A novel metal-organic framework based on mixed ligands as a highly-selective luminescent sensor for Cr2O72− and nitroaromatic compounds

Accepted Manuscript A novel metal-organic framework based on mixed ligands as a highly-selective luminescent sensor for Cr2O72− and nitroaromatic compounds

Feng Guo PII: DOI: Reference:

S1387-7003(19)30067-X https://doi.org/10.1016/j.inoche.2019.02.026 INOCHE 7284

To appear in:

Inorganic Chemistry Communications

Received date: Revised date: Accepted date:

17 January 2019 16 February 2019 16 February 2019

Please cite this article as: F. Guo, A novel metal-organic framework based on mixed ligands as a highly-selective luminescent sensor for Cr2O72− and nitroaromatic compounds, Inorganic Chemistry Communications, https://doi.org/10.1016/ j.inoche.2019.02.026

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT 1

A novel metal-organic framework based on mixed ligands as a highly-selective luminescent sensor for Cr2O72– and nitroaromatic compounds

a

PT

Feng Guo, a*

Chongqing Key Laboratory of Inorganic Special Functional Materials, School of

RI

Chemistry and Chemical Engineering, Yangtze Normal University, Fuling, Chongqing

SC

408100, China.

NU

Corresponding Authors: Prof. Feng Guo

AC

CE

PT E

D

MA

E-mail address: [email protected]

ACCEPTED MANUSCRIPT 2

Abstract A novel 3D metal-organic framework, namely [Mn2(HBTC)2(TIAB)]n, was successfully synthesized by mixing two rigid ligands 1,2,4,5-tetrakis(1-imidazolyl) benzene (TIAB) and 1,3,5-benzenetricarboxylic acid (H3BTC). The resultant sample was investigated in detail by single crystal X-ray diffraction, elemental analysis of C,

PT

H and N, powder X-ray diffraction pattern, thermogravimetric analysis, and luminescent properties. In virtue of its stability and luminescence properties, the

RI

resultant [Mn2(HBTC)2(TIAB)]n can be applied as a bifunctional luminescent sensor

SC

for Cr2O72– and nitroaromatic compounds. In addition, it can be recycled at least four

Keywords:

Metal-organic

Cr2O72–;

NU

times due to the excellent stability.

framework;

compound;

MA

luminescence; sensor.

nitroaromatic

Metal-organic frameworks (MOFs)[1-6] are a common class of inorganic-organic

D

hybrid material, which have been implemented in various applications, including gas

PT E

sorption,[7-11] biological molecular immobilization,[12-15] luminescence detector,[16-22] heterogeneous catalysis,[23-27] and optics device,[28-30] because they have relatively high BET surface area, remarkable designability, multiformity and functionality. To

CE

date, lots of MOFs have been successfully prepared.[31-35] Among all the applications, detecting contaminantsusing luminescent MOFs as sensors have drawn much

AC

attention due to their outstanding advantages, such as rapid-response, prominent selectivity, high sensitivity and excellent reusability.[16-22] MOFs contain two different parts including bridging organic linkers and multiple metal ions/clusters, which can be considered and designed as emitted sources for luminescent sensors. The organic ligands not only are able to apply to construct interesting MOFs, but also can be introduced targeted groups to increase the luminescent detectability towards heavy metal ions, organic vapour solvents and some toxic molecules. Additionally, the mixed ligand strategy always can be adopted to fabricate novel luminescence MOFs to extensively use as sensor materials.[36-38] Cr2O72– and nitroaromatic compounds are

ACCEPTED MANUSCRIPT 3

the most wide spread toxic contaminants in many fields to cause various security and environmental puzzles all over the world. Meanwhile, the poor stability of luminescence MOFs limits their actual use of industrialization in detection applications. Thus, it is remarkably important to design and prepare such efficient and stable luminescence MOFs by the mixed ligand strategy as useful sensors tomonitor

PT

Cr2O72– and nitroaromatic compounds for security and environmental protection. In this work, we selected two rigid organic ligands 1,2,4,5-tetrakis(1-imidazolyl)

RI

benzene (TIAB) and 1,3,5-benzenetricarboxylic acid (H3BTC), because they have

SC

multiform coordination nodes, different coordinated atoms, and rigid structures to feasibly generate MOFs. Mn(II) ion is a commonly used inorganic centre to

MOFs

with

outstanding

NU

self-assemble with two rigid organic ligands TIAB and H3BTC to fabricate novel properties.

