Two 2D-MOFs based on two flexible ligands: structural control and fluorescence sensing on FeIII cation and CrVI-containing anions

Author’s Accepted Manuscript Two 2D-MOFs based on two flexible ligands: structural control and fluorescence sensing on FeIII cation and CrVI-containing anions Xiu-Fang Yang, Dan-Yang Yu, Xi-Ming Li, KeWei Zhang, Wen-Huan Huang www.elsevier.com/locate/yjssc

PII: DOI: Reference:

S0022-4596(19)30052-0 https://doi.org/10.1016/j.jssc.2019.02.006 YJSSC20604

To appear in: Journal of Solid State Chemistry Received date: 17 December 2018 Revised date: 30 January 2019 Accepted date: 3 February 2019 Cite this article as: Xiu-Fang Yang, Dan-Yang Yu, Xi-Ming Li, Ke-Wei Zhang and Wen-Huan Huang, Two 2D-MOFs based on two flexible ligands: structural control and fluorescence sensing on FeIII cation and CrVI-containing anions, Journal of Solid State Chemistry, https://doi.org/10.1016/j.jssc.2019.02.006 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 galley proof before it is published in its final citable 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.

Two 2D-MOFs based on two flexible ligands: structural control and fluorescence sensing on FeIII cation and CrVI-containing anions Xiu-Fang Yang, Dan-Yang Yu, Xi-Ming Li, Ke-Wei Zhang, Wen-Huan Huang* Shaanxi Key Laboratory of Chemical Additives for Industry, College

of

Chemistry

and

Chemical Engineering, Shaanxi University of Science and Technology, 710021, Xi’an, China.

Abstract: Based on flexible ligands 4,4'-((5-carboxy-1,3-phenylene)bis(oxy))dibenzoic acid (H3cpbda), two flexible N-donor ligands with the similar molecular length, 3-bis(1H-imidazol -1-yl)propane (bip) and 1,3-bis(pyridin-4-yl)propane (bpp), were introduced to assemble MOFs with different metals. Two 2D-MOFs, [Cd1.5(cpbda)(bip)0.5(H2O)]n (1) and [Cu(Hcpbda)(bpp)(H2O)]n (2), were successfully synthesized and characterized by singlecrystal X-ray diffraction, power X-ray diffraction, thermal-gravimetric analysis and fluorescence spectroscopy. The different terminal functional groups (imidazole and pyridine) in bip and bpp ligands generate different molecular coordination angels, which show diverse terminal type and bridged type in two 2D structures. The sensing results of 1 on metal cations and anions and magnetic property of 2 were studied. The influences of various N-donor ligands in assembly of flexible MOFs accompany with H3cpbda are also summarized.

Graphical Abstract:

Keywords: flexible ligand; 2D MOFs; chemosensor; fluorescence quenching, magnetism.

1. Introduction Metal organic frameworks (MOF) is a group of excellent solid materials for their integration of the inorganic metal center and functional organic building blocks via different chemical or physical interactions. The structural design and construction of MOF with different novel molecular structures attracted tremendous interests of many scientists for their controllable application in gas storage/separation[1-5], magnetism[6-8], luminescence[9-11], chemosensor[12-14],

electrical

conductivity[15-17],

catalysis[18-20],

energy

storage

and

conversion[21-24]. Since the framework of MIL-53 showed great breathing effect, the flexible porous MOFs have become another attractive MOF group for their structural conversions and been widely researched[25-28]. One effective approach to assemble flexible MOFs is changing synthesis methods, such as using large molecular solvents. Crystal structures would make changes by the departure of the solvents. However, the flexibility could be more effective controlled by

selection of ligands[29-30]. Lots of flexible organic ligands with different molecular configuration have been employed to construct novel dynamic MOFs, such as breathing selective separation, asymmetric catalysis frameworks, and other excellent applications[31-32]. Particularly, numbers of fluorescence complexes which assembled from flexible ligands have been synthesized as the chemo-sensors. They are of great importance for public health and environment protection due to their detection abilities on heavy metal ions and toxic organic matters[33-34]. As scheme 1 shown, carboxylic acid 4,4'-((5-carboxy-1,3-phenylene)bis(oxy))dibenzoic acid (H3cpbda) was an excellent building block for flexible MOF: i) H3cpbda is a tridentate carboxylic ligand, which can generates lots of coordination modes to combine with different number of metal ions; ii) two ether groups in H3cpbda ligand can flexibly rotate and bend to different bond angels, forming different molecular configurations, “T”, “Y”, “M” shaped, and so on, which have given birth to a series of isomeric MOFs [35-39]. According to the previous research, different rigid N-donor ligands reacting with H3cpbda ligands induced H3cpbda ligands showed various molecular configurations and generated diverse structural MOFs. For example, terminal-type rigid N-donor ligands induced lowdimensional structures while bridged-type generated high-dimensional ones

