregation-induced

emission (AIE) effect has been designed and synthesized. By using such ligand, a novel multifunctional metal-organic framework Zn-TCPP has been successfully constructed. The cross linkage of dinuclear Zn2(COO)4 clusters and organic TCPP4- ligands results in the 3D channel structure of Zn-TCPP, which has a four connected lvt topology with the point symbol of {42.84}. Zn-TCPP not only displays bright blue luminescence arising from the matrix coordination-induced emission effect of TCPP4- ligand, but also exhibits effective detection for picric acid (PA) and Fe3+ ions. In addition, the activated Zn-TCPP possesses highly porous framework with BET surface area of 984 m2 g-1 and CO2 adsorption capacity up to 135 cm3 g-1 at 273 K and 732 mmHg. This work represents a successful example of constructing MOFs with desired functions based on the designed organic ligand.

ACS Paragon Plus Environment


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 22

INTRODUCTION Metal-organic frameworks (MOFs) are hybrid inorganic-organic crystalline materials composed of metal ions/clusters and organic linkers.1-5 Emerging as a new class of porous materials, MOFs have attracted more attention in recent years.6 A large variety of MOFs with desired topological frameworks and functions has been synthesized through considering the organic ligand, the framework structure, the surface area, the channel size and functional groups.7-10 The tunable porous structure and the combined advantages of inorganic and organic polymers endow MOFs with broad potential applications in gas adsorption/separation,11-14 heterogeneous catalysis,15 photovoltaic

conversion,16-20

molecular

magnetism,21-22

luminescent

sensing17,23-26/recognition,27-28 drug/guest storage29-32 and so on. Over the past few decades, the rising level of atmospheric CO2 that causes global warming is destroying our living environment.33-35 Thus, decreasing the concentration of CO2 in atmosphere is an urgent task, which motivates more researchers developing various methods and materials for CO2 capture and sequestration. Physical adsorption of CO2 on porous solids including molecular sieves, carbon-based materials, MOFs and porous organic polymers, has been proven to be an effective and promising approach to alternate the traditional amine-based chemical absorption that suffers high cost, corrosion and chemical decomposition in the regeneration process. In various porous materials, MOFs exhibit excellent performance for CO2 adsorption due to their defined structures, regular channels and/or cages and high surface area. Meanwhile, the presence of unsaturated open metal sites and chemical functionalities (such as acids, amines, hydroxyl groups and N-containing heterocycles) could increase the affinity between MOFs and CO2.36-39 Furthermore, the pore wall could be decorated by functional groups to improve the adsorption capacity and selectivity of CO2.40-42 On the other hand, MOFs can be used as sensor materials to detect and identify the organic species and metal ions. Such detection is mainly based on the luminescent quenching or enhancement of lanthanide ions or the luminescent organic ligands. A notable example is that Li et al. reported the first highly luminescent MOF to detect nitroaromatic compounds 2,4-dinitrotoluene (DNT) and 2,3-dimethyl-2,3-dinitrobutane


Page 3 of 22

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(DMNB) in the vapor phase.43 Considering the living environment and healthy, the exploitation of bi-functional chemosensor for detecting nitroaromatic compounds that can harm personal and environmental safety and the metal ions (i.e. Fe3+) that are indispensable for the human body is of great significance.44 In general, the design and synthesis of functional organic ligands is crucial to achieve the multifunctional MOFs with CO2 capture and sensing properties. In the previous

reports,

the

rigid

and

highly

symmetric

tetracarboxylic

ligand

4,4′,4′′,4′′′-benzene-1,2,4,5-tetrayltetrabenzoic acid (H4BTTB) has been widely used to synthesize pillared paddlewheel porous MOFs with diverse properties such as gas sorption/separation,45 catalysis46 and energy transfer.47 Tetraphenylethylene-based molecules with aggregation-induced emission (AIE) effect have been utilized to construct

MOFs,48-50

luminescent

porous

organic

polymers

(POPs)51-54

and

inorganic-organic hybrid materials.55-56 As a new kind of AIEgen, tetraphenylpyrazine and its derivatives have high symmetry and rigid skeleton, which can be easily prepared under mild reaction conditions.57 Therefore, the tetraphenylpyrazine-based carboxylic acid ligand will show promising prospect in the construction of functional MOFs. In

this

paper,

a

new

tetraphenylpyrazine-based

tetracarboxylic

ligand

2,3,5,6-tetrakis(4-carboxyphenyl)pyrazine (H4TCPP, Scheme 1) has been designed and synthesized based on the following reasons. Firstly, H4TCPP possesses a rigid skeleton similar to H4BTTB, which can be easily synthesized from methyl 4-formylbenzoate.57 Secondly, there are two N atoms within the pyrazine core, which is propitious to enhance the adsorption ability for CO2 and the sensing selectivity for analytes. Finally and most importantly, the AIE effect of H4TCPP will endow MOFs with interesting luminescent property. By using this ligand, a new multifunctional Zn-TCPP MOF with lvt topology has been successfully constructed. The activated Zn-TCPP possesses high CO2 adsorption capacity up to 135 cm3 g-1 at 273 K and 732 mmHg. Zn-TCPP displays bright blue luminescence benefiting from the matrix coordination-induced emission effect of TCPP4- ligand, which can be used as a sensor to detect picric acid (PA) and Fe3+ ions.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Scheme 1. Design and synthesis diagram of H4TCPP ligand.