A

novel

3D

Mn-MOF

(namely

MA

[Mn2(HBTC)2(TIAB)]n) has been achieved by the mixed ligand strategy via heating MnCl2, TIAB and H3BTC in a mixture solvent of N,N-dimethylformamide (DMF)

D

and H2O at 120 °C after 3 days.[39] The resultant sample was measured and

PT E

characterized in detail by single crystal and powder X-ray diffraction, C, H and Nelemental analysis, luminescent properties, and thermogravimetric analysis. Because of high stability and luminescence property, it can be founded as a high-efficient

AC

recyclability.

CE

luminescent sensor for Cr2O72– and nitroaromatic compounds with outstanding

From the single-crystal X-ray diffraction result, it displayed that the resultant sample crystallizes in the monoclinic with C2/c space group and contains a three-dimensional (3D) structure.[40] Compared with the reported MOFs or coordinated compounds based on H3BTC[41, 42] and TIAB[43, 44], the as-synthesized sample was constructed by H3BTC and TIAB simultaneously, which is the first reported in all MOFs. As seen in Fig. S1, the asymmetric unit contains one independent Mn(II) ion, one second TIAB molecule and a partly deprotonated HBTC2– ligand. As founded in Fig. 1a, each Mn(II) ion is six-coordinated with four

ACCEPTED MANUSCRIPT 4

oxygen atoms from three carboxylate groups of different HBTC2- ligands and two nitrogen atoms from two different TIAB ligands (Mn-O = 2.1968(17) and Mn-N = 2.2083(20) Å). Two Mn(II) ions can be connected each other by the oxygen atoms from functional carboxylate groups to form binuclear Mn(II) clusters. The MnMn distance in this binuclear cluster is about 4.6779(6) Å. The HBTC2– ligand was three-connected via only one coordinated mode as 3-1: 1: 1: 1 (Fig. 1b). The

PT

neutral TIAB is linked with four Mn(II) ions based on a coordination mode as 4-1:

RI

1: 1: 1 (Fig. 1c). The binuclear Mn(II) clusters were further connected by these

CE

PT E

D

MA

NU

SC

ligands to construct a 3D construction finally (Figs. 1d and 1e).

AC

Fig. 1. (a) The binuclear Mn(II) clusters; (b) the coordination mode of partly deprotonated HBTC2– ligand; (c) the coordination mode of TIAB ligand; (d and e) viewing of the 3D structure (all hydrogen atoms are removed for clarity, and C, gray; O, red; N, blue; Mn, green).

The measured powder X-ray diffraction profile of the prepared sample was almost similar with those of the characteristic signals of the simulated one from the obtained single crystal structure, illustrating that the obtained sample was pure (Fig. 2a). As shown in Fig. 2b, the thermogravimetric analyses (TGA) data of the as-synthesized sample in air was collected, which exhibited a significant weight loss

ACCEPTED MANUSCRIPT 5

after increasing the temperature to 300 °C. The slight weight loss before 300 °C was mainly attributed to the small amount of adsorbed water molecules on the surface of Mn-MOF. The corresponding PXRD profile of the as-synthesized sample after heating at 300 °C for 30 minutes obviously exhibited thatit possessed the outstanding heating stability (Fig. S2). Finally, the residual sample decomposed completely with

MA

NU

SC

RI

PT

the increasing temperature.

Fig. 2. (a) PXRD curves of the simulated (black) and experimental (red) samples; (b) TGA data of

PT E

D

the as-synthesized sample.

Due to the extensively potential luminescent sensing ability, the solid-state luminescent property of the resultant sample was measured at indoor temperature. As

CE

displayed in Fig. 3a, the resultant sample showed a significant broad emission band at 407 nm under excitation wavelength at 342 nm, which is significantly similar with the

AC

H3BTC organic ligand (Fig. S3).[45] The results indicated that the luminescent property is primary attributed to the ligand-to-metal and the intraligand transition like the other previous literature.[46-49] Fig. S4 shown the luminescent emission intensities of the as-synthesized sample dispersed in different solvents, which clearly illustrated the relative strong emission luminescence in DMF. In addition, the resultant sample can retain its luminescent property at least for one day in DMF (Fig. S5). More importantly, the resultant sample showed a significant luminescence quenching performance after encountering the Cr2O72– in Fig. 3a. To investigate the luminescent detectability towards Cr2O72–, the luminescent intensity remarkably decreased with

