Two new luminescent Zn(II) compounds constructed from guanazole and aromatic polycarboxylate ligands

Accepted Manuscript Two new luminescent Zn(II) compounds constructed from guanazole and aromatic polycarboxylate ligands Haixiang Zhao, Yanli Dong, Haiping Liu PII:

S0022-2860(15)30348-3

DOI:

10.1016/j.molstruc.2015.10.046

Reference:

MOLSTR 21891

To appear in:

Journal of Molecular Structure

Received Date: 15 July 2015 Revised Date:

9 October 2015

Accepted Date: 19 October 2015

Please cite this article as: H. Zhao, Y. Dong, H. Liu, Two new luminescent Zn(II) compounds constructed from guanazole and aromatic polycarboxylate ligands, Journal of Molecular Structure (2015), doi: 10.1016/j.molstruc.2015.10.046. 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.

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Presented here are two new Zn(II) compounds, [(CH3)2NH2]2n[Zn3(bpt)2(datrz)2]n (1) and

[(CH3)2NH2)]n[Zn2(bptc)(datrz)]n·n(H2O)

(2)

(H3bpt

=

biphenyl-3,4’,5-tricarboxylic acid, H4bptc = biphenyl-3,3΄,5,5΄-tetracarboxylic acid, Hdatrz =3,5-diamino-1,2,4-triazole). Compound 1 features a trinodal (3, 4,

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6)-connected topological network with the point symbol of {4.62}2{4.64.8}{46.64.85}.

Compound 2 displays a binodal (4, 6)-connected topological network with the point

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symbol of {32.62.72}{34.42.64.75}.

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Two new luminescent Zn(II) compounds constructed from guanazole and aromatic polycarboxylate ligands

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Haixiang Zhao1,*, Yanli Dong2, Haiping Liu1 1

College of Science, Hebei North University, Zhangjiakou, 075000, China.

2

College of Sciences, Agricultural University of Hebei, Baoding 071001, China.

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Corresponding authors: [email protected]

Abstract

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Two new Zn(II) compounds, namely [(CH3)2NH2]2n[Zn3(bpt)2(datrz)2]n (1) and [(CH3)2NH2)]n[Zn2(bptc)(datrz)]n·n(H2O) (2) (H3bpt = biphenyl-3,4’,5-tricarboxylic acid,

H4bptc

=

biphenyl-3,3΄,5,5΄-tetracarboxylic

acid,

Hdatrz

=3,5-diamino-1,2,4-triazole), have been obtained by the self-assemble reactions of Zn(NO3)2, 3,5-diamino-1,2,4-triazole, aromatic polycarboxylate ligands under solvothermal conditions. Single crystal X-ray structural analyses reveal that both

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compounds display three-dimensional (3D) frameworks. Compound 1 features a trinodal (3, 4, 6)-connected topological network with the point symbol of {4.62}2{4.64.8}{46.64.85}. Compound 2 displays a binodal (4, 6)-connected topological network with the point symbol of {32.62.72}{34.42.64.75}. In addition, the

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thermal stabilities and luminescent properties of compounds 1 and 2 were also investigated in the solid state at room temperature.

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Keywords: Zn(II) compounds; Solvothermal synthesis; Topology; Luminescence

1. Introduction

Over the past few decades, metal-organic frameworks (MOFs) have been

extensively studied for their intriguing topological frameworks and huge potential applications as functional materials in the realm of luminescence, catalysis, magnetism and gas separation [1-5]. One common method for the construction of MOFs is the hydrothermal or solvothermal self-assembly of metal ions and organic ligands. Through this method, numerous MOFs have been successfully obtained and 1

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structurally characterized [6-9]. However, it is still a great challenge in crystal engineering to obtain the MOFs with predictable frameworks and properties. It is well known that the structures and properties of MOFs greatly depend on the structure of

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the organic ligands, the coordination geometry and electronic characteristics of the metal ions [10-12]. Thus, selection of appropriate organic ligands and metal ions are

the most important for the construction of desired MOFs with potential properties. In addition, the synthetic strategy is also a key factor for the design and construction of

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MOFs. Among the widely used strategies for the construction of MOFs, the

mixed-ligand self-assemble strategy, which combines the N-containing and O-containing ligands together, has been proven to be one of the most effective

ligands

provides

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methods to synthesize MOFs [13-15]. The combination of two different kinds of possibilities

to

result

in

various

3D

structures.