[36]

. Moreover,

another example of a flexible secondary N-donor ligand adopted different molecular configuration and induced the formation of two different H3cpbda ligand-based isomers [35]. However, the examples are still insufficient for finding out the secret of secondary N-donor ligands induction effects, more structures based on both two types of rigid and flexible Ndonor ligands should be synthesized and studied. Based on above, two more flexible N-donor ligands, 1,3-bis(1H-imidazol -1-yl)propane (bip) and 1,3-bis(pyridin-4-yl)propane (bpp), were introduced in H3cpbda-based MOF system. Interestingly. these two ligands contain different functional N-heterocyclic coordination groups, however, the similar molecular lengths (Scheme 1). Moreover, the rotation of sequential three methylene groups gives the bip and bpp ligands great flexibilities and largerange coordination directions. Successfully, two 2D sheet MOFs based on the bip and bpp

secondary ligands, [Cd1.5(cpbda)(bip)0.5(H2O)]n (1), [Cu(Hcpbda)(bpp)(H2O)]n (2), were hydrothermally synthesized. Two MOFs were characterized by single-crystal X-ray diffraction, power X-ray diffraction, thermal-gravimetric analysis and fluorescence spectroscopy. Owing to the good stabilities and fluorescence of complex 1, the sensing experiments of 1 on sixteen cations (Ag+, Ba2+, Bi3+, Ca2+, Cd2+, Co2+, Cr3+, Cu2+, Fe3+, Mg2+, Mn2+, Na+, Ni2+, Pb2+, Sr2+, Zn2+) and eleven anions (CO32-, Cr2O72-, CrO42-, SO42-, Br-, Cl-, ClO3-, PO43-, I-, NO3-, SCN-) were implemented, and the further titration processes showed 1 sensitively detects the Fe(III) cation and Cr(VI)-containing anions (Cr2O72-, CrO42-) by quenching responses.

Scheme 1: Structures of three flexible ligands H3cpbda, bip and bpp ligands.

2. Experimental 2.1 Materials and measurements The reagents were used directly as supplied commercially without further purification. Elemental analyses (C, H, N) were determined with a Perkin-Elmer model 240C automatic instrument. The X-ray powder diffraction pattern was recorded with a Pigaku D/Max 3III diffractometer. Thermal analysis was determined with a Netzsch STA 449C microanalyzer under flowing N2 atmosphere at a heating rate of 10 ºC /min. Luminescence spectra for the solid samples were investigated with a Hitachi F-4500 fluorescence spectrophotometer. 2.2 Preparation of [Cd1.5(cpbda)(bip)0.5(H2O)]n (1)