ACCEPTED MANUSCRIPT 6

the increasing concentration (Fig. 3b). As we know, the Stern-Volmer equation: I0/I = 1 + Ksv[Q] can be applied to calculate the Ksv value and further quantitatively confirmed the detectability. Herein, the I0 and I are the luminescent intensities of the origin and after adding analyte, [Q] is the molar concentration (M–1), and Ksv value is the Stern-Volmer constant. If the results of I0/I vs [Q] are linear, the Ksv value is able to confirm accurately. As the insert result in Fig. 3b, the corresponding Ksv value of

PT

Cr2O72– was calculated about 8.9 × 103 M–1. Meanwhile, the detection limit of Cr2O72–

RI

can be calculated from 3δ/Slope (δ：standard error).[50] The corresponding detection limit of Cr2O72– is 1.25 × 10–5 mol L–1. The compared results of the reported MOFs

SC

were listed in Table S1. The UV-Vis overlap of Cr2O72– and the excitation spectra of the resultant sample are mainly attributed to the excitation light competition (Fig. S6).

NU

The anti-interference and sensitivity experiments of Cr2O72– were further investigated and explored in detail (Fig. S7), which displayed that the prepared crystal has

AC

CE

PT E

D

MA

excellent selectivity for Cr2O72– by the luminescence quenching.

–4

Fig. 3. (a) The corresponding emission spectra of the resultant sample in different ions (1×10

M); (b) the titrating experiment with Cr2O72– at different concentrations from 1.05× 10–5 to 1.0 × 10–4 mol L–1 with the insert Stern-Volmer result. Meanwhile, the ground powder also exhibited remarkably luminescence quenching effect for common nitroaromatic compounds, including 3,5-dinitrobenzoicacid (3,5-DNBA), nitrobenzene

1,3-dinitrobenzene (NB),

4-nitrobenzoic

(1,3-DNB), acid

2,4-dinitrotoluene(2,4-DNT),

(4-NBA),

4-nitrotoluene

(4-NT),

ACCEPTED MANUSCRIPT 7

1-bromo-4-nitrobenzene (1-Br-4-NB), and picric acid (PA). As illustrated in Fig. 4a, it showed the highest luminescence performance towards PA among all the used nitroaromatic compounds. The luminescence titration experiment also clearly showed the luminescent intensity significantly decreased with the increasing concentration of PA in DMF solution. In the low concentration range of PA, the Ksv value can be accurately calculated by the Stern-Volmer equation, which is about 1.12 × 104 M–1.

PT

Furthermore, the corresponding detection limit of PA is 3.08 × 10–5 mol L–1. The

RI

UV-Vis adsorption results obviously exhibited that the excitation spectra and the adsorption band of PA has large overlap, leading to the excitation light competition

SC

(Fig. S8). In addition, the selectivity of PA was studied and performed in detail. The

CE

PT E

D

MA

outstanding selectivity for PA (Fig. S9).

NU

anti-interference and sensitivity experiment displayed that the prepared sample has

Fig. 4. (a) The corresponding emission spectra of the resultant sample in different nitroaromatic compounds; (b) the titrating experiment with PA at different concentrations from 4.4 × 10–6 to 5.0

AC

× 10–4 mol L–1 with the Stern-Volmer data.

Furthermore, another important property for the sensing material is the recyclability. The resultant sample was easily recollected and further reused after the sequential detected experiments. As founded in Fig. 5, the sensing detection ability of the recollected sample can almost retain very well after recycling four times for Cr2O72– and PA, which is mainly ascribed to the high stability of this MOF material. The luminescence intensity is easily regained after washing with fresh DMF several times. The recycled PXRD profiles of the reused crystals after four times displayed that the

ACCEPTED MANUSCRIPT 8

SC

RI

PT

framework of this MOF can be retained very well (Fig. S10).

NU

Fig. 5. The recyclability for the as-synthesized MOF for the Cr2O72– (a) and PA (b).

In summary, a novel 3D Mn(II)-MOF with high stability is successfully designed

MA

and fabricated by the mixed ligand strategy, which can be further considered as a luminescent sensor for Cr2O72– and PA. Meanwhile, the resultant sample also possesses the excellent recyclability at least four times.