3,5-diamino-1,2,4-triazole (Hdatrz) is a good multidentate N-containing organic ligands which can bridge metal ions in various coordination modes. O-containing polycarboxylate ligands have multiple bonding sites and high affinity to transition

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metal ions. The combination of polycarboxylate and Hdatrz ligands can result in various intriguing topological frameworks with promising potential properties. To date, only few examples of Zn(II) compounds constructed from Hdatrz and polycarboxylate ligands [16-17]. Compared with traditional hydrothermal conditions,

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the solvothermal conditions not only can greatly enhance the solubility of the organic ligands, but also the organic solvents can act as templates directing the synthesis of

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MOFs. On the basis of aforementioned points, herein, we selected Hdatrz and two different polycarboxylate ligands as the mixed ligands to constructed two new Zn(II) compounds,

namely

[(CH3)2NH2]2n[Zn3(bpt)2(datrz)2]n

(1)

and

[(CH3)2NH2)]n[Zn2(bptc)(datrz)]n·n(H2O) (2) (H3bpt = biphenyl-3,4’,5-tricarboxylic

acid,

H4bptc

=

biphenyl-3,3΄,5,5΄-tetracarboxylic

acid,

Hdatrz

=3,5-diamino-1,2,4-triazole). Compound 1 features a 3D framework with trinodal (3, 4, 6)-connected topology, and compound 2 features a 3D framework with binodal (4,6)-connected topology.

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2. Experimental 2.1. Materials and instrumentation All reagents and solvents employed in this work were commercially available and

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used without further purification. Elemental analyses (C, H and N) were determined with an elemental Vario EL III analyzer. Infrared spectrum using the KBr pellet was measured on a Nicolet Magna 750 FT-IR spectrometer in the range of 400-4000 cm–1.

Powder X-ray diffraction (PXRD) analyses were recorded on a PANalytical X'Pert

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Pro powder diffractometer with Cu/Kα radiation (λ = 1.54056 Å) with a step size of 0.05°. Thermal analyses were carried out on a NETSCHZ STA–449C thermoanalyzer

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with a heating rate of 10 °C/min under a nitrogen atmosphere. Fluorescence spectra of the solid samples were performed on an Edinburgh Analytical instrument FLS920. 2.2. Synthesis of [(CH3)2NH2]2n[Zn3(bpt)2(datrz)2]n (1)

A mixture of Zn(NO3)2·6H2O (0.030 g, 0.1 mmol), H3bpt (0.025 g, 0.1 mmol), Hdatrz (0.01 g, 0.1mmol), DMF (3 mL) and CH3OH (1 mL) was placed in a small vial at 90 ºC for 72 h and then cooled to room temperature slowly. Colorless block

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crystals were obtained in 42% yield based on Zn(NO3)2·6H2O. Anal. calcd. for C36H29N11O12Zn3 (1004.88): C, 42.99; H, 2.89; N, 15.33%. Found: C, 42.89; H, 2.85; N, 15.42%. IR (cm-1): 3422(w), 1712(m), 1675(s), 1587(m), 1509(m), 1389(m), 1378(m), 1109(w), 1025(w), 958(m), 893(m), 826(m), 778(w), 690(w), 674(w),

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589(w), 562(w).

