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Synthesis, structure and properties of a novel 3D pentanuclear [Zn5(OH)2]8 + cluster-based (3,4,11)-connected coordination polymer
Synthesis, structure and properties of a novel 3D pentanuclear [Zn 5 (OH)2 ]8 + cluster-based (3,4,11)-connected coordination polymer Wei-Qiu Kan, Shi-Zheng Wen, Yu-He Kan, Hua-You Hu, Lin Yang, Dan Li PII: DOI: Reference:
S1387-7003(15)30070-8 doi: 10.1016/j.inoche.2015.08.026 INOCHE 6096
To appear in:
Inorganic Chemistry Communications
Received date: Revised date: Accepted date:
13 May 2015 24 June 2015 29 August 2015
Please cite this article as: Wei-Qiu Kan, Shi-Zheng Wen, Yu-He Kan, Hua-You Hu, Lin Yang, Dan Li, Synthesis, structure and properties of a novel 3D pentanuclear [Zn5 (OH)2 ]8 + cluster-based (3,4,11)-connected coordination polymer, Inorganic Chemistry Communications (2015), doi: 10.1016/j.inoche.2015.08.026
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, structure and properties of a novel 3D pentanuclear
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[Zn5(OH)2]8+ cluster-based (3,4,11)-connected coordination polymer
Wei-Qiu Kana, Shi-Zheng Wena,b,*, Yu-He Kana, Hua-You Hua, Lin Yanga, Dan
Jiangsu Province Key Laboratory for Chemistry of Low-Dimensional Materials,
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a
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Lia
School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huaian a
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223300, People’s Republic of China
Huaian Key Laboratory of Functional Materials for Informatics, School of Physics
and Electronic Electrical Engineering, Huaiyin Normal University, Huaian 223300,
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* Correspondence author
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People’s Republic of China
E-mail: [email protected] (S. Wen)
CE
Tel : +86 517 83525663
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Fax: +86 517 83525663
ABSTRACT
A novel coordination polymer based on the multidentate N-donor ligand 1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole (3,3'-tmbpt) and 1,2,4,5-benzenetetracarboxylate anion (btec), namely, [Zn5(3,3'-tmbpt)(btec)2(OH)2] (1), has been synthesized hydrothermally. Compound 1 displays a rare 3D (3,4,11)-connected framework based on a [Zn5(OH)2]8+ cluster. The optical band gap and photoluminescent property of compound 1 have been studied.
Keywords: Pentanuclear cluster; highly connected; coordination polymer; optical band gap; photoluminescence 1
ACCEPTED MANUSCRIPT
Coordination polymers (CPs) have provoked significant interest in recent years because of their diverse structures and various applications in the fields of sensors
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[1,2], catalysts [3,4], nonlinear optics [5,6], and so on. Out of the large number of CPs, highly connected structures (the number of connections ≥ 8) have attracted particular
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attention because of their robust framework stabilities and remarkable surface areas [7-10]. However, the design and synthesis of highly connected structures remains a
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challenge because of the limited coordination number of single metal ion and the steric hindrance of the organic ligands.
and
multidentate
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Our previous work demonstrated that the combination of polycarboxylate anions N-donor
ligands
1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(pyridyl)-1,2,4-triazole (tmbpt) can construct CPs with highly connected structures [11-14]. The polycarboxylate anions can chelate
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metal ions into metal clusters, which can increase the connectivity number of the nodes in the structure. The multidentate N-donor ligands tmbpt can extend the metal
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clusters into highly connected structures.
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In this work, we report a (3,4,11)-connected CP synthesized by the assembly of 1,2,4,5-benzenetetracarboxylate
anion
(btec,
scheme
(3,3'-tmbpt,
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1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole
S1),
scheme 1) and Zn(II) ion under hydrothermal condition [15]. This compound has been characterized by single-crystal X-ray diffraction analysis [16], infrared spectra (IR), elemental analysis and thermogravimetric analysis (TGA). The optical band gap and photoluminescent property of the compound have also been studied.
Scheme 1. The structures of H4btec and 3,3'-tmbpt.