Complex 1 was obtained by the reaction of Cd(NO3)2·4H2O (0.1 mmol/30.9 mg), H3cpbda (0.05 mmol/19.7 mg), bip (0.05 mmol/8.8 mg), methanol (EtOH, 4 mL), H2O (5mL) were mixed in a 25mL Teflon-lined stainless-steel vessel. The mixture was sealed and heated at 140 oC for 72 h, and then cooled to room temperature at a rate of 5 oC /h. Finally, the transparent crystal of 2 was collected in 55% yield. The transparent crystal of 1 were isolated by washing with EtOH/H2O, and then dried in air. 2.3 Preparation of [Cu(Hcpbda)(bpp)(H2O)]n (2) Complex 2 was obtained by the reaction of Cu(NO3)2·3H2O (0.1 mmol/24.2 mg), H3cpbda (0.05 mmol/19.7 mg), bpp (0.05 mmol/9.9 mg), methanol (EtOH, 4 mL), H2O (5mL) were mixed in a 25mL Teflon-lined stainless-steel vessel. The mixture was sealed and heated at 140 oC for 72 h, and then cooled to room temperature at a rate of 5 oC /h. Finally, the wathet blue crystal of 3 was collected in 50% yield. The wathet blue crystal of 2 were isolated by washing with EtOH/H2O, and then dried in air. 2.4 Preparation of luminescent complexes suspension solutions 10 mg of complexes 1 were introduced into 5mL of different M(NO3)x (M = Ag+, Ba2+, Bi3+, Ca2+, Cd2+, Co2+, Cr3+, Cu2+, Fe3+, Mg2+, Mn2+, Na+, Ni2+, Pb2+, Sr2+, Zn2+) and Kx(A) (A = CO32-, Cr2O72-, CrO42-, SO42-, Br-, Cl-, ClO3-, PO43-, I-, NO3-, SCN-), the concentration of the ion solutions is 500 ppm (5mg metal salt was dissolved into 10mL water). After the soaking of the solid crystal samples, the solutions were placed into the supersonic vibration instrument, after the 2h vibration at 40 KHz, the luminescent suspension solutions were preapared. The emission data of the solutions were recorded at the extinction wavelength of 280 nm. 2.5 Crystallographic data collection and structure determination Single-crystal X-ray diffraction analyses of the compounds 1 were carried out on a Bruker SMART APEX II CCD diffractometer equipped with a graphite monochromated Mo radiation (λ = 0.71073 Å) by using /ω scan technique at room temperature. The structures were solved using direct methods and successive Fourier difference synthesis (SHELXS-97)

[40]

, and refined using the full-matrix least-squares method on F2 with

anisotropic thermal parameters for all non-hydrogen atoms (SHELXL-97)

[41]

. All non-

hydrogen atoms were refined anisotropically. The hydrogen atoms of organic ligands were placed in calculated positions and refined using a riding on attached atoms with isotropic thermal parameters 1.2 times those of their carrier atoms. The crystallographic data for 1-2 are listed in Table 1, the selected bond lengths and angels of 1-2 are listed in Table S1-S2. Table 1. Crystallographic data and details of diffraction experiments for complexes 1. Complex 1 Formula

Dcalcd.[g·cm-3]

C51H38Cd3N4O18

-1

1.824

Mr

1332.04

μ [mm ]

1.388

Crystal system

monoclinic

F [000]

2632.0

Space group

C2/c

θ [º]

4.52-50.02

a (Å)

10.678(2)

Reflections

???

b (Å)

17.613(3)

Rint

0.0232

c (Å)

26.167(5)

T(K)

296(2)

α (°)

90

Goof

1.033

β (°)

100.139(3)

γ (°)

90

V [Å3]

4844.7(16)

R [I > 2σ(I)]

wR2= 0.1029 R (all data)

Z

R1=0.0376

4

R1=0.0424 wR2= 0.1069

Complex 2 Formula

C34H26CuN2O9

Dcalcd.[g·cm-3]

1.161

Mr

670.11

μ [mm-1]

0.617

Crystal system

monoclinic

F [000]

1380

Space group

P2(1)/c

θ [º]

1.48- 27.37

a (Å)

10.142(2)

Reflections

21639 / 8407

b (Å)

19.023(4)

Rint

0.1018

c (Å)

20.182(4)

T(K)

296(2)

α (°)

90

Goof

1.029

β (°)

100.001(5)

γ (°)

90

3

V [Å ]

R [I > 2σ(I)]

wR2= 0.1777

3834.6(13) R (all data)

Z

R1=0.0750

4

R 1= Σ(|Fo|–|Fc|)/Σ|Fo|; wR2 = [Σw(Fo2 – Fc2)2/Σw(Fo2) 2]1/2

3. Results and discussion 3.1 Crystal structure of [Cd1.5(cpbda)(bip)0.5(H2O)]n (1)

R1=0.1754 wR2= 0.1941

Single-crystal X-ray diffraction analysis showes that 1 crystallizes in the C2/c space group. As shown in Fig. 1a, the asymmetric unit of 1 contains one and a half Cd(II) cations, one deprotonated cpbda3- ligand, a half bip ligands and one coordinated water molecule. The Cd1 atom bonds with five oxygen atoms from three cpbda3- ligands, one nitrogen atoms from bip ligand, and one water molecule, which forming a distorted CdO6N single-cap trigonal prism. Cd2 atom connects with six oxygen atoms from four capbda3- ligands, revealing a distorted CdO6 octahedron. The Cd-O bonds distances range from 2.208(3) (Cd1-O8) to 2.571(3) (Cd1-O2) Å, the Cd–N bond distances is 2.230(4) (Cd1-N1) Å, the bond angels around Cd(II) cations are in the range of 53.16(12)° (O1-Cd1-O2) to 177.36(18)° (O4-Cd2O4).