PT E

D

Appendix A. Supplementary data The luminescent spectra and crystal table are listed in the supporting information. The

AC

References

CE

CCDC reference number is1888285.

[1] W.-M. Liao, J.-H. Zhang, Z. Wang, Y.-L. Lu, S.-Y. Yin, H.-P. Wang, Y.-N. Fan, M. Pan,

C.-Y.

Su,

Semiconductive

amine-functionalized

Co(II)-MOF

for

visible-light-driven hydrogen evolution and CO2 reduction, Inorg. Chem. 57 (2018) 11436-11442. [2] L. Zhu, X.-Q. Liu, H.-L. Jiang, L.-B. Sun, Metal-organic frameworks for heterogeneous basic catalysis, Chem. Rev. 117 (2017) 8129-8176. [3] H. He, J. A. Perman, G. Zhu, S. Ma, Metal-organic frameworks for CO2 chemical transformations, Small 12 (2016) 6309-6324.

ACCEPTED MANUSCRIPT 9

[4] M. Chen, Z.-W. Wang, E. C. Sanudo, H. Zhao, C.-S. Liu, Two self-interpenetrating magnetic Mn(II) metal-organic frameworks assembled from rigid or flexible tripodal multicarboxylate ligands, Inorg. Chem. Commun. 43 (2014) 121-125. [5] H. He, J. Du, H. Su, Y. Yuan, Y. Song, F. Sun, Four new metal-organic

5-phenyldiazenyl)isophthalicacid:

syntheses,

PT

frameworks based on bi-,tetra-, penta-, and hexa-nuclear clusters derived from structures

properties,

RI

CrystEngComm 17 (2015) 1201-1209.

and

[6] S. Zhang, H. He, F. Sun, N. Zhao, J. Du, Q. Pan, G. Zhu, A novel adenine-based

SC

zinc(II) metal-organic framework featuring the Lewis basic sites for heterogeneous catalysis, Inorg. Chem. Commun. 79 (2017) 55-59.

NU

[7] H.-Y. Liu, J. Liu, G.-M. Gao, H.-Y. Wang, Assembly of two metal-organic frameworks based on distinct cobalt dimeric building blocks induced by ligand

MA

modification: gas adsorption and magnetic properties, Inorg. Chem. 57 (2018) 10401-10409.

D

[8] H. He, F. Sun, S. Ma, G. Zhu, Reticular synthesis of a series of HKUST-like

9071-9076.

PT E

MOFs with carbon dioxide capture and separation, Inorg. Chem. 55 (2016)

[9] D. Liu, G. Wen, W. Zhou, Two anionic low-connectivity microporous

CE

indium-organic frameworks with selectivity adsorption of CO2 over CH4, Inorg. Chem. Commun. 95 (2018) 22-26.

AC

[10] H. He, F. Sun, B. Aguila, J. A. Perman, S. Ma, G. Zhu, A bifunctional metal-organic framework featuring the combination of open metal sites and Lewis basic sites for selective gas adsorption and heterogeneous cascade catalysis, J. Mater. Chem. A 4 (2016) 15240-15246. [11] H. He, Y. Song, C. Zhang, F. Sun, R. Yuan, Z. Bian, L. Gao, G. Zhu, A highly robust metal-organic framework based on an aromatic 12-carboxyl ligand with highly selective adsorption of CO2 over CH4, Chem. Commun. 51 (2015) 9463-9466. [12] X. Lian, Y. Huang, Y. Zhu, Y. Fang, R. Zhao, E. Joseph, J. Li, J.-P. Pellois, H.-C.

ACCEPTED MANUSCRIPT 10

Zhou, Enzyme-MOF nanoreactor activates nontoxic paracetamol for cancer therapy, Angew. Chem., Int. Ed. 57 (2018), 5725-5730. [13] H. He, H. Han, H. Shi, Y. Tian, F. Sun, Y. Song, Q. Li, G. Zhu, Construction of thermophilic lipase-embedded metal-organic frameworks via biomimetic mineralization: a biocatalyst for ester hydrolysis and kinetic resolution, ACS Appl.

PT

Mater. Interfaces 8 (2016) 24517-24524. [14] M. B. Majewski, A. J. Howarth, P. Li, M. R. Wasielewski, J. T. Hupp, O. K. Farha,

RI

Enzyme encapsulation in metal-organic frameworks for applications in catalysis, CrystEngComm 19 (2017) 4082-4091.

