Synthesis, characterization and electrochemical properties of two metal cobalt complexes constructed by tetradentate carboxylic

Accepted Manuscript Synthesis, characterization and electrochemical properties of two metal cobalt complexes constructed by tetradentate carboxylic Lingshu Meng, Lun Zhao, Changjiang Zhao, Xin Liu PII:

S0022-2860(18)31330-9

DOI:

https://doi.org/10.1016/j.molstruc.2018.11.026

Reference:

MOLSTR 25855

To appear in:

Journal of Molecular Structure

Received Date: 24 July 2018 Revised Date:

6 November 2018

Accepted Date: 8 November 2018

Please cite this article as: L. Meng, L. Zhao, C. Zhao, X. Liu, Synthesis, characterization and electrochemical properties of two metal cobalt complexes constructed by tetradentate carboxylic, Journal of Molecular Structure (2018), doi: https://doi.org/10.1016/j.molstruc.2018.11.026. 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

Synthesis, Characterization and Electrochemical

2

Properties of Two Metal Cobalt Complexes

3

Constructed by Tetradentate Carboxylic

4

Lingshu Meng, Lun Zhao* , Changjiang Zhao, Xin Liu

College of Chemistry, Changchun Normal University, Changchun, 130032, Jilin, P. R. China; *Correspondence: E-mail: [email protected]; Tel.: +86-431-86168903(L Zhao)

Abstract: Two new three-dimensional coordination polymers (CPs), [Co(H2L2-)(bibp)]·2H2O (1) and [Co2(L4-)(bib)2]·8H2O (2) (bib = 1,4-diimidazolyl butane, bibp = 4,4'-diimidazolylbiphenyl) been

solvo-/hydrothermal

prepared

based

on

tetradentate

ligand

SC

have

5,5-(pentane-1,4-diylbis(oxy))diisophthalic acid (H4L). In CP 1, two chains was formed by Co(II) ion with ligands H2L2- and bibp, respectively, then two chains form into a 2D layer through Co(II) ion. The same two 2D layers constitute a AB layer by inverted manner, then a 3D

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5 6 7 8 9 10 11 12 13 14 15 16 17

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1

framework was obtained through the combination of AB layer by π-π stacking. In CP 2, Co (II) atoms are connected by neighboring carboxylic acid ligands L4- to generate 2D layer, then being further connected with nitrogen-containing ligand bib, the 2D layer form a 3D supramolecular network through Co(II) ions. In addition, the electrochemical behaviors of complexes 1 and 2 have been reported.

Keywords: Coordination polymers; Tetradentate carboxylic ligands; Electrochemical behaviors

20

1. Introduction

Great attention has been made in the study of metal-organic coordination polymers (CPs) during recent years, owing to their versatile architectures[1,2,3] and potential applications in

EP

heterogeneous catalysis[4,5], gas adsorption[6,7], magnetism[8,9] and luminescence[10,11]. However, it is still a quite challenging task for synthetic CPs with certain properties. Because crystallization was a complicated process and affected by many factors, such as the selection of

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21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37

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18 19

the metal centers, organic ligands, and experimental conditions. Because of the diversity of coordination, tetradentate carboxylic can be react with

transition metal ions and nitrogen-containing ligands to form a variety of spatial topologies. J. Yang

and

colleagues

designed

and

synthesized

three

new

CPs

by

terphenyl-3,3',5,5'-tetracarboxylic acid and zinc nitrate. All complexes exhibit 3D 4-connected networks and good luminescence properties that can be acted as potential luminescent probes or sensors for detecting small organic molecules and toxic substances[12]. Z. Zhu and co-workers

synthesized

six

new

5,5'-(1,4/1,3-phenylenebis(methoxy))diisophthalic

coordination acid

and

polymers

different

ligands

with under

solvothermal conditions, and indicated that complexes exhibit antiferromagnetic couplings between carboxyl-bridging Co(II) ions by variable-temperature magnetic studies[13]. In this article, new metal cobalt complexes have been synthesized under hydrothermal/

ACCEPTED MANUSCRIPT solvothermal conditions, namely, [Co(H2L2-)(bibp)]·2H2O (1) and [Co2(L4-)(bib)2]·8H2O (2). The structures of these complexes are characterized by X-ray crystallography, IR spectra, TG, and elemental analysis in detail. In addition, we probed the electrochemical behavior of 1 and 2 at glassy carbon cathodes with the aid of cyclic voltammetry. COOH