As shown in Fig. 1b, parallel Y-shaped cpbda3- ligands bond with Cd(II) ions in three directions to assemble a 2D double-layer. The flexible bip ligands bend to be U-shaped terminal building blocks, which play the key roles for the assembly of final 3D structure, coordinate to Cd(II) atoms from the two sides of the 2D layer (Fig. 1c). As the Fig. 1d shown, the 2D layers are further stacking to be 3D structure, in which the U-shpaed terminal bip block occupy the coordination sites and fill into the gaps between the layers to prevent the extension from 2D to 3D structure.

Fig.1 The crystal structure of 1. (a) The coordination environment of Cd(II) in 1. Symmetry codes: A, -0.5+x, 1.5– y, -0.5+z; B, 2–x, y, 0.5–z; C, -1+x, y, z; D, 1-x, y,1.5-z; E, 2-x, y,1.5- z. (b) The 2D sheet is constructed by Yshaped cpbda3- ligand and Cd2+, viewing along the b axis; (c) The bip terminal ligands bond with Cd cations at the two sides of 2D sheet, viewing along the a axis; (d) the 2D layers stacking to be 3D structure.

3.2 Crystal structure of [Cu(Hcpbda)(bpp)(H2O)] n (2) Single crystal X-ray diffraction results shows that complex 2 crystallizes in a P2(1)/c space group. The asymmetric unit of 2 contains one independent Cu(II) cations, one Hcpbda2ligand, one bpp ligand and one coordinated water molecule (Fig. 2a). The Cu1 atom bonds with two oxygen atoms from two T-shaped Hcpbda2- ligands, one water oxygen atom, two nitrogen atoms from two bridged bpp ligands, which forming a distorted CuO3N2 trigonal bipyramidal geometry structures. The Cu-O bonds distances are in range of 1.924(4) (Cu1-O7) to 1.944(3) (Cu1-O1) Å, The Cu-N bonds distances are in range of 1.999(5) (Cu1N1) to 2.005(5) (Cu1-N2) Å, the bond angels around the Cu(II) cations are in the range of 87.65(17)° (O7-Cu1-N1) to 175.8(2)° (N1-Cu1-N2). As the Fig. 2b shown, one carboxylic group in Hcpbda2- ligand does not attend the coordination, and two deprotonated carboxylic groups which showing a V-shaped coordination mode coordinate with Cu(II) cations to be 1D chains. On the other side, the bpp ligand in 2 exhibits a typical bridged coordination mode to connect with Cu(II) in another direction, which combine the 1D chains to be (4,4)-net (Fig. 2c). The 2D layers are stacking in ABAB type to further assemble the 3D structure, which is shown in Fig. 2d along the a axis. Compare the crystal structure with 1, the 2D net of 1 is forming form the Y-shaped cpbda3- ligands, which could combine more metal ions to be a double-layer. The terminal bip give the crucial role to prevent the further assembly from 2D to 3D structure. In 2, the bpp ligands act as bridges to connect with uncomplete deprotonated V-shaped Hcpbda2- in a 1:1 ratio to be (4,4)-net, which is an important component of 2D structure.

Fig.2 The crystal structure of 2. (a) The coordination environment of Cd(II) in 1. Symmetry codes: A, -1+x, 0.5–y, -0.5+z; B, x,0.5–y, 0.5+z; (b) The 1D chain is connect by V-shaped Hcpbda2- and Cu2+, then bond with bpp ligands; (c) The 2D sheet could be simplified as (4,4)-net, viewing along the a axis; (d) the 2D layers are ABAB stacking to be 3D structure, viewing along the a axis.