SC

[15] K. Liang, C. J. Coghlan, S. G. Bell, C. Doonan, P. Falcaro, Enzyme encapsulation in zeolitic imidazolate frameworks: a comparison between controlled

NU

co-precipitation and biomimetic mineralisation, Chem. Commun. 52 (2016) 473-476.

MA

[16] H. He, Q.-Q. Zhu, F. Sun, G. Zhu, Two 3D metal-organic frameworks based on CoII and ZnII clusters for Knoevenagel condensation reaction and highly selective

D

luminescence sensing, Cryst. Growth Des. 18 (2018) 5573-5581.

PT E

[17] T. Gao, B.-X. Dong, Y.-M. Pan, W.-L. Liu, Y.-L. Teng, Highly sensitive and recyclable sensing of Fe3+ ions based on a luminescent anionic [Cd(DMIPA)]2framework with exposed thioether group in the snowflake-like channels, J. Solid

CE

State Chem. 270 (2019) 493-499. [18] S.-Q. Wang, H. He, Construction and structural diversification of eight rare-earth

AC

MIIIcoordination complexes with 5-bromonicotinic acid N-oxide, Inorg. Chem. Commun. 97 (2018) 63-68. [19] H. He, Y. Song, F. Sun, Z. Bian, L. Gao, G. Zhu, A porous metal-organic framework formed by a V-shaped ligand and Zn(II) ion with highly selective sensing for nitroaromatic explosives, J. Mater. Chem. A 3 (2015) 16598-16603. [20] B.-X. Dong, Y.-M. Pan, W.-L. Liu, Y.-L. Teng, An ultrastable luminescent metal-organic framework for selective sensing of nitroaromatic compounds and nitroimidazole-based drug molecules, Cryst. Growth Des. 18 (2018) 431-440. [21] H. He, S.-H. Chen, D.-Y. Zhang, R. Hao, C. Zhang, E.-C. Yang, X.-J. Zhao, A

ACCEPTED MANUSCRIPT 11

micrometer-sized europium(III)-organic framework for selective sensing of the Cr2O72− anion and picric acid in water systems. Dalton Trans. 46 (2017) 13502-13509. [22] H. He, S.-H. Chen, D.-Y. Zhang, E.-C. Yang, X.-J. Zhao, A luminescent metal–organic framework as an ideal chemosensor for nitroaromatic compounds.

PT

RSC Adv. 7 (2017) 38871-38876. [23] X. Yan, K. Wang, X. Xu, S. Wang, Q. Ning, W. Xiao, N. Zhang, Z. Chen, C. Chen,

RI

Brønsted basicity in metal-organic framework-808 and its application in base-free catalysis, Inorg. Chem. 57 (2018) 8033-8036.

SC

[24] H. He, D.-Y. Zhang, F. Guo, F. Sun, A versatile microporous Zinc(II) metal-organic framework for selective gas adsorption, cooperative catalysis, and

NU

luminescent sensing. Inorg. Chem. 57 (2018) 7314-7320. [25] H. He, Y.-Q. Xue, S.-Q. Wang, Q.-Q. Zhu, J. Chen, C.-P. Li, M. Du, A bimetal-organic

framework

MA

double-walled

for

antibiotics

sensing

and

size-selective catalysis, Inorg. Chem. 57 (2018) 15062-15068.

D

[26] Y. Zhang, Y. Wang, L. Liu, N. Wei, M.-L. Gao, D. Zhao, Z.-B. Han, Robust

tandem

PT E

bifunctional lanthanide cluster based metal-organic frameworks (MOFs) for deacetalization–Knoevenagel

2193-2198.

reaction,

Inorg. Chem.

57

(2018)

CE

[27] H. He, Q. Sun, W. Gao, J. A. Perman, F. Sun, G. Zhu, B. Aguila, K. Forrest, B. Space, S. Ma, A stable metal-organic framework featuring a local buffer

AC

environment for carbon dioxide fixation, Angew. Chem., Int. Ed. 57 (2018), 4657-4662.

[28] D. Zhang, Z.-Z. Xue, J. Pan, M.-M. Shang, Y. Mu, S.-D. Han, G.-M. Wang, Solvated lanthanide cationic template strategy for constructing iodoargentates with photoluminescence and white light emission, Cryst. Growth Des. 18 (2018) 7041-7047. [29] H. He, F. Sun, T. Borjigin, N. Zhao, G. Zhu, Tunable colors and white-light emission based on a microporous luminescent Zn(II)-MOF, Dalton Trans. 43 (2014) 3716-3721.