EXPERIMENTAL SECTION Materials and characterizations. All the chemicals were of reagent grade quality and obtained from commercials sources without further purification. The IR absorption spectra were recorded within the 400-4000cm-1 region on a Nicolet Impact 410 FTIR spectrometer with KBr pellets. Powder X-ray diffraction (PXRD) patterns were collected on a Rigaku D-Max 2550 diffractometer using Cu-Kα radiation (λ = 0.15418 nm) in a 2θ range of 4-40o with a scan speed of 12o min-1 at room temperature. The elemental analyses (C, H and N) were performed using a Perkin-Elmer 2400 elemental analyzer. Thermogravimetric analyses (TGA) were performed on a TGA Q500 V20.10 Build 36 thermogravimetric analyzer from room temperature to 800 oC in air atmosphere with a heating rate of 10 oC min-1. Fluorescence measurements were carried out on a SHIMADZU RF-5302 PC fluorescence spectrophotometer and FLUOROMAX-4. The point symbol and topological analysis were conducted using the TOPOS 4.0 program package.58 Crystal structure determination. Data was collected on a BRUKER SMART APEX Ⅱ CCD diffractometer for Zn-TCPP with graphite-monochromated Mo Kα radiation (λ = 0.71073 nm). Data processing was accomplished with the SAINT processing program.59 The structure was


Page 4 of 22

Page 5 of 22

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


solved by direct method and refined by full-matrix least-squares methods with SHELXTL-97 program package.60 All non-hydrogen atoms were refined with anisotropic displacement parameters. The hydrogen atoms on the aromatic rings were geometrically placed with isotropic thermal parameters 1.2 times that of the attached carbon atom. Attempts to locate and model the highly disordered solvent molecules in the pores were unsuccessful. Therefore, the SQUEEZE routine of PLATON was used to remove the diffraction contribution from guests to produce a set of solvent-free diffraction intensities.61-62 Summary of the crystallographic data and refinement parameters are given in Table S1. The selected bond lengths and angles of Zn-TCPP are given in Table S2. The asymmetric unit of Zn-TCPP is shown in Figure S1. Synthesis of 2,3,5,6-tetrakis(4-(methoxycarbonyl)phenyl)pyrazine To a solution of vitamin B1 (360 mg, 0.27 mmol) in the mixture solvent of CH3OH (6 mL) and H2O (2 mL) was dropwise added NaOH (1 mL, 2 M) to adjust pH of 9-10, then added methyl 4-formylbenzoate (3.0 g, 18.29 mmol). After being stirred one hour in the ice water bath, the reaction mixture was heated at 60 oC for one hour and at 85 oC for one hour, and the precipitate was formed. After filtering, the product dimethyl 4,4'-(1-hydroxy-2-oxoethane-1,2-diyl)dibenzoate was obtained. Then, to a solution of this product (1.64 g, 5.00 mmol) and ammonium acetate (1.155 g, 15.00 mmol) in acetic acid 5 mL was added acetic anhydride (765 mg, 7.50 mmol). After stirred for 12 h at 120 oC under N2, the precipitate was formed. Filtration and washing with H2O and diethyl ether afforded 2,3,5,6-tetrakis(4-(methoxycarbonyl)phenyl)pyrazine as a yellow solid (0.86 g, 1.40 mmol). 1H NMR (300 MHz, CDCl3): δ = 8.01 (dt, J1 = 9.0 Hz, J2 = 2.1 Hz, 8H), 8.42 (dt, J1 = 8.7 Hz, J2 = 1.8 Hz, 8H), 3.93 (s, 12H). 13C NMR (75 MHz, CDCl3): δ = 166.5, 148.2, 141.9, 130.6, 129.9, 129.7, 52.2. C36H28N2O8. CHN elemental analysis (%) for C36H28N2O8: C, 70.12; H, 4.55; N, 4.55. Found: C, 69.74; H, 4.97; N. 4.46. IR: 3424(w), 3000(w), 2950(m), 2842(w), 1938(w), 1727(s), 1608(m), 1569(w), 1509(w), 1436(m), 1390(m), 1278(s), 1182(m), 1116(m), 1016(m), 964(w), 863(m), 829(w), 775(m), 713(m), 624(w), 538(w), 499(w). Synthesis of 2,3,5,6-tetrakis(4-carboxyphenyl)pyrazine