3.3 XRPD and TGA Results The XPRD patterns of complexes 1-2 are matching well with the simulated results from the single-crystal X-ray data (Fig. S8-S9) which indicates the pure single phases of these two compounds. Then, the TGA measurement is carried out under the N2 atmosphere in order to identify the thermal stabilities of 1-2, (Fig. S10). The curves of 1-2 show a weight loss of 2.9% (calcd. 2.7 %) for 1 at 110 oC and another weight loss of 2.9% (calcd. 2.7 %) for 2 at 100 oC, which should be attribute to the loss of coordinated water molecules. The complexes keep their skeletons stable before 325 oC, and then the frameworks rapid decompose. After 700 oC, the rest metal oxides solids observed are 31.8 % (CdO calcd. 29.0 %) for 1 and 11.8 % (CuO calcd. 11.9 %) for 2. 3.4 Luminescence Properties Fluorescent properties of Zn or Cd coordination polymers and their potential applications as fluorescent-emitting materials are attractive. As Fig.3a shown, the solid-state luminescent

spectra of free ligands (H3cpbda, bip) and complex 1 were investigated. The emission peaks of H3cpbda, bip ligands at 360, 382 nm (λex = 280 nm), were assigned to the intra ligand π*→π or π*→n electronic transitions. Complex 1 showed photoluminescence with emission maximum at 352 nm, which is attributed to ligand-to-metal charge transfer (LMCT), metal-toligand charge transfer (MLCT) or intra-ligand (π*→n / π* or π*→π) emission.

Fig. 3 The luminescence (a) Solid-state luminescent properties of ligand (H3cpbda, bip,) and complex 1; (b) the luminescence intensities of complex 1 in different solvents.

The fluorescence emissions of 1 in different solvents (DMF, ethanol, methanol, acetonitrile, water, hexane, and acetone) were investigated by suspending complex 1 (1 mg) powers in the different solvents (1mL). As shown in Fig.3b, the spectra showed luminescent emissions with different intensities around 350 nm (excitation at 300 nm) in above solvents except an emission enhancement around 380 nm of 1 in water and a quenching effect in acetone solvent. 3.5 Detection of the Fe(III) cation and Cr(VI)-containing anions To probe the sensing properties of 1 on metal cations and anions, 10 mg of compound 1 was dispersed into 5 mL of different M(NO3)x (M = Ag+, Ba2+, Bi3+, Ca2+, Cd2+, Co2+, Cr3+, Cu2+, Fe3+, Mg2+, Mn2+, Na+, Ni2+, Pb2+, Sr2+, Zn2+) and Kx(A) (A = CO32-, Cr2O72-, CrO42-, SO42-, Br-, Cl-, ClO3-, PO43-, I-, NO3-, SCN-) solutions to be suspensions, and the emission data were recorded for luminescence studies. The luminescence emissions of sixteen cations and eleven anions suspensions showed a sequence of Cd2+ > Zn2+ > Na+ > Ca2+ > Pb2+ > Co2+ > Mn2+ > Mg2+ > Sr2+ > Ba2+ > Cu2+ > Ni2+ > Ag+ > Bi3+ > Cr3+ > Fe3+ and another sequence of

ClO3- > NO3- > SO42- > Br- > Cl- > I- > SCN- > PO43- > CO32- > CrO42- > Cr2O72-. The Fe3+ cation (Figure 4) and Cr2O72‒, CrO42‒ anions (Figure 5) of 1 suspension exhibited distinctly luminescent quenching effects.

Fig. 4 (a) The visual change on the addition of various metal cations. (b) Comparison of the relative luminescence intensities of 1 suspension with sixteen cations.

Fig. 5 (a) The visual change on the addition of various anions. (b) Comparison of the relative luminescence intensities of 1 suspension with eleven anions.

In order to further detect the sensing sensitivities of complex 1 on these three ions, the titration experiments were conducted. The suspensions of 1 were prepared by dispersing 10 mg complexes into 3mL H2O. Introducing the Cr3+ as the comparison, the concentrations of cations (Fe3+) and anions (CrO42‒, Cr2O72‒) were increased from 0 to 1667 ppm to monitor the luminescent emission responses (Fig. S11). As Fig. S11a shown, along with the injections of Cr3+ solution, the luminescence slowly decreased and showing the quenching of 26.7% at 164 ppm, 35.5% at 323 ppm, 38.7% at 476 ppm, and 41.7% at 625 ppm. The final 53.9% quenching effect is observed at 1667 ppm. However, the Fe3+ cation, CrO42‒ and Cr2O72‒ anions give remarkable 95.4%, 99.7% and 99.6% quenching effects at 164 ppm, respectively.