HOOC O

O

COOH

HOOC

5,5’-(pentane-1,4diylbis(oxy)) diisophthalic acid (H4L) N

N N

N

N

N

4,4'-bis(imidazol-1-yl)biphenyl (bibp)

1,4-bis(imidazolyl)butane (bib)

44

2 Experimental section

45

2.1 Materials and methods

61 62 63 64 65 66 67

All of the chemicals were reagent grade quality obtained from merchant sources and used without further purification. IR spectra were carried out a Thermo Nicolet Avatar 360 IR spectrometer with KBr Pellets. Elemental analyses (C, H and N) were measured on

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Perkin-Elmer 240C analyzer. TGA was performed on a Perkin-Elmer TG-7 analyzer heated from 25 to 700 °C under nitrogen. Powder X-ray diffraction (PXRD) data were recorded on D2 PHASER

A26-X1

XRD

diffractometer

of

Bruker

Corporation.

All

electrochemical

measurements were carried out by a DF-2002 electrochemical workstation at 25 °C.

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2.2 Synthesis of[Co(H2L2-)(bibp)]·2H2O (1)

A mixture of CoCl2·6H2O (0.0237 g, 0.1 mmol), bibp ligand (0.0286 g, 0.1 mmol), H4L (0.0432 g, 0.1 mmol) and H2O (10 mL) was transferred to a 20 mL Parr Teflon-lined stainless steel vessel and kept at 160 °C for 3 days. After slow cooling to room temperature, purple

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54 55 56 57 58 59 60

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Scheme 1 Molecular structure of ligands

42 43

53

N

SC

N

46 47 48 49 50 51 52

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38 39 40 41

crystals of 1 were obtained (yield: ca. 63% based on H4L ligand). Anal. Calc. for C39H34CoN4O12(%): C, 57.86; H, 4.23; N, 6.92. Found: C, 58.71; H,4.32; N, 6.73. IR (KBr, cm−1): 3447(s), 3122(s), 2938(s), 1705(m),1636(s), 1518(m), 1458(s), 1124(s), 1064(m), 1382(m), 1275(m), 841(s), 795(s).

2.3 Synthesis of[Co2(L4-)(bib)2]·8H2O (2) A mixture of CoCl2·6H2O (0.0237 g, 0.1 mmol), bib ligand (0.0190 g, 0.1 mmol), H4L (0.0432 g, 0.1 mmol), DMF (8 mL) and H2O (2 mL) was transferred to a 20 mL Parr Teflon-lined stainless steel vessel and kept at 80 °C for 3 days. After slow cooling to room temperature, purple crystals of 2 were obtained (yield: ca. 59% based on H4L ligand). Anal. Calc. for C41H60Co2N8O18(%):C, 45.99; H, 5.65; N, 10.46. Found: C, 45.32; H, 5.59; N, 10.33. IR (KBr, cm−1): 3447 (s), 2938 (s),1704 (m), 1605 (s), 1518 (w), 1550(w), 1124(m), 1063 (m), 1382 (m), 1312 (s),840

ACCEPTED MANUSCRIPT (s), 821 (s).

O M

O

M

O

O

O

O

O

O

HO

O

O

M

M

a

O

O

M

b

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2.4 X-ray crystallography

X-ray single-crystal diffraction data of all complexes were collected on a Rigaku SCX-mini diffractometer single-crystal X-ray diffraction data were collected on a Bruker SMART APEXⅡCCD diffractometer with Mo-Kα radiation (λ = 0.71073 Å) by ω scan mode. All the structures were solved by Direct Method of SHELXS-97. The coordinates of non-hydrogen were shown in Table 1.

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atoms were determined by the anisotropy of the atoms. The crystallographic data measured Table1. Crystal data and structure refinement for 1 and 2

Compound 1

Compound2

1857351

1857352

Molecular Formula

C39H34CoN4O12

C41H60Co2N8O18

Fw

809.63

1070.83

Crystal system

Triclinic

Monoclinic

Space group

P-1

P2(1)/n

a/ A

10.1554

17.7303

b/ A

11.9594

17.0357

c/ A

15.8024

18.0262

α/(°)

98.896

90

β/(°)

101.966

109.062

γ/(°)

102.393

90

V/nm3

1793.5(4)

5146.2(5)

CCDC No.