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

To a solution of 2,3,5,6-tetrakis(4-(methoxycarbonyl)phenyl)pyrazine (1.021 g, 1.66 mmol) in THF-H2O (1:1, 30 mL) was added NaOH (0.796 g, 19.90 mmol). The mixture was refluxed for about 12 h and THF was evaporated. The solution was acidified to pH of 4-5 with HCl (2 M). The precipitate was filtered and washed with H2O to obtain H4TCPP as a yellow solid (0.918 g, 1.64 mmol). 1H NMR (300 MHz, DMSO-d6): δ = 13.10 (br, 4H), 7.94 (d, J = 8.4 Hz, 8H), 7.68 (d, J = 8.4 Hz, 8H). 13C NMR (75 MHz, DMSO-d6): δ = 166.9, 148.2, 141.5, 131.1, 129.9, 129.3. IR (cm-1): 3453(w), 3002(m), 2657(w), 2526(w), 1941(w), 1702(s), 1608(m), 1569(m), 1511(m), 1388(3), 1317(w), 1176(m), 1010(m), 1106(m), 860(m), 775(m), 717(m), 622(w), 543(m). Synthesis of Zn-TCPP [Zn2(TCPP)(DMF)2] Zn(NO3)2·6H2O (10 mg, 0.0336 mmol) and H4TCPP (4 mg, 0.0071 mmol) were dissolved in DMF (1 mL) and ethanol (0.5 mL), and then HNO3 (150 µL, 2.7 M in DMF) was added. The solution was sealed in a 20 mL vial and heated at 85 oC for 24 hours, then cooled to room temperature. Colorless block-shaped crystals were collected by filtration. The agreement between the experiment and simulated PXRD patterns indicates the phase purity of as-synthesized Zn-TCPP (Figure S3). IR (cm-1): 3448(m), 3066(w), 2931(w), 1660(m), 1616(s), 1531(s), 1405(s), 1384(s), 1178(w), 1093(m), 1091(m), 1012(m), 865(m), 784(m), 713(m), 595(w), 545(w), 426(w). Synthesis of the micrometer-size phase of Zn-TCPP’ Zn(NO3)2·6H2O (0.1 g, 0.336 mmol) and H4TCPP (40 mg, 0.071 mmol) were dissolved in a mixture of DMF (10 mL) and ethanol (5 mL), and then HNO3 (1.5 mL, 2.7 M in DMF) was added. The mixture was sealed in a 100 mL flask and heated at 85 o

C with stirring on oil bath for 24 hours. The powder product was obtained from the

mother liquor by centrifugation and dried in air at room temperature. PXRD and SEM study indicated that Zn-TCPP’ has the same structure with that of Zn-TCPP. Experiment for the gas adsorption measurements The N2 and CO2 gas adsorption measurements were performed on Micromeritics


Page 6 of 22

Page 7 of 22

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


ASAP 2020 surface area and porosity analyzer. Before gas adsorption measurements, the samples were immersed in anhydrous ethanol for 7 days to remove the guest molecules in the channels and then were degassed using the “outgas” function of the surface area analyzer at 85 oC for 10 h. Experiment for the luminescent properties of H4TCPP and Zn-TCPP H4TCPP was well-dispersed in DMF with ultrasound for about 10 minutes and then different amount of water was added into DMF to detect the AIE effect of H4TCPP. In addition, the same amount of Zn-TCPP and H4TCPP were pressed into slice to detect the fluorescence of Zn-TCPP and H4TCPP in solid state. Experiment for the detection of nitro compounds and metal ions 0.5 mg of micrometer-size Zn-TCPP’ was well-dispersed in a solution of 2 mL ethanol with stirring for about 10 minutes and then diverse amounts of nitroaromatic compounds were added to a quartz cuvette containing 2 mL ethanol suspension of Zn-TCPP’ for luminescent detection experiment. The experiment for the detection of metal ions is same with that of the detection of nitro compounds. RESULTS AND DISCUSSION Syntheses and characterizations of H4TCPP, Zn-TCPP and Zn-TCPP’ As depicted in Scheme 1, 2,3,5,6-tetrakis(4-(methoxycarbonyl)phenyl)pyrazine was synthesized by the reaction of methyl 4-formylbenzoate and vitamin B1 under the pH of 9-10.

Then

the

ligand

of

H4TCPP

was

synthesized

2,3,5,6-tetrakis(4-(methoxycarbonyl)phenyl)pyrazine. The 1H and

by 13

hydrolysis

of

C NMR spectra of

H4TCPP prove the validation of H4TCPP. The colorless block-shaped Zn-TCPP crystals and micrometer-size phase of Zn-TCPP’ were obtained by the solvothermal reaction of H4TCPP and Zn(NO3)2·6H2O in the presence of HNO3 at 85 oC for 24 h. The agreement between the experiment and simulated PXRD patterns indicates the phase purity of Zn-TCPP and Zn-TCPP’ (Figure S3). Infrared spectroscopy is used to characterize the functional groups of Zn-TCPP. As shown in Figure S4, the absence of absorption around 1700 cm-1 demonstrates that the H4TCPP are completely