2.3. Synthesis of [(CH3)2NH2)]n[Zn2(bptc)(datrz)]n·n(H2O)(2)

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The synthesis of compound 2 was similar to that of 1, but with H4bptc (0.093 g,

0.1 mmol) in place of H3bpt. Colorless crystals of 2 were obtained in 38% yield based on Zn(NO3)2·6H2O . Elemental analyses calcd. for C20H18N6O9Zn2 (617.18): C, 38.89;

H, 2.92; N, 13.61%. Found: C, 38.86; H, 2.97; N, 13.67%. IR data (KBr pellet): 3450(s), 3179(m), 1652(m), 1626(m), 1550(s), 1478(s), 1431(m), 1182(s), 1135(m), 1034(m), 826(w), 807(m), 787(w), 610(m), 550(m), 519(m), 486(w). 2.4. X-ray crystallography Suitable single crystals of 1 and 2 were carefully selected under an optical

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microscope and glued to thin glass fibers. Structural measurements were performed with

a

computer–controlled

Oxford

Xcalibur

E

diffractometer

with

graphite–monochromated Mo–Kα radiation (λ = 0.71073 Å) at T = 293(2) K. Absorption corrections were made using the SADABS program [18]. The structures

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were solved by direct methods and refined by full–matrix least–square methods on F2

by using the SHELXL–97 program package [19]. All non–hydrogen atoms were

refined anisotropically. The H atoms attached to their parent atoms of organic ligands

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were geometrically placed and refined using a riding model. Crystal data, as well as details of data collection and refinements of 1 and 2 are summarized in Table 1,

3. Results and discussion

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selected bond lengths and angles are given in Table 2.

3.1. Crystal structure of compound 1

Single crystal X-ray diffraction analysis reveals that compound 1 crystallizes in the monoclinic C2/c space group and features a 3D framework with (3,4,6)-connected topology. There are one and a half Zn(II) ions, one bpt3- ligand, one datrz- ligand and

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one dimethylamine cations. As shown in Figure 1a, both Zn1 and Zn2 are four-coordinated with tetrahedral coordination geometries, which are defined by two carboxylate oxygen atoms and two nitrogen atoms. The Zn-O and Zn-N distances are in the range of 1.914(4)-1.936(3) Å, 1.954(5)-1.994(4) Å, respectively. Two

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symmetry-related Zn2 ions are bridged by two datrz- ligands into a dinuclear [Zn2(datrz)2] unit with the Zn…Zn separation of 3.678 Å (Figure 1b). These dinuclear

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[Zn2(datrz)2] units and all Zn1 ions are further connected together via the connection

of L3- and datrz- ligands, affording a 3D framework of 1 (Figure 1c). In 1, each datrz-

ligand links three Zn(II) ions in µ 3-N1, N2, N3 mode and each bpt3- ligand links three

Zn(II) ions with its three carboxylate groups in uniform monodentate mode. From a topological viewpoint, each bpt3- ligand links two dinuclear [Zn2(datrz)2] units and one Zn1 ion, and it can be considered as a 3-connected node. Each Zn1 ion is surrounded by two dinuclear [Zn2(datrz)2] units and two Zn1 ions, and it can be

reduced into a 4-connected node. Each dinuclear [Zn2(datrz)2] unit is connected by

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two Zn1 ions and four bpt3- ligands, so it can be viewed as 6-connected node. The datrz- ligands act as 2-connected spacers. As a result, the 3D framework of 1 can be simplified into a new trinodal (3,4,6)-connected topological network with the point

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symbol of {4.62}2{4.64.8}{46.64.85} (Figure 1d). 3.2. Crystal structure of compound 2

Single crystal X-ray diffraction analysis reveals that compound 2 crystallizes in

monoclinic C2/m space group and features a 3D framework with (4, 6)-connected

topology. The asymmetric unit of 2 contains two halves Zn(II) ions, half of bptc4-

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ligand, half datrz- ligand, half of dimethylamine cation and half of lattice water molecule. As shown in Figure 2a, Zn1 is five-coordinated with a square pyramidal

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geometry, which is defined by four carboxylate oxygen atoms and one nitrogen atom. Zn2 is tetrahedrally coordinated by two carboxylate oxygen atoms and two nitrogen atoms. The Zn-O and Zn-N distances locate in the range of 1.909(4)-2.071(3) Å, 1.967(3)-2.007(5) Å, respectively. Notably, two symmetry-related Zn1 ions are bridged by four carboxylate groups into a paddle wheel shaped dinuclear [Zn2(COO)4]