After that the 98.8% quenching of Fe3+ is detected at 323 ppm, which exhibiting an order of Cr3+ << Fe3+ < CrVI-containing anion (Cr2O72‒ and CrO42‒). The above excellent detection performance on three ions with high sensitivities could be attributed to the photo induced electron transfer or resonance energy transfer or both[42-45]. The two-dimensional and flexible structure explores more active sites and provides fast transfer speed for host-guest process compare with three-dimensional structure. The rational selection of inorganic and organic building blocks is significant for further construction of MOF chemo-sensors. As the Figure 6a shown, the PXRD of recycled crystal sample was implemented, which indicated that the compound could be reused for detection. The recyclability tests of compound 1 on Fe3+, CrO42- and Cr2O72- were recorded by luminescent test for eight times, which revealed it has a good stability and reutilization (Figure 6b).

Fig. 6 (a) The PXRD of recycled samples. (b) the recyclability of 1 on Fe3+, CrO42- and Cr2O72-.

3.6 The magnetic property of complex 2. The antiferromagnetic behavior of 2 is shown in Fig. S13, which could be commonly observed at almost all the mononuclear Cu-complexes. Therefore, it was not discussed in detail. 3.7 The influence of secondary N-donor ligands and molecular configuration of H3cpbda The control of different dimensional MOFs is divided into three approaches: 1) selection of metal cations for their different atom radius and coordination number; 2) the choice of secondary N-donor ligand in various aspects, such as ligand type (flexible or rigid), length, coordination functional groups et al.;. 3) synthesis methods, such as reactant, solvents,

temperature, pH values. As it was mentioned above, the coordination modes and molecular configurations of flexible ligand H3cpbda are crucial factors for the construction of MOF. Combined with the early reported research works in our group, the influence of secondary Ndonor ligands and molecular configuration of H3cpbda will be discussed by two parts (Fig. 7). As the five different molecular configuration types of H3cpbda in different MOF below, although three carboxyl groups were deprotonated, the T and Y shaped configurations which have larger molecule angels tend to assemble 3D structures with different porous channel shapes. However, cpbda3- with W shape is good for assembly low dimensional structures because of its small angels of three carboxyl groups. The V and I shape with uncoordinated carboxyl acid groups show low coordination numbers, and their uncoordinated arms prevent the further assembly of high-dimension structures. Four rigid N-donor ligands and three flexible ligands were also investigated for their influence on the structural construction. The rigid nature gave more accurate coordination modes, the only influence factors are the coordination bond angels (70o for 2,2-bpy and phen, or 180o for 4,4-bpy and bpe), the ligand length and size of the rigid ligands. The 2,2-bpy and phen are prone to generate low dimensional structures, while the 4,4-bpy and phen are easy for building high dimensional frameworks. Moreover, the long ligand is easy to generate interpenetration structure comparing with the short ones. Flexible N-donor ligands are more complex for their diverse molecular configuration, such as the bpa with two various configurations[35], and the different molecular coordination angels of bip and bpp ligands generates totally various structures and the properties in this work.

Fig. 7 (a) The visual change on the addition of various anions. (b) Comparison of the relative luminescence intensities of 1 suspension with eleven anions.

4. Conclusions In summary, two flexible N-donor ligands with different molecular coordination angels were invited for assembly of two novel 2D-sheet MOFs with H3cpbda. Complex 1 with the bip and Y shaped cpbda3- ligands generated a functional Cd complex for efficient detection of FeIII and CrVI-containing anions by luminescent quenching effects. Compare two structures, it was found that the bip with 144o coordination angel bended and bonded with Cd cations, which prevented the further assembly of 2D to 3D structure in 1. The bpp ligands with 180o coordinated angel acted as bridged blocks in 2D structure of 2. Based on the previous research and this work, 1) the solvents and pH values palyed the key factors for the deprotonation and the molecular configurations of multi-carboxyl acid ligand (H3cpbda), which was directly influence the final structural dimensions and the porous shapes; 2) N-donor ligands exhibited clear coordination number and modes in construction of MOFs. The only factor for rigid ones was the bond angels of N-M-N, which was crucial for structural dimension. However, the influence factors of flexible ones were complex. The various solvents, molecular coordination angels, and other factors all induced the exhibition of different molecular configurations and final structural dimensions. This work made a conclusion and gave great examples of