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

deprotonated. In addition, the identical IR spectra of Zn-TCPP and Zn-TCPP’ further illustrates that they are isostructural. The SEM image of Zn-TCPP’ displays a rod-like morphology, which indicates the crystalline nature as shown in Figure S5. It is worth mentioning that Zn-TCPP exhibit high thermal stability, and can be stable up to 350 oC (Figure S6 and S7). Crystal structure of Zn-TCPP Single-crystal X-ray diffraction analysis reveals that Zn-TCPP crystallizes in an orthorhombic space group of Imma. As shown in Figure 1, its framework is composed of paddlewheel dinuclear Zn2(COO)4 clusters and organic TCPP4- ligands which can be simplified as a pair of 4-c nodes (Figure 1a). Each Zn2(COO)4 cluster is linked by four organic ligands, and the axial positions of the cluster are coordinated by two DMF molecules (Figure 1b), which could be removed to form unsaturated open metal sites. Each organic ligand is linked by four Zn2(COO)4 clusters. The connection of Zn2(COO)4 clusters and organic ligands constructs a highly porous framework with interconnected 3D channels along the [001], [010] and [100] directions (Figure 1c, d, S2). It should be noted that these channels are partially blocked by the coordinated DMF molecules. Calculation by PLATON reveals that the free space per unit cell is approximately 4669.2 Å3 upon removal of the guest molecules, corresponding to 68.0% of the crystal volume (6864.8 Å3). From the topological perspective, Zn2(COO)4 cluster can be viewed square geometry, and organic ligand can be simplified as a pair of rectangle geometries. The cross link of these two geometries results in the 3D (4,4)-connected framework (Figure 1e, f). Meanwhile, topological analysis suggests that Zn-TCPP possesses a four connected lvt topology with the point symbol of {42.84}.


Page 8 of 22

Page 9 of 22

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 1. Description of Zn-TCPP structure: (a and b) dinuclear Zn SBU and organic ligand viewed as a pair of 4-c nodes; c) the 3D framework of Zn-TCPP; d) space-filling model of channels along the [001] direction; e) polyhedral view of the lvt topology; f) the lvt topology. The coordinated DMF molecules and H atoms are omitted for clarity. (color modes: Zn, green , N , blue, O red, C gray).



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 2. a) N2 adsorption and desorption isotherms of Zn-TCPP at 77 K (inset: pore size distribution of activated Zn-TCPP); b) CO2 uptakes of Zn-TCPP at 273 K and 298 K. Gas adsorption property Inspired by the large void volume and high thermal stability of Zn-TCPP, the permanent porosity of activated Zn-TCPP has been explored by using low-pressure N2 adsorption-desorption at 77 K. Figure 2a and Table S3 shows the N2 sorption isotherm and porous properties of the activated Zn-TCPP. According to the IUPAC classification, it exhibits Type I nitrogen gas sorption isotherm with type IV character at higher relative pressure that may be caused in the activation process. The calculated Brunanur-Emmett-Teller (BET) surface area is of 984 m2 g-1. The pore size distribution of activated Zn-TCPP is calculated by using non-local density functional theory (NLDFT). The result indicates that there are three main pores centered at 0.84, 1.56 and 1.84 nm, respectively (Figure 2a inset and S2). Furthermore, the CO2 adsorption property of Zn-TCPP has been investigated. The adsorption amounts of CO2 reach 135 and 101 cm3 g-1 at 273 K and 298 K under 732 mmHg, respectively (Figure 2b), which


Page 10 of 22

Page 11 of 22

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


is comparable to the value of Zn-BTTB (128 cm3 g-1 at 273 K and 1 atm).63 The isosteric heat (Qst) of adsorption for Zn-TCPP has been calculated by fitting the CO2 adsorption isotherms measured at 273 K and 298 K to the virial equation (Figure S8). At zero-coverage, the Qst of CO2 for Zn-TCPP is 19.8 kJ mol-1 (Figure S9).

Figure 3. a) Luminescent spectra of H4TCPP in DMF-water mixtures with different water fractions (insert: the luminescent photograph of H4TCPP in DMF-water mixtures under 365 nm UV light); b) luminescent spectra of H4TCPP and Zn-TCPP in the solid state. AIE effect of H4TCPP and luminescent property of Zn-TCPP According to the restriction of intramolecular rotation (RIR) mechanism of AIE, the H4TCPP ligand as a new kind of AIEgen would possess the AIE effect. Thus, the luminescent behaviors of H4TCPP ligand in DMF-H2O mixture solvents with different water fractions have been studied. As shown in Figure 3a, the emission of H4TCPP in pure DMF solvent is very weak, but such emission is enhanced with the addition of water. The strongest emission is exhibited when the water fraction reaches 35%, afterwards, then the emission intensity decreases as the water fraction further increases. ACS Paragon Plus Environment