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unit with the Zn1…Zn1 separation of 3.012 Å, and two symmetry-related Zn2 ions also are bridged by two datrz- ligands into another dinuclear [Zn2(datrz)2] unit with the Zn2…Zn2 separation of 3.614 Å (Figures 2b and 2c). These dinuclear units are further connected together via the connection of datrz- and bptc4- ligands, generating a

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3D anionic framework with the channels occupied by the dimethylamine cations (Figure 2d). The datrz- ligand links three Zn(II) ions in µ 3-N1, N2, N3 mode, and the

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bptc4- ligand links six Zn(II) ions with two carboxylate groups in monodentate mode and the other two carboxylate groups in bis-monodentate mode. To better understand this framework of 2, topological analysis method was used to simplify the organic

ligands and the dinuclear units. Each bptc4- ligand links four dinuclear units, and each dinuclear unit (dinuclear [Zn2(COO)4] unit or dinuclear [Zn2(datrz)2] unit) is bonded

to four bptc4- ligands and two dinuclear units via the connection of datrz- ligands. So the bptc4- ligands and the dinuclear units can be viewed as 4-, 6-connected nodes, respectively, and the datrz- ligands can be reduced into linear linkers. Based on this simplification, the whole framework of 2 can be simplified into a bimodal (4, 5

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6)-connected topological network with the point symbol of {32.62.72}{34.42.64.75} (Figure 2e). 3.3. Powder X-ray diffraction patterns and thermal analyses of compounds 1 and 2

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The phase purities of bulk samples of compounds 1 and 2 have been confirmed by the powder X-ray diffraction analyses. As shown in Figure 3, the major peak positions of the bulk solids of compounds 1 and 2 match well with those of the

simulated patterns based on respective single crystal X-ray diffraction data, indicating

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that the synthesized compounds are in pure phase. In addition, the thermal behaviors of compounds 1 and 2 were also investigated by thermalgravimetric analysis (TGA)

under N2 atmosphers in the temperature range of 30-800 ºC. For compound 1, there is

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no obvious weight loss in the temperature range of 30-270 ºC, and after 270 ºC, the framework started to collapse accompanied by the decomposition of the organic components. The residue of the powder may be ZnO (obsd: 24.98%, calcd: 24.18%) (Figure 3c). For compound 2, the weight loss corresponding to the departure of the lattice water molecule is observed from to (obsd: 2.72%, calcd: 2.92%). The

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framework can be stable up to 271 ºC, where the framework begins to collapse owing to the decomposition of the organic ligands. Finally, the remnants are 27.52%, corresponding to the formation of ZnO (calcd: 26.24%) (Figure 3d). 3.4. Photoluminescent properties of compounds 1 and 2

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Metal-organic frameworks with d10 transition metal ions have attracted intense interest from chemists owing to their potential applications in photochemistry,

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chemical sensors, and electroluminescent displays [20-22]. In this work, the luminescent properties of compounds 1 and 2 as well as the free ligands (H3bpt,

H4bptc and Hdatrz) were investigated in the solid state at room temperature. The free

H3bpt, H4bptc and Hdatrz ligands display intense emission peaks at 388 nm (λex = 345 nm), 402 nm (λex = 345 nm), 435 nm (λex = 340 nm), respectively, which can be

assigned to the π*-n or π*-π transitions (Figure 3b). Under the excitation light of 340 nm, compounds 1 and 2 show broad emission bands centered at 442 nm and 445 nm, respectively (Figure 3a). Notably, the luminescent emission peaks of compounds 1 6

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and 2 are similar to that of free Hdatrz ligand with red-shifts of 7 nm and 10 nm, respectively. The absence of the carboxylate-based ligands (H3bpt and H4bptc) emission bands further indicates that the luminescence of compounds 1 and 2 can be

4. Conclusion In

summary,

two

new

luminescent

Zn(II)

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attributed to Hdatrz intraligand charge transfer [23].

compounds

based

on

3,5-diamino-1,2,4-triazole mixed with two different aromatic polycarboxylate ligands

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have been prepared under solvothermal conditions. The two compounds both possess 3D frameworks but with different topologies. Compound 1 displays a trinodal

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(3,4,6)-connected topological network, and compound 2 displays a binodal (4.6)-connected topological network. The high thermal stabilities and intense luminescent properties of compounds 1 and 2 indicate that they can be used as new photoactive materials.