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72 73 74 75 76 77 78

O

Scheme 2 Crystallographically established coordination modes of the carboxylic groups in compounds (a,b)

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71

O

O

O

70

O M

O

RI PT

HO

SC

68 69

ACCEPTED MANUSCRIPT 2

4

Dc/(g⋅cm−3)

1.499

1.382

F(000)

838

2240

GOF on F2

1.046

1.044

R1/wR2[ I>2σ(I)]

0.0781, 0.2312

0.0808, 0.2454

R1/wR2 (all data)

0.1143, 0.2665

0.1325, 0.2908

79

3.Results and discussion

80

3.1 Structure description of 1

100 101 102

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the triclinic crystal system, P-1 space group. The asymmetric unit contains one crystallographically independent Co(II) ion, one bibp ligand, one carboxylic acid H2L2- ligand and two uncoordinated H2O molecules (Fig. 1a, the uncoordinated H2O molecules do not

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shown). In asymmetric structural units, the Co(II) ion with two carboxylic O atoms from two H2L2- ligands and two nitrogen atoms from two bibp ligands, forming a twisty tetrahedron geometry. The two carboxyl groups of the ligand H2L2- are bridged by monodentate coordination, and the remaining two carboxyl groups are uncoordinated (as show in Scheme 2a). The distances of Co-O bonds range from 1.981(19) to 1.985(16) Å, and the Co-N bonds range from 2.047(19) to 2.06(2) Å. In this polymer, two chains was formed by Co(II) ion with ligands H2L2- and bibp, respectively, then two chains form into a 2D layer through Co(II) ion

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(Fig. 1b). Based on the above connection mode, each Co(II) ion connects two carboxylate ligands (H2L2-) and two nitrogen-containing ligands (bibp), can be simplified as a 4-connected node. Thus the 2D layer can be described as an uninodal 4-connected framework with topological structure. The same two 2D layers constitute a AB layer by inverted manner (Fig. 1c left), then a 3D framework was obtained through the combination of AB layer by π-π stacking, the distance between the two layers is 3.624 Å (Fig. 1d).

EP

99

The X-ray crystallographic analysis shows that the coordination polymer 1 crystallizes in

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81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98

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Z

107 108 109 110 111 112 113 114 115 116 117 118

through the combination with Co (II) ion. (c) View of 3D net topology structure composed of ABAB layers. (d) View of 3D net structure by π-π stacking .

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106

Fig. 1 (a) The coordination environment of the Co(II) ions in 1. (b) Two chains form into a 2D layer

3.2 Structure description of 2

Single crystal X-ray diffraction analysis shows that compound 2 crystallizes in a P2(1)/n

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103 104 105

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SC

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space group, with two crystallographically independent Co(II) ions, one carboxylic acid L4ligand, two bib ligands and eight uncoordinated H2O molecules in the asymmetric unit. As shown in Fig. 2a, both two Co(II) ions are four-coordinated by two carboxylic O atoms from two L4- ligands and two nitrogen atoms from two bib ligands to constitute a distorted tetrahedron geometry. In the asymmetric units, two carboxyl groups of the ligand L4constitute the same coordination mode, and they are bridged by monodentate coordination (as show in Scheme 2b). Within the framework, the distances of Co-O bonds range from 1.961(3) to 1.995(3)Å, and the Co-N bonds range from 2.004(4) to 2.042(4) Å. In compound 2, Co (II) atoms are connected by neighboring carboxylic acid ligands L4- to generate 2D layer, then being further connected with nitrogen-containing ligand bib, the 2D layer form a 3D supramolecular network through Co(II) ions (Fig. 2bcd). As a result of the spatial nature of a

ACCEPTED MANUSCRIPT single network, three identical networks interpenetrate each other to form a triple interpenetrating 3D supramolecular network (Fig. 2e).

AC C

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SC

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119 120

121 122 123 124

Fig. 2 (a) The coordination environment of the Co(II) ions in 2. (b) View of 2D layer structure. (c) View of 3D net structure. (d) View of 3D topology. (e) View of 3-fold interpenetrated 3D net framework.

4. PXRD and thermogravimetric analysis (TGA)

ACCEPTED MANUSCRIPT In order to confirm the phase purity of these complexes, PXRD of complexes 1 and 2 were recorded at room temperature. As shown in Figure 3, the peak positions of the theoretical and experimental PXRD patterns are in good agreement with each other, which clearly indicates the high purity and homogeneity of these samples.