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Because water is a poor solvent for H4TCPP, the addition of water will result in the formation of nanoaggregates of H4TCPP, giving rise to the AIE effect of H4TCPP. The emission intensity decreases at high water fraction (>40%) may be caused by the presence of four carboxylic acid groups of H4TCPP. In MOF materials, the organic ligands with AIE effect will show luminescence arising from the matrix coordination-induced emission effect.48 As shown in Figure 3b, the solid H4TCPP ligand shows a bright blue emission at 456 nm upon excitation at 386 nm. Meanwhile, Zn-TCPP displays a slight blue-shifted emission at 449 nm compared with H4TCPP when excitation upon 391 nm. The quantum yield of H4TCPP in solid state is 3.08%, while this value of Zn-TCPP increases to 6.55%. These results are mainly caused by the restriction of intramolecular rotation of TCPP4- due to the coordination of carboxyl group with Zn ions. In addition, the framework of Zn-TCPP keeps the TCPP4- ligands separated well with a certain distance, thus decreasing the intermolecular luminescent quenching of TCPP4-. This indicates that MOFs constructed by AIE-based ligands will present excellent luminescence than that of organic ligand itself. Detection for nitroaromatic compounds and metal ions Encouraged by the luminescence of Zn-TCPP, its selective sensing ability for various nitroaromatic compounds and metal ions has been studied. Picric acid (PA), 2,4-dinitrophenol (2,4-DNP), 2,4-dinitrotoluene (2,4-DNT), 4-nitrotoluene (4-NT), 4-nitrobenzaldehyde (4-NBA) and nitrobenzene (NB) are selected as detection candidates for nitroaromatic compounds. Micrometer-size phase of Zn-TCPP’ can be well dispersed in ethanol to form homogeneous suspension. As shown in Figure 4, different degrees of fluorescence quenching of Zn-TCPP’-ethanol suspension can be observed. And the extent of quenching is as the following order: PA > 2,4-DNP > 2,4-DNT > 4-Cl-NB > 4-NBA > 4-NT. Among these nitroaromatic compounds, PA shows the most effective quenching about 77.8%. The reason may be that there is free N group of pyrazine on the pore surface, which favors to interact with the hydroxyl group of PA, thus enhancing the charge transfer effect from excited state of the electron


Page 12 of 22

Page 13 of 22

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


donating Zn-TCPP framework to electron withdrawing PA molecules.

Figure 4. Luminescent quenching intensity (plotted as quench percentage) of Zn-TCPP’-ethanol suspension in presence of different nitroaromatic compounds with the concentration of 56.60 µM.

Figure 5. a) Luminescent quenching of Zn-TCPP’ dispersed in ethanol by gradual addition of PA-ethanol solution ([PA] = 1×10-3 M); b) Stern-Volmer plot of Io/I versus PA concentration in Zn-TCPP’-ethanol suspension (insert: the selected area enlarged view).



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 14 of 22

To further investigate the sensing ability of Zn-TCPP’ for PA, the emission spectra are measured by the gradual addition of PA solution into a suspension of 0.5 mg of Zn-TCPP’ dispersed in 2 mL of an ethanol solution. As shown in Figure 5a, the fluorescent intensity obviously decreases with the increasing PA amount. When the concentration of PA reaches 5.98 µM, 12.7% quenching could be observed. The Stern-Volmer plot of relative luminescent intensity (Io/I, Io and I are the luminescence intensities of Zn-TCPP’ suspension before and after the addition of PA, respectively) and the concentration of PA are shown in Figure 5b. The Stern-Volmer plot is almost linear at the low concentration and is upward curve at the higher concentration, indicating that the quenching mechanism can be explained by a combination of the dynamic and static mechanisms. The quenching constant (Ksv, Io/I = 1 + Ksv×[M], where [M] is the molar concentration of Zn-TCPP’ for PA) at low concentration is 3.59×104 M-1, which is comparable to those of previously reported MOF-based sensors, such as UIO-67-dcppy

(2.9×104

M-1),64

[Cd(NDC)0.5(PCA)]

(3.5×104

M-1),65

and

[Tb(1,3,5-BTC)] (3.42×104 M−1).66

Figure 6. Luminescent quenching intensity (plotted as quench percentage) of Zn-TCPP’-ethanol suspension in present of different metal ions with the concentration of 56.60 µM.


Page 15 of 22

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 7. a) Luminescent quenching of Zn-TCPP’ dispersed in ethanol by gradual addition of Fe3+-ethanol solution ([Fe3+] = 1×10-3 M); b) Stern-Volmer plot of Io/I versus the concentration of Fe3+ in Zn-TCPP’-ethanol suspension. In addition, we also study the sensing ability of Zn-TCPP for various metal ions by using the same method. The luminescent spectra of Zn-TCPP’ immersed in the solutions of different nitrate salts of Fe3+, Cd3+, Cr3+, Zn2+, Sr2+, In3+, Ni2+, Co2+, Ba2+, Li+, Mg2+, and FeCl2 with concentrations of 56.60 µM have been shown in Figure 6.A luminescent quenching of 39% is observed in the presence of Fe3+ ions, which is significantly more than other metal ions. It is noted that the existence of Fe3+ ion or PA will decrease the crystallinity of Zn-TCPP’, but the Zn-TCPP framework is kept intact