5. Supplementary material

CCDC Nos. 1412024 for compound 1 and 1412025 for compound 2 contain the

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supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax:

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(internat.) +44 1223/336 033; E-mail: [email protected]].

Acknowledgements

This work was supported by Grants from the Sci-technical Support Project of Hebei

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Province (14227115D).

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[5] Y. B. Zhang, H. Furukawa, N. Ko, W. X. Nie, H. J. Park, S. Okajima, K. E. Cordova, H. X. Deng, J. Kim, O. M. Yaghi, J. Am. Chem. Soc. 2015, 137, 2641. [6] Y. Q. Chen, S. J. Liu, Y. W. Li, G. R. Li, K. H. He, Z. Chang, X. H. Bu, CrystEngComm 2013,

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[13] N. N. Ma, F. Guo, J. Inorg. Organomet. Polym. 2013, 23, 1177.

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[14] M. Du, C. P. Li, C. S. Liu, S. M. Fang, Coord. Chem. Rev. 2013, 257, 1282. [15] J. X. Yang, X. Zhang, J. K. Cheng, J. Zhang, Y. G. Yao, Cryst. Growth & Des. 2012, 12, 333.

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[17] G. Xing, Q. Liu, Y. Zhang, S. Zhang, Y. L. Dong, Z. Anorg. Allg. Chem. 2015, 641, 1556. [18] G. M. Sheldrick, SADABS, University of Göttingen: Göttingen, Germany, 1996.

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[19] Sheldrick, G. M. SHELXS 97, Program for Solution of Crystal Structures, University of Göttingen, Göttingen, Germany, 1997.

[20] Y. Cui, Y. Yue, G. Qian, B. Chen, Chem. Soc. Rev. 2012, 112, 1126. [21] Z. Hu, B. J. Deibert, J. Li, Chem. Soc. Rev. 2014, 43, 5815.

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Table 1 Crystal data and structure refinements for compounds 1 and 2.

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2 C20H18N6O9Zn2 617.18 Monoclinic C2/m 18.8226(10) 18.6427(8) 14.2485(5) 90.00 130.175(3) 90.00 3820.3(3) 4 1.073 1.295 7465 3464 (Rint = 0.0248) 1.026 R=0.0598, wR2= 0.1903 R=0.0703, wR2= 0.2033

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Formula Fw (g/mol) Crystal system Space group a (Å) b (Å) c (Å) α(°) β(°) γ(°) Volume (Å3) Z Density (cm3/g) Abs. coeff. (mm-1) Total reflections Unique reflections Goodness of fit on F2 Final R indices [I>2sigma(I2)] R (all data)

1 C36H29N11O12Zn3 1004.88 Monoclinic C2/c 28.3006(15) 20.085(3) 15.4335(12) 90.00 92.498(5) 90.00 8764.4(16) 4 1.761 0.850 17271 8552 (Rint = 0.0721) 0.952 R=0.0873, wR2= 0.2117 R=0.1301, wR2= 0.2485

Table 2 Selected bond lengths (Å) and angles (°) for compounds 1 and 2.

1.936(3) 1.994(4) 1.914(4) 1.954(5) 135.7(3) 100.47(16) 105.92(15) 116.62(15) 114.0(2) 101.93(17)

Zn(1)-O(1)a Zn(1)-N(3)c Zn(2)-O(6) Zn(2)-N(2)e O(1)-Zn(1)-N(3)b O(1)-Zn(1)-N(3)c N(3)b-Zn(1)-N(3)c O(4)d-Zn(2)-N(1) O(4)d-Zn(2)-N(2)e N(1)-Zn(2)-N(2)e

1.936(3) 1.994(4) 1.925(3) 1.978(5) 105.92(15) 100.47(15) 105.6(3) 103.41(17) 112.5(2) 108.44(17)

2.007(5) 2.035(3) 2.071(3) 1.909(4) 1.967(3)