Compound 1 displays a rare 3D (3,4,11)-connected framework based on a [Zn5(OH)2]8+ cluster. As shown in Fig. 1, the asymmetric unit of 1 consists of five Zn(II) ions, one 3,3'-tmbpt ligand, two btec anions and two hydroxyl groups. Zn1, Zn2 and Zn3 are six-coordinated in distorted octahedral coordination geometries, but 2
ACCEPTED MANUSCRIPT their coordination environments are different. Zn1 is coordinated by two nitrogen atoms from two different 3,3'-tmbpt ligands and four oxygen atoms from two individual btec anions and one hydroxyl group. Zn2 is coordinated by six oxygen
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atoms from four different btec anions and two hydroxyl groups. However, Zn3 is coordinated by one nitrogen atom from one 3,3'-tmbpt ligand and five oxygen atoms
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from three distinct btec anions and one hydroxyl group. Zn4 is four-coordinated by four oxygen atoms from three different btec anions and one hydroxyl group. Zn5 is
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five-coordinated by five oxygen atoms from four distinct btec anions and one hydroxyl group. The Zn-N bond lengths range from 2.146(7) to 2.240(7) Å, and the
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Zn-O distances are in the range of 1.941(5)-2.339(5) Å. The Zn-N and Zn-O bond lengths are in the normal ranges as other Zn(II)-containing CPs [17,18]. Zn1 to Zn5 are connected by two hydroxyl groups to generate a pentanuclear [Zn5(OH)2]8+ cluster.
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Each [Zn5(OH)2]8+ cluster is surrounded by eleven organic ligands (three 3,3'-tmbpt ligands and eight btec anions), each 3,3'-tmbpt ligand is connected to three
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[Zn5(OH)2]8+ clusters, and each btec anion is linked by four [Zn5(OH)2]8+ clusters. In this way, the [Zn5(OH)2]8+ clusters are connected by the btec anions to form a 3D
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framework containing large channels with the dimension of about 11.6 ×11.6 Å2 (Fig. 2a and Fig. S2). The 3,3'-tmbpt ligands, which are located in the channels in pairs,
2b).
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link the Zn(II) ions in tridentate modes to form a complicated 3D framework (Fig.
Fig. 1. View of the coordination environments of Zn(II) ions. Symmetry codes: #1 x 1/2, -y + 1/2, z + 1/2; #2 –x + 5/2, y + 1/2, -z + 1/2; #3 –x + 3, -y, -z + 1; #4 –x + 7/2, y 1/2, -z + 1/2; #5 x - 1, y, z; #6 –x + 5/2, y - 1/2, -z + 1/2; #7 x + 1/2, -y - 1/2, z + 1/2; #8 –x + 3, -y - 1, -z + 1. Fig. 2. (a) View of the 3D framework formed by the [Zn5(OH)2]8+ clusters and the btec anions. (b) View of the 3D framework formed by the [Zn5(OH)2]8+ clusters, btec anions and 3,3'-tmbpt ligands.
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ACCEPTED MANUSCRIPT From a topological point of view, each 3,3'-tmbpt ligand can be considered as a 3-connected node, each btec anion can be viewed as a 4-connected node, and each [Zn5(OH)2]8+ cluster can be regarded as a 11-connected node (Fig. S1). Thus, the
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complicated 3D framework can be simplified as a (3,4,11)-connected framework with a Schläfli symbol of (42·6)(44·62)2(426·627·82) (Fig. 3). It should be noted that although
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more and more highly connected frameworks have been reported in recent years, most of the reported ones are based on the even highly connected nodes, and only few
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examples of highly connected frameworks containing odd highly connected nodes,
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such as 11-connected nodes, have been reported [19-23].
Fig. 3. (a) View of the 3D (3,4,11)-connected framework with a Schläfli symbol of
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(42·6)(44·62)2(426·627·82).
CPs containing d10 metal centers have attractive photoluminescent properties
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[24,25]. Therefore, in this work, the solid-state photoluminescent properties of 3,3'-tmbpt, H4btec and compound 1 were studied at room temperature. The emission
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peaks of 3,3'-tmbpt and H4btec are located at 441 nm [12] and 380 nm [26], respectively. These emission peaks may be caused by the π*–n or π*–π transition as
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previously reported [11-13]. When excited at 339 nm, compound 1 shows emission peak at 381 nm (Fig. 4). This emission should originate from the btec anion, because similar peak also appears for the H4btec.
Fig. 4. Solid state excitation (left) and emission (right) spectra of compound 1 at room temperature.