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 16 of 22

(Figure S13). The luminescent intensity of Zn-TCPP’ could be regenerated after washing with ethanol, which illustrates the reusability of Zn-TCPP’ for sensing of Fe3+ in ethanol (Figure S12). For better understanding of the selectively sensing ability of Zn-TCPP’ for Fe3+ ions, the luminescent titration of the Zn-TCPP’ suspension in ethanol has been investigated with the gradual addition of Fe3+-ethanol solution. As shown in Figure 7a, the luminescent intensity decreases gradually with the increasing concentration of Fe3+ ions. The Stern-Volmer plot of relative luminescent intensity and the concentration of Fe(NO3)3 is shown in Figure 7b. The calculated Ksv is 1.08×104 M-1, which

is

comparable

to

some

known

MOF-based

sensors,

such

as

[La(TPT)(DMSO)2]·H2O (1.36×104 M−1),67 [La(TAIP)(DMF)2](DMF)0.5 (8.86×103 M-1),68 and Eu-MOF-LIC-1 (2.87×104 M−1).69 CONCLUSION In conclusion, we have successfully synthesized a novel Zn-TCPP MOF by using designed rigid and symmetrical H4TCPP ligand containing pyrazine moiety with AIE effect. Zn-TCPP possesses a 3D four connected lvt topology structure, which is constructed by the connection of dinuclear Zn2(COO)4 clusters and organic H4TCPP ligands. The large void volume of Zn-TCPP endows its high BET surface area and CO2 uptake. Due to the AIE effect of H4TCPP, Zn-TCPP presents luminescent property due to the matrix coordination-induced emission effect of TCPP4- ligand. Such fluorescent response can be used to selectively detect PA and Fe3+ ion. This work will prompt further

design

of

multifunctional

MOF

materials

based

on

the

tetraphenylpyrazine-based functional organic ligands. ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/ X-ray crystallographic data for Zn-TCPP in CIF format. The crystal data and structure refinement, the selected bond lengths and angles. The asymmetric unit, PXRD patterns, TGA, and IR spectra of Zn-TCPP. Luminescent titrations of different volume


Page 17 of 22

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


of NAC for Zn-TCPP in ethanol suspensions. CCDC numbers are 1516214 for Zn-TCPP. AUTHOR INFORMATION Corresponding Authors Email: [email protected] (Z.L.); [email protected] (J.L.) Notes The authors declare no competing financial interest. ACKNOWLEDGMENTS We thank the National Natural Science Foundation of China (Grants: 21471064, 21671075 and 21621001) for support to this work. REFERENCES (1) Yaghi, O. M.; O’Keeffe, M.; Ockwig, N. W.; Chae, H. K.; Eddaoudi, M.; Kim, J. Nature 2003, 423, 705-714. (2) Kitagawa, S.; Kitaura, R.; Noro, S. Angew. Chem., Int. Ed. 2004, 43, 2334-2375. (3) Zhang, J.-P.; Zhang, Y.-B.; Lin, J.-B.; Chen, X.-M. Chem. Rev. 2012, 112, 1001-1033. (4) Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M. Science 2013, 341, 1230444. (5) He, Y. B.; Li, B.; O’Keeffe, M.; Chen, B. L. Chem. Soc. Rev. 2014, 43, 5618-5656. (6) Zhou, H.-C.; Long, J. R.; Yaghi, O. M. Chem. Rev. 2012, 112, 673-674. (7) Lu, W. G.; Wei, Z. W.; Gu, Z.-Y.; Liu, T.-F.; Park, J.; Park, J.; Tian, J.; Zhang, M. W.; Zhang, Q.; Gentle III, T.; Bosch, M.; Zhou, H.-C. Chem. Soc. Rev. 2014, 43, 5561-5593. (8) Bai, Y.; Dou, Y. B.; Xie, L.-H.; Rutledge, W.; Li, J.-R.; Zhou, H.-C. Chem. Soc. Rev. 2016, 45, 2327-2367. (9) Lin, Z.-J.; Lü, J.; Hong, M. C.; Cao, R. Chem. Soc. Rev. 2014, 43, 5867-5895. (10) Tian, D.; Chen, Q.; Li, Y.; Zhang, Y.-H.; Chang, Z.; Bu X.-H. Angew. Chem., Int. Ed. 2014, 53, 837-841.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(11) Banerjee, R.; Phan, A.; Wang, B.; Knobler, C.; Furukawa, H.; O’Keeffe, M.; Yaghi, O. M. Science 2008, 319, 939-943. (12) Li, J.-R.; Sculley, J.; Zhou, H.-C. Chem. Rev. 2012, 112, 869-932. (13) Zhang, Z. J.; Zhao, Y. G.; Gong, Q. H.; Li, Z.; Li, J. Chem. Commun. 2013, 49, 653-661. (14) Suh, M. P.; Park, H. J.; Prasad, T. K.; Lim, D.-W. Chem. Rev. 2012, 112, 782-835. (15) Lee, J. Y.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. T.; Hupp, J. T. Chem. Soc. Rev. 2009, 38, 1450-1459. (16) Cui, Y. J.; Yue, Y. F.; Qian, G. D.; Chen, B. L. Chem. Rev. 2012, 112, 1126-1162. (17) Rocha, J.; Carlos, L. D.; Paz, F. A. A.; Ananias, D. Chem. Soc. Rev. 2011, 40, 926-940. (18) Sava, D. F.; Rohwer, L. E. S.; Rodriguez, M. A.; Nenoff, T. M. J. Am. Chem. Soc. 2012, 134, 3983-3986. (19) Sun, C.-Y.; Wang, X.-L.; Zhang, X.; Qin, C.; Li, P.; Su, Z.-M.; Zhu, D.-X.; Shan, G.-G.; Shao, K.-Z.; Wu, H.; Li, J. Nat. Commun. 2013, 4, 2717. (20) Stavila, V.; Talin, A. A.; Allendorf, M. D. Chem. Soc. Rev. 2014, 43, 5994-6110. (21) Kurmoo, M. Chem. Soc. Rev. 2009, 38, 1353-1379. (22) Weng, D.-F.; Wang, Z.-M.; Gao, S. Chem. Soc. Rev. 2011, 40, 3157-3181. (23) Kreno, L. E.; Leong, K.; Farha, O. K.; Allendorf, M.; Van Duyne, R. P.; Hupp, J. T. Chem. Rev. 2012, 112, 1105-1125. (24) Allendorf, M. D.; Bauer, C. A.; Bhakta, R. K.; Houk, R. J. T. Chem. Soc. Rev. 2009, 38, 1330-1352. (25) Heine, J.; Müller-Buschbaum, K. Chem. Soc. Rev. 2013, 42, 9232-9242. (26) Hu, Z. C.; Deibert, B. J.; Li, J. Chem. Soc. Rev. 2014, 43, 5815-5840. (27) Jiang, H.-L.; Tastu, Y.; Lu, Z.-H.; Xu, Q. J. Am. Chem. Soc. 2010, 132, 5586-5587. (28) Chen, B. L.; Xiang, S. C.; Qian, G. D. Acc. Chem. Res. 2010, 43, 1115-1124. (29) Rocca, J. D.; Liu, D. M.; Lin, W. B. Acc. Chem. Res. 2011, 44, 957-968. (30) Horcajada, P.; Gref, R.; Baati, T.; Allan, P. K.; Maurin,G.; Couvreur, P.; Férey, G.; Morris, R. E.; Serre, C. Chem. Rev. 2012, 112, 1232-1268. (31) McKinlay, A. C.; Morris, R. E.; Horcajada, P.; Férey, G.; Gref, R.; Couvreur, P.;