ACCEPTED MANUSCRIPT 12

[30] Y. Wang, S.-H. Xing, F.-Y. Bai, Y.-H. Xing, L.-X. Sun, Stable Lanthanide-organic framework materials constructed by a triazolylcarboxylateligand: multifunction detection and white luminescence tuning, Inorg. Chem. 57 (2018) 12850-12859. [31] Q. Sun, X. Zhu, N. Zhang, B. Zhang, J. Lu, H. Liu, Auxiliary ligand-assisted structural variation of two Co(II) metal-organic frameworks: Syntheses, crystal

PT

structure and magnetic properties, Inorg. Chem. Commun. 99 (2019) 172-175. [32] H. He, F. Sun, H. Su, J. Jia, Q. Li, G. Zhu, Syntheses, structures and propertiesof

three

metal-organic

frameworks

based

on

RI

luminescence

5-(4-(2H-tetrazol-5-yl)phenoxy)isophthalic acid, CrystEngComm 16 (2014)

SC

339-343.

[33] J. Li, X. Luo, Y. Zhou, L. Zhang, Q. Huo, Y. Liu, Two metal-organic frameworks

NU

with structural varieties derived from cis-trans isomerism nodes and effective detection of nitroaromatic explosives, Cryst. Growth Des. 18 (2018) 1857-1863.

MA

[34] Z.-W. Zhai, S.-H. Yang, M. Cao, L.-K. Li, C.-X. Du, S.-Q. Zang, Rational design of three two-fold interpenetrated metal-organic frameworks: luminescent

D

Zn/Cd-metal-organic frameworks for detection of 2,4,6-trinitrophenol and

PT E

nitrofurazone in the aqueous phase, Cryst. Growth Des. 18 (2018) 7173-7182. [35] H. He, F. Sun, N. Zhao, R. Yuan, G. Zhu, Three novel zinc(II) metal-organic frameworksbased on three tetrazolate ligands: synthesis, structures and

CE

photoluminescence, RSC Adv. 4 (2014) 21535-21540. [36] L.-G. Yu, Y.-G. Sun, Z.-L. Wang, Mixed-ligand strategy affording two new

AC

metal-organic frameworks: Photocatalytic, luminescent and anti-lung cancer properties, J. Mol. Struct. 1180 (2019) 209-214. [37] H. He, Q.-Q. Zhu, C.-P. Li, M. Du, Design of a highly-stable pillar-layer Zinc(II) porous framework for rapid, reversible, and multi-responsive luminescent sensor in water, Cryst. Growth Des. 19 (2019) 694-703. [38] F. Li, Y.-S. Hong, K.-X. Zuo, Q. Sun, E.-Q. Gao, Highly selective fluorescent probe for Hg2+ and MnO4− by the two-foldinterpenetrating metal-organic framework with nitro functionalized linkers, J. Solid State Chem. 270 (2019), 509-515.

ACCEPTED MANUSCRIPT 13

[39] Synthesis of [Mn2(HBTC)2(TIAB)]n:A mixture of MnCl2 (25.2 mg, 0.1 mmol), TIAB (34.2 mg，0.1 mmol) and H3BTC (21 mg，0.1 mmol) was dissolved in a mixed solution of N,N-Dimethylformamide (DMF, 5 mL) and H2O (1 mL) in a 23.0 mL Teflon-lined autoclave and sonicated about 15 minutes, which was further put into 120°C oven for 3 days. The achieved samples can be collected

PT

directly after cooling to room temperature and further washed with fresh DMF for several times. Yield: 67% (based on H3BTC). Anal. calcd for C36H22O12N8Mn2: C

RI

49.77, H 2.53, N 12.90%; found: C 49.68, H 2.59, N 12.87%.