assemble various dimensional coordination polymers with excellent luminescent properties, using multi-carboxyl acid with different N-donor ligand. Acknowledgements The Research Program of the Shaanxi Provincial Department of Education (15JK1105, 16JK1108), Natural Science Foundation of Shaanxi Province (Grant 2017JQ2021), The Open Foundation of Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education. The open Foundation of State Key Laboratory of Structural Chemistry (20180024), The open Foundation of Key Laboratory of Coal to Ethylene Glycol and Its Related Technology (201801). Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at http: // References [1] F. J. Zhao, Y. X. Tan, W. Wang, Z. Ju, D. Q. Yuan. Inorg. Chem., 2018, 57(21): 1331213317. [2] J. I. Choi, H. Chun, M. S. Lah, J. Am. Chem. Soc., 2018, 140(34): 10915-10920 [3] M. Zeeshan, V. Nozari, M. B. Yagci, T. Isik, U. Unal, V. Ortalan, S. Keskin, A. Uzun. J. Am. Chem. Soc., 2018, 140(32): 10113-10116. [4] H. Huang, H. Sato, T. Aida. J. Am. Chem. Soc., 2017, 139(26): 8784-8787 [5] L. Yang, X. Cui, Y. Zhang, Q. Yang, H. Xing, J. Mater. Chem. A, 2018, 6(47): 2445224458. [6] A. Kultaeva, T. Biktagirov, P. Neugebauer, H. Bamberger, J. Bergmann, J. et al. J. Phys. Chem. C, 2018, 122(46): 26642-26651. [7] Z. C. Shao, C. Huang, J. Dang, Q. Wu, Y. Y. Liu, J. Ding, H. W. Hou. Chem. Mater., 2018, 30(21): 7979-7987. [8] H. Meng, C. Zhao, M. Nie C. R. Wang, T. S. Wang. ACS Appl. Mater. Interfaces., 2018, 10(38): 32607-32612. [9] M. Gutierrez, C. Martin, K. Kennes, J. Hofkens M. Van der Auweraer, F. Sanchez, A. Douhal. Adv. Optical Mater., 2018, 6: 1701060. [10] X. G. Yang, X. Q. Lin, Y. B. Zhao, Y. S. Zhao, D. P. Yan. Angew. Chem. Int. Ed., 2017, 56(27): 7853-7857. [11] W. Huang, F. Pan, Y. Liu, S. Huang, Y. Li, J. Yong, Y. Li, A. M. Kirillov, D. Wu. Inorg. Chem., 2017, 56: 6362-6370. [12]X. H. Zhao, S. N. Ma, H. Long, H. Yuan, C. Y. Tang, K. Ping, Y. H. Tsang. ACS Appl. Mater. Interfaces., 2018, 10(4): 3986-3993. [13] J. Wieme, K. Lejaeghere, G. Kresse, V. Van Speybroeck. Nat. Commun., 2018, 9(1): 110. [14] X. L. Hu, C. Qin, X. L. Wang, K. Z. Shao, Z. M. Su. Chem. Commun., 2015, 51: 1752117524. [15] R. Dong, P. Han, H. Arora, M. Ballabio, M. Karakus, Z. Zhang, C. Shekhar, P. Adler, P. Petkov, A. Erbe, et al. Nat. Mater., 2018, 17(11): 1027-1032.