Page 18 of 22

Page 19 of 22

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Serre C. Angew. Chem., Int. Ed. 2010, 49, 6260-6266. (32) Wang, H.; Xu, J.; Zhang, D.-S.; Chen, Q.; Wen, R.-M.; Chang, Z.; Bu X.-H. Angew. Chem., Int. Ed. 2015, 54, 5966-5970. (33) Lü, J.; Perez-Krap, C.; Suyetin, M.; Alsmail, N. H.; Yan, Y.; Yang, S. H.; Lewis, W.; Bichoutskaia, E.; Tang, C. C.; Blake, A. J.; Cao, R.; Schröder, M. J. Am. Chem. Soc. 2014, 136, 12828-12831. (34) Phan, D. T.; Maeder, M.; Burns, R. C.; Puxty, G. Environ. Sci. Technol. 2014, 48, 4623-4629. (35) Qian, D.; Lei, C.; Wang, E.-M.; Li, W.-C.; Lu, A.-H. ChemSusChem 2014, 7, 291-298. (36) Britt, D.; Furukawa, H.; Wang, B.; Glover, T. G.; Yaghi, O. M. Proc. Natl. Acad. Sci. U. S. A. 2009, 106, 20637-20640. (37) Lee, Y.-G.; Moon, H. R.; Cheon, Y. E.; Suh, M. P. Angew. Chem., Int. Ed. 2008, 47, 7741-7745. (38) Liang, Z. Q.; Du, J. J.; Sun, L. B.; Xu, J.; Mu, Y.; Li, Y.; Yu, J. H.; Xu, R. R. Inorg. Chem. 2013, 52, 10720-10722. (39) Zhang, S.-M.; Chang, Z.; Hu, T.-L.; Bu, X.-H. Inorg. Chem. 2010, 49, 11581-11586. (40) Sumida, K.; Rogow, D. L.; Mason, J. A.; McDonald, T. M.; Bloch, E. D.; Herm, Z. R.; Bae T. H.; Long, J. R. Chem. Rev. 2012, 112, 724-781. (41) Cohen, S. M. Chem. Rev. 2012, 112, 970-1000. (42) Gao, Q.; Xu, J.; Cao, D. P.; Chang, Z.; Bu X.-H. Angew. Chem., Int. Ed. 2016, 55, 15027-15030. (43) Lan, A. J.; Li, K. H.; Wu, H. H.; Olson, D. H.; Emge, T. J.; Ki, W.; Hong, M. C.; Li, J. Angew. Chem., Int. Ed. 2009, 48, 2334-2338. (44) Song, X.-Z.; Song, S.-Y.; Zhao, S.-N.; Hao, Z.-M.; Zhu, M.; Meng, X.; Wu, L.-L.; Zhang, H.-J. Adv. Funct. Mater. 2014, 24, 4034–4041. (45) Mulfort, K. L.; Farha, O. K.; Malliakas, C. D.; Kanatzidis, M. G.; Hupp, J. T. Chem. Eur. J. 2010, 16, 276-281. (46) Shultz, A. M.; Farha, O. K.; Adhikari, D.; Sarjeant, A. A.; Hupp, J. T.; Nguyen, S. T.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Inorg. Chem. 2011, 50, 3174-3176. (47) Jin, S. Y.; Son, H.-J.; Farha, O. K.; Wiederrecht, G. P.; Hupp, J. T. J. Am. Chem. Soc. 2013, 135, 955-958. (48) Shustova, N. B.; McCarthy, B. D.; Dincă, M. J. Am. Chem. Soc. 2011, 133, 20126-20129. (49) Zhang, M.; Feng, G. X.; Song, Z. G.; Zhou, Y.-P.; Chao, H.-Y.; Yuan, D. Q.; Tan, T. T. Y.; Guo, Z. G.; Hu, Z. G.; Tang, B. Z.; Liu, B.; Zhao, D. J. Am. Chem. Soc. 2014, 136, 7241-7244. (50) Hu, Z. C.; Huang, G. X.; Lustig, W. P.; Wang, F. M.; Wang, H.; Teat, S. J.; Banerjee, D.; Zhang, D. Q.; Li, J. Chem. Commun. 