[40] Crystal data: C18H11O6N4Mn: Fw = 434.25, monoclinic, space group C2/c, a =

SC

22.364(2), b = 8.3422(8), c = 19.7364(19) Å, α = 90, β = 90.660(2), γ = 90, V = 3681.8(6) Å3, Z = 8, Dc = 1.567 g cm-3, μ = 0.762 mm-1, R(int) = 0.419, Nref =

NU

3807, R1 = 0.0392, wR2 = 0.0923 [I > 2σ(I)], R1 = 0.0546, wR2 = 0.0965 [all data], GOF = 1.060. The large single crystal data of [Mn2(HBTC)2(TIAB)]n was

MA

measured on a Bruker SMART CCD diffractometer with Mo Kα (λ = 0.71073 Å) radiation. The corresponding crystal structure was determined by the direct

D

method with SHELXT 6 and refined with full-matrix least-squares technique by

PT E

applying SHELXL-2015[51-53] through OLEX2 interface program.[54] All the non-hydrogen atoms can be added byusing the anisotropic displacement parameters. All the selected bond lengths and angles are both listed and

CE

summarised in Table S2.

[41] Y.-J. Qi, D. Zhao, X.-X. Li, X. Ma, W.-X. Zheng, S.-T. Zheng, Indium-based

AC

heterometal-organic frameworks with different nanoscale cages: syntheses, structures, and gas adsorption properties, Cryst. Growth Des. 17 (2017) 1159-1165.

[42] X. Gao, M. Liu, J. Lan, L. Liang, X. Zhang, J. Sun, Lewis acid-base bifunctional crystals with a three-dimensional framework for selective coupling of CO2 and epoxides under mild and solvent-free conditions, Cryst. Growth Des. 17 (2017) 51-57. [43] D. Samanta, P. S. Mukherjee, Self-assembled multicomponent Pd6 aggregates showing low-humidity proton conduction, Chem. Commun. 50 (2014)

ACCEPTED MANUSCRIPT 14

1595-1598. [44] D. Samanta, P. S. Mukherjee, Multicomponent self-sorting of a Pd7 molecular boat and its use in catalytic Knoevenagel condensation, Chem. Commun. 49 (2013) 4307-4309. [45] M. J. Manos, E. E. Moushi, G. S. Papaefstathiou, A. Tasiopoulos, New Zn2+ metal

PT

organic frameworks with unique network topologies from the combination of trimesicacid and amino-alcohols, Cryst. Growth Des. 12 (2012) 5471-5480.

frameworks, Chem. Rev. 112 (2012) 1126-1162.

RI

[46] Y. Cui, Y. Yue, G. Qian, B. Chen, Luminescent functional metal-organic

SC

[47] J. Heine, K. Müller-Buschbaum, Engineering metal-based luminescence in coordination polymers and metal-organic frameworks, Chem. Soc. Rev. 42 (2013)

NU

9232-9242.

[48] Z. Hu, B. J. Deibert, J. Li, Luminescent metal-organic frameworks for chemical

MA

sensing and explosive detection, Chem. Soc. Rev. 43(2014) 5815-5840. [49] R.-B. Lin, S.-Y. Liu, J.-W. Ye, X.-Y. Li, J.-P. Zhang, Photoluminescent

D

metal-organic frameworks for gas sensing, Adv. Sci. 3 (2016) 1500434.

PT E

[50] K. Qu, J. Wang, J. Ren, X. Qu, Carbon dots prepared by hydrothermal treatment of dopamine as an effective fluorescent sensing platform for the label-free detection of Iron(III) ions and dopamine, Chem. Eur. J. 19 (2013) 7243-7249.

CE

[51] G. M. Sheldrick, Phase Annealing in SHELX-90-direct methods for larger structures, ActaCryst. A 46 (1990) 467-473.

AC

[52] G. M. Sheldrick, A short history of SHELX, Acta Cryst. A 64 (2008) 112-122. [53] G. M. Sheldrick, Crystal Structure Refinement with SHELXL. Acta Cryst. C 71 (2015), 3-8.

[54] O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard, H. Puschmann, OLEX2: a complete structure solution, refinement and analysis program, J. Appl. Cryst. 42 (2009) 339-341.

ACCEPTED MANUSCRIPT 15

PT

Graphical Abstract-Pictogram

AC

CE

PT E

D

MA

NU

SC

RI

This work presents a new 3D luminescent metal-organic framework. It can be used as a luminescence sensor for PA and Cr2O72- with excellent recyclability.

ACCEPTED MANUSCRIPT 16

Highlights

AC

CE

PT E

D

MA

NU

SC

RI

PT

1. A novel 3D MOF was successfully fabricated by the mixed ligand strategy. 2. It can be implemented as a luminescence sensor for Cr2O72- and PA. 3. It has good recyclability at least four times.