Zn(1)-O(1)a Zn(1)-O(2)b Zn(2)-O(4)d Zn(2)-N(2)e N(1)-Zn(1)-O(1)a

2.035(3) 2.071(3) 1.909(4) 1.967(3) 101.06(14)

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Compound 1 Zn(1)-O(1) Zn(1)-N(3)b Zn(2)-O(4)d Zn(2)-N(1) O(1)-Zn(1)-O(1)a O(1)a-Zn(1)-N(3)b O(1)a-Zn(1)-N(3)c O(4)d-Zn(2)-O(6) O(6)-Zn(2)-N(1) O(6)-Zn(2)-N(2)e Compound 2 Zn(1)-N(1) Zn(1)-O(1) Zn(1)-O(2)c Zn(2)-O(4) Zn(2)-N(2)f

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N(1)-Zn(1)-O(1) 101.06(14) O(1)a-Zn(1)-O(1) 93.3(2) b a b N(1)-Zn(1)-O(2) 101.16(14) O(1) -Zn(1)-O(2) 157.44(13) b c O(1)-Zn(1)-O(2) 86.18(16) N(1)-Zn(1)-O(2) 101.16(14) a c c O(1) -Zn(1)-O(2) 86.18(16) O(1)-Zn(1)-O(2) 157.44(13) O(2)b-Zn(1)-O(2)c 85.8(2) O(4)d-Zn(2)-O(4) 108.8(3) d e f O(4) -Zn(2)-N(2) 103.20(15) O(4)-Zn(2)-N(2) 115.06(19) d f f O(4) -Zn(2)-N(2) 115.06(19) O(4)-Zn(2)-N(2) 103.20(15) e f N(2) -Zn(2)-N(2) 111.94(19) Symmetry codes: compound 1 (a) –x + 1, y, –z + 5/2; (b) x + 1/2, –y + 1/2, z + 1/2; (c) –x + 1/2,

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–y + 1/2, –z + 2; (d) x, –y, z – 1/2; (e) –x, –y, –z + 2. compound 2 (a) x, –y + 1, z; (b) –x – 1, y, –z; (c) –x – 1, –y + 1, –z; (d) –x, y, –z + 1; (e) –x – 1/2, –y + 1/2, –z + 1; (f) x + 1/2, –y + 1/2, z.

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Figure 1 (a) View of the coordination environments of Zn(II) ions in 1. All hydrogen atoms were omitted for clarity. Symmetry codes: (a) –x + 1, y, –z + 5/2; (b) x + 1/2, –y + 1/2, z + 1/2; (c) –x + 1/2, –y + 1/2, –z + 2; (d) x, –y, z – 1/2; (e) –x, –y, –z + 2. (b) The dinuclear [Zn2(datrz)2] unit. (c) The 3D framework of 1. (d) Schematic representation of the (3,4,6)-connected topological network for 1.

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Figure 2 (a) View of the coordination environments of Zn(II) ions in 2. All hydrogen atoms were omitted for clarity. Symmetry codes: (a) x, –y + 1, z; (b) –x – 1, y, –z; (c) –x – 1, –y + 1, –z; (d) –x, y, –z + 1; (e) –x – 1/2, –y + 1/2, –z + 1; (f) x + 1/2, –y + 1/2, z. (b) Paddle wheel shaped dinuclear [Zn2(COO)4] unit. (c) The dinuclear [Zn2(datrz)2] unit. (d) The 3D framework of 2. (d) Schematic representation of the (4,6)-connected topological network for 2.

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Fig. 3. The PXRD patterns (a) for compound 1 and (b) for compound 2. The TG curves (c) for compound 1 and (d) for compound 2.

Figure 4 (a) The luminescent emission spectra for compounds 1 and 2 in the solid state at room temperature. (b) The luminescent emission spectra of free ligands (H3bpt, H4bptc and Hdatrz).

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(1) Organic carboxylate tuned two different Zn(II) compounds. (2) Compound 1 features a rinodal (3, 4, 6)-connected topological network, and compound 2 features a binodal (4, 6)-connected topological network. (3) These two compounds exhibit intense luminescence at room temperature.