2015, 51, 3045-3048. (51) Dalapati, S.; Gu, C.; Jiang, D. L. Small 2016, 12, 6513-6527. (52) Sun, L. B.; Zou, Y. C.; Liang, Z. Q.; Yu, J. H.; Xu, R. R. Polym. Chem. 2014, 5, 471-478. (53) Sun, L. B.; Liang, Z. Q.; Yu, J. H. Polym. Chem. 2015, 6, 917-924. (54) Sun, L. B.; Liang, Z. Q.; Yu, J. H. Acta Chim. Sinica 2015, 73, 611-616. (55) Li, D. D.; Yu, J. H. Small 2016, 12, 6478-6494. (56) Li, D. D.; Miao, C. L.; Wang, X. D.; Yu, X. H.; Yu, J. H.; Xu, R. R. Chem. Commun. 2013, 49, 9549-9551. (57) Chen, M.; Li, L. Z.; Nie, H.; Tong, J. Q.; Yan, L. L.; Xu, B.; Sun, J. Z.; Tian, W. J.; Zhao, Z. J.; Qin, A. J.; Tang, B. Z. Chem. Sci. 2015, 6, 1932-1937. (58) Blatov, V. A. Struct. Chem. 2012, 23, 955-963. (59) SAINT, version 6.02a, Bruker AXS Inc., Madison, WI, USA, 2000. (60) Sheldrick, G. M. Acta Crystallogr., Sect. A: Fundam. Crystallogr. 2008, 64, 112-122. (61) Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7-13. (62) Spek, A. L.; Acta Crystallogr. Sect. D: Biol. Crystallogr. 2009, 65, 148-155. (63) Farha, O. K.; Mulfort, K. L.; Hupp, J. T. Inorg. Chem. 2008, 47, 10223-10225. (64) Nagarkar, S. S.; Desai, A. V.; Ghosh, S. K. Chem. Commun. 2014, 50, 8915-8918. (65) Nagarkar, S. S.; Joarder, B.; Chaudhari, A. K.; Mukherjee, S.; Ghosh, S. K. Angew. Chem., Int. Ed. 2013, 125, 2953-2957.


Page 20 of 22

Page 21 of 22

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(66) Xiao, J.-D.; Qiu, L.-G.; Ke, F.; Yuan, Y.-P.; Xu, G.-S.; Wang, Y.-M.; Jiang, X. J. Mater. Chem. A 2013, 1, 8745-8752. (67) Zhang, C. Q.; Yan, Y.; Pan, Q. H.; Sun, L. B.; He, H. M.; Liu, Y. L.; Liang, Z. Q.; Li, J. Y. Dalton Trans. 2015, 44, 13340-13346. (68) Wang, D.; Sun, L. B.; Hao, C. Q.; Yan, Y.; Liang, Z. Q. RSC. Adv. 2016, 6, 57828-57834. (69) Hao, J.-N.; Yan, B. J. Mater. Chem. C 2014, 2, 6758-6764.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 22 of 22

Manuscript title: A multifunctional zinc metal-organic framework based on designed H4TCPP ligand with AIE effect: CO2 adsorption, luminescence and sensing property Author list: Yangyang Jiang, Libo Sun, Jianfeng Du, Yuchuan Liu, Huaizhong Shi, Zhiqiang Liang and Jiyang Li TOC graphic

Synopsis: A porous luminescent MOF is constructed by using a novel designed tetraphenylpyrazine-based ligand with aggregation-induced emission effect, which exhibits high CO2 adsorption capacity and effective detection for picric acid and Fe3+ ions.


Multifunctional Zinc MetalâOrganic Framework ... - ACS Publications

Recommend Documents

Multifunctional Zinc MetalâOrganic Framework ... - ACS Publications