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125 126 127 128

compound 1

compound 2

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a

0

10

20

30

40

2theta

50

0

10

20

b 30

40

50

2theta

Fig.3 Experimental (a) and simulated (b) PXRD patterns of compound 1 and 2

The thermostabilities of the frameworks were characterized by TGA (Fig. 4). The thermal

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stability properties of complexes 1 and 2 were performed under N2 atmosphere at a ramp rate of 10°C/min and the temperature ranged from 25 °C to 700 °C. For 1, an obviously decomposing at the range of 25-160°C with 2.35% (calcd. 4.46%) occurred because of the release of two free H2O molecules; the framework then began decomposed after 320°C. The final residue was 35.60%. The first weight loss of compound 2 occurred at the range of 25-95°C

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with 8.92% (calcd. 13.41%) due to the full release of free water molecule, and the framework began decomposed after 330°C. The final residue was 42.04%. In all, complexes 1 and 2 show good thermostabilities under 300°C.

AC C

129 130 131 132 133 134 135 136 137 138 139 140

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b

a

ACCEPTED MANUSCRIPT

100

60

2

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weight(%)

80

40

1

20

0

300

4000

Temperature( C)

500

600

700

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5.Electrochemical properties

In order to study the redox properties of the Co(II) complexes, the 1 and 2 bulk-modified carbon paste electrode (1-CPE and 2-CPE) becomes the optimal choice due to their insolubility in water and common organic solvents. The cyclic voltammetry studies of the 1-CPE and 2-CPE were performed on 1 M H2SO4 aqueous solution are recorded in Fig. 5. It can clearly observe a redox couple at the 1-CPE and 2-CPE, which could be ascribed to the redox of

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Co(III)/Co(II), respectively. The mean peak potential E1/2 = (Epa + Epc)/2 is 531.5 mV (50 mV/s) for 1, 525.5 mV for 2 (50 mV/s).

-5

compound 1

-6

8.0x10

-6

I/A

AC C

4.0x10

-5

8.0x10

EP

1.2x10

compound 2 -5

4.0x10

0.0

I/A

143 144 145 146 147 148 149

200

Fig. 4 The TGA diagrams of complexes 1 and 2

141 142

100

SC

0

0.0

-6

-4.0x10

-5

-4.0x10

-6

-8.0x10

-5

-5

-1.2x10

0.2

0.4

0.6

Potential/V

150

-8.0x10

0.8

1.0

0.0

0.2

0.4

0.6

0.8

1.0

Potential/V

Fig.5 Cyclic voltammograms of 1-CPE and 2-CPE in 1 M H2SO4 aqueous solution at 50 mV/s

ACCEPTED MANUSCRIPT Scan rates effect on the electrochemical behavior of the 1-CPE and 2-CPE were

151 152 153 154 155 156 157 158

investigated in 1 M H2SO4 solution. As shown in Fig. 6, with the scan rates increasing from 30 to 200 mV/s, the peak potentials changed gradually: the cathodic peak potentials moved to the negative direction and the homologous anodic peak potentials shifted to the positive direction. This signified that the redox processes are proliferation-confined because the peak currents increased linearly with the square root of the scan rates in inset of Fig. 6. Also, the CV maps of Co(II) ions.

-4

3.0x10

-5

1.4x10

-5

1.2x10

-5

-4

R =0.98696

1.0x10

1.2x10 -4 1.0x10 -5 8.0x10 -5 6.0x10

-4

2.5x10

2

-5

4.0x10

-4

1.4x10

1/2

ip,a=-1.8103E-6+3.53283E-5*V

-5

2.5x10

-5

2.0x10

-5

1.5x10

-4

2.0x10

Ipa Ipc

6.0x10

-6

4.0x10

0.0

1.5x10

1/2

-5

-2.0x10

-6

2

1.0x10

-4.0x10

R =0.96320

-4.0x10 -5 -6.0x10 -5 -8.0x10

-4

2

R =0.53509

-6

1/2

ip,c=1.31402E-5-2.52569E-4*V

-5

ip,c=-3.4022E-6-4.81844E-6*V

-2.0x10

Ipa Ipc

-5

4.0x10 -5 2.0x10 0.0

-4

-6

2.0x10

2

R =0.99226

-4

-1.0x10

-6

-6.0x10

0.15

0.20

0.25

0.30

0.35

0.40

5.0x10

V

I/A

1.0x10

0.15

-5

0.45

1/2

-5 -6

I/A

5.0x10 0.0

0.20

0.25

0.30

0.35

0.40

0.45

1/2

V

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3.0x10

-6

I/A

-5

I/A

-6

8.0x10

-5

3.5x10

1/2

ip,a=-2.48358E-5+3.658E-4*V

SC

-5

4.5x10

RI PT

1-CPE and 2-CPE are variant due to the different coordination environments and modes of