[16] W. H. Li, K. Ding, H. R. Tian, M. S. Yao, B. Nath, W. H. Deng, Y. B. Wang, G. Xu. Adv. Funct. Mater., 2017, 27: 1702067. [17] H. Zhong, Z. H. Fu, J. M. Taylor, G. Xu, R. H. Wang. Adv. Funct. Mater., 2017, 27: 1701465 [18] Y. B. Huang, J. Liang, X. S. Wang, R. Cao. Chem. Soc. Rev., 2017, 46: 126-157. [19] A. Szecsenyi, G. Li, J. Gascon, E. A. Pidko. Chem. Sci., 2018, 9(33): 6765-6773. [20] H. D. Park, M. Dinca, Y. Roman-Leshkov. J. Am. Chem. Soc., 2018, 140(34): 1066910672. [21] M. Zhang, Q. Dai, H. G. Zheng, M. Chen, L. M. Dai. Adv. Mater., 2018, 30: 1705431. [22] X. L. Wang, L. Z. Dong, M. Q. Y. Li, Y. Q. Lan, et al. Angew. Chem. Int. Ed., 2018, 57: 9660. [23] X. Wang, H. Xiao, C. Chen, D. S. Wang, L. Gu, X. D. Han, J. Li, Y. D. Li. J. Am. Chem. Soc. 2018, 140(45): 15336-15341. [24] S. Wang, X. Wang, X. W. Lou. J. Am. Chem. Soc., 2018, 140 (45): 15145-15148. [25] C. Volkringer and S. M. Cohen. Angew. Chem. Int. Ed., 2010, 49, 4644-4648. [26] Y. Han, J. F. Zhai, L. L. Zhang, S. J. Dong. Nanoscale, 2016, 8: 1033-1039. [27] C. Kong, H. Du, L. Chen, B. L. Chen. Energy Environ. Sci., 2017, 10: 1812-1819. [28] Y. Y. Zhao, X. Zhang, B. Wang, et al. J. Am. Chem. Soc., 2018, 140(36): 11179-11183. [29] A. Kondo, T. Fujii, K. Maeda. Dalton Trans., 2014, 43(22): 8174-8177. [30] Y. X. Shi, W. X. Li, W. H. Zhang, J. P. Lang. Inorg. Chem., 2018, 57(14): 8627-8633. [31] L. Yang, X. Cui, Y. Zhang, Q. Yang, H. B. Xing. J. Mater. Chem. A., 2018, 6(47): 24452-24458. [32] H. Yangt, F. Guo, P. Lama, W. Y. Gao, S. Q. Ma, et al. ACS Cent. Sci., 2018, 4(9): 11941200. [33] Yin, Z.; Wan, S.; Yang, J.; Kurmoo, M.; Zeng, M. H. Coord. Chem. Rev., 2019, 378: 500-512. [34] X. Zhang, Y. Zhang, D, Yue, G. D. Qian. Small, 2018, 14: 1801563. [35] W. H. Huang, J. Z. Li, Y. Y. Wang, et al. Dalton Trans., 2016, 45: 15060-15066. [36] W. H. Huang, Y. N. Zhang, Y. Y. Wang, et al. Inorg. Chim. Acta, 2015, 433: 52-62. [37] W. H. Huang, J. Z. Li, Y. Y. Wang, et al. RSC Adv., 2015, 5: 97127-97132. [38] W. H. Huang, G. P. Yang, Y. Y. Wang, et al. Cryst. Growth Des., 2013, 13: 66-73. [39] W. H. Huang, X. J. Luan, Y. Y. Wang, et al. CrystEngComm., 2013, 15: 10389-10398. [40] Sheldrick G M. SHELXL-97, Program for Crystal Structure Determination, University of Göttingen, Germany, 1997. [41] Sheldrick G M. SHELXL-97, Program for Crystal Structure Refinement, University of Göttingen, Germany, 1997. [42] J. C. Sanchez, A. G. DiPasquale, A. L. Rheingold, W. C. Trogler, Chem. Mater., 2007, 19: 6459-6470. [43] A. J. Lan, K. H. Li, H. H. Wu, et al, Angew. Chem. Int. Ed., 2009, 48: 2334-2338. [44] S. Pramanik, C. Zheng, X. Zhang, et al, J. Am. Chem.Soc., 2011, 133: 4153-4155. [45] S. S. Nagarkar, B. Joarder, A. K. Chaudhari,et al, Angew. Chem. Int. Ed., 2013, 52: 2881-2885.

Highlights 1) 2D-sheet MOFs could be used as a chemical stable sensor 2) Configuration of flexible multi-carboxylic acid 3) The different influence factors of two types of N-donor ligands