0.0 -5

-6

30mV/s 50mV/s 70mV/s 90mV/s 100mV/s 130mV/s 150mV/s 170mV/s 200mV/s

-5.0x10

-5

-1.0x10

-5

-1.5x10

1-CPE

-5

-2.0x10

-5

-2.5x10

-5

-3.0x10

-5

-3.5x10

30mV/s 50mV/s 70mV/s 90mV/s 110mV/s 130mV/s 150mV/s 170mV/s 200mV/s

-5.0x10

-4

-1.0x10

-4

-1.5x10

2-CPE

-4

-2.0x10

-4

-2.5x10

-4

-3.0x10

0.2

0.4

0.6

0.8

0.0

0.2

0.4

0.6

0.8

Potential/V

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Potential/V

1.0

Fig.6 Cyclic voltammograms of 1-CPE and 2-CPE in 1 M H2SO4 aqueous solution at different scan rates

160

(ranging from 30 to 200 mV/s). Two inserts show the plot of the cathodic peak currents vs. scan rates.

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6.Conclusions

In this investigation, we have reported the synthesis and characterization of two Co(II) complexes with nitrogen-containing ligands. The polymer was analyzed using PXRD, IR and

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162 163 164 165 166 167 168 169 170 171 172 173 174 175

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159

TGA. In brief, for polymer 1, Co (II) ion form into two chains respectively by combining with ligands H4L and bibp, then two chains form into a 2D layer through the combination with Co (II) ion. For polymer 2, Co (II) atoms are connected by neighboring carboxylic acid ligands H4L to generate 2D layer, then being further connected with nitrogen-containing ligand bib ligand, the 2D layer form a 3D supramolecular network through Co(II) ions. The TGA results disclose that these coordination polymers are quite stable. In particular, the anhydrous

framework of 1 has excellent thermotolerance up to 363 °C. In addition, the

electrochemical behavior of the CP 1 and 2 prove that they may be good candidates for potential applications in electrochemical fields. Notes The authors declare no competing financial interest.

1.0

ACCEPTED MANUSCRIPT 176 177 178 179 180

Acknowledgements: The authors gratefully acknowledge the financial Supported by the

181

Appendix A. Supplementary material

182 183 184 185

CCDC 1857351.1857352 contain the supplementary crystallographic data for complexes 1-2

and The 13th Five Science and Technology Research of Jilin Province Department of Education (No. JJKH20181174KJ) and Graduate Education Innovation Fund project of Changchun

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Normal University(No. cscxy2018002).

respectively. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via WWW.ccdc.cam.ac.uk/data_request/cif. Supplementary data associated with

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this article can be found, in the online version, at http:

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(c) Y. Zhao, R. G. Li, L. C. Mu, C. Li. Cryst. Growth Des. 17 (2017) 2923. [11] (a) A. Garai, S. Sasmal, K. Biradha. Cryst. Growth Des. 16 (2016) 4457; (b) M. D. Allendorf, C. A. Bauer, R. K. Bhakta, R. J. T. Houk. Chem. Soc. Rev. 38 (2009) 1330;

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(c) Y. W. Dong, R. Q. Fan, X. M. Wang, P. Wang, H. J. Zhang, L. G. Wei, W. Chen, Y. L.Yang. Cryst. Growth Des. 16 (2016) 3366.

[12] J. Yang, L. L. Zhang, X. Q. Wang, R. M. Wang, F. N. Dai, D. F. Sun, RSC Adv. 77 (2015) 62982 [13] Z. Zhu, C. G. Xu, M. Wang, X. Zhang, H. Wang, Q. D. Luo, S. Y. Bi, Y. H. Fan. Cryst. Growth

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ACCEPTED MANUSCRIPT 1. Highlights
Tetradentate carboxylic ligand is a good building block.
The electrochemical behavior of Co(II) complexes was studied by cyclic voltammetry.
Two coordination polymers of metallic cobalt with 2D and 3D structures were

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synthesized by 5,5-(pentane-1,4-diylbis(oxy)) diisophthalic acid and two different nitrogen containing ligands.

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2. The Graphical Abstract