In order to investigate the conductivity of compound 1, diffuse reflection spectrum data for powder samples of 1 were collected to obtain the band gap (Eg). Fig. S3 shows the F versus E plot. The values of F were converted from the reflectivity according to the Kubelka−Munk function: F = (1 − R)2/(2R) (R is the reflectivity at a certain wavelength) [27]. The intersection point between the energy axis at F = 0 and 4
ACCEPTED MANUSCRIPT the line extrapolated from the linear portion of the adsorption edge in the plot can be considered as the band gap [27]. The Eg of compound 1 is 3.87 eV, which is in the
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normal range as observed in other CPs [12,28].
The thermal stability of compound 1 has been studied by TGA. The experiment
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was carried out under N2 atmosphere at a heating rate of 10 °C/min. The TGA curve (Fig. S4) indicated that there was no chemical decomposition up to 370 °C. The
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framework decomposed in the temperature range of 370-558°C. The remaining
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weight is 34.8%, corresponding to the formation of ZnO (observed: 35.0%).
In conclusion, a novel 3D (3,4,11)-connected framework based on the multidentate N-donor ligand 3,3'-tmbpt and the polycarboxylate anion btec has been prepared
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hydrothermally. Compound 1 represents a rare case of CP based on the odd highly connected nodes. In addition, the luminescent spectra indicate that compound 1 emits
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blue light at room temperature. The diffuse reflection spectrum indicates that
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compound 1 may be a potential wide band gap semiconductive material.
Acknowledgments
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This work was supported by the National Science Foundation of China (21401063, 21403081 and 21202058), the Jiangsu Province NSF (Grant Nos. BK20140452 and BK20140453), and Open Fund of Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials (Project No. JSKC13137).
Appendix A. Supplementary material CCDC 1058119 contains the supplementary crystallographic data for this paper. The 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 this article can be found, in the online version, at doi:???
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[15] A mixture of 3,3'-tmbpt (0.03 g, 0.1 mmol), Zn(CH3COO)2·2H2O (0.066 g, 0.3
mmol), H4btec (0.038 g, 0.15 mmol), NaOH (0.024 g, 0.6 mmol) and water (8 mL)
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was placed in a Teflon reactor. The mixture was heated at 130 °C for 3 days. After cooling to ambient temperature, colorless crystals of 1 were obtained in a 62% yield. Anal. calcd for C35H18Zn5N8O18, (Mr = 1165.42): C, 36.07; H, 1.56; N, 9.61. Found: C, 36.19; H, 1.66; N, 9.52%. IR data (KBr, cm−1): 3447 (m), 1609 (s), 1538 (m), 1488 (m), 1424 (s), 1368 (s), 1318 (m), 1276 (w), 1197 (w), 1134 (m), 1040 (w), 875 (w), 820 (w), 754 (w), 700 (w), 676 (w), 616 (w), 544 (w), 519 (w). [16] Crystallographic diffraction data for compound 1 was recorded on an Oxford
Diffraction Gemini R CCD with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) at 293 K. Absorption correction was applied using multi-scan technique. The hydrogen atoms on C atoms were generated geometrically and refined using a riding model with d(C-H) = 0.93-0.97 Å and Uiso = 1.2Ueq (C). The hydrogen atoms of hydroxyl groups were located from different Fourier maps and 7
ACCEPTED MANUSCRIPT refined as riding atoms with d(O-H) = 0.76-0.90 Å and Uiso = 1.5Ueq (O). Crystal data for 1: C35H18Zn5N8O18, M = 1165.42, monoclinic, space group P21/n, T = 293(2) K, a = 15.0988(6) Å, b = 15.5888(5) Å, c = 17.1086(7) Å, β = 112.926(5)°,
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V = 3708.8(2) Å3, Z = 4, Dc = 2.087 g·cm−3, a total of 15084 reflections were collected, 6770 of which were unique (Rint = 0.0566), final R1 = 0.0663 for I>2σ(I),
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wR2 = 0.1514 for all data, GOOF = 1.069.
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ACCEPTED MANUSCRIPT on blue emitters with small singlet–triplet splitting and ambipolar transport property, Adv. Funct. Mater. 23 (2013) 2672–2680. [25] G. De Santis, L. Fabbrizzi, M. Licchelli, A. Poggi, A. Taglietti, Molecular
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Figure captions
Fig. 1. View of the coordination environments of Zn(II) ions. Symmetry codes: #1 x -
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1/2, -y + 1/2, z + 1/2; #2 –x + 5/2, y + 1/2, -z + 1/2; #3 –x + 3, -y, -z + 1; #4 –x + 7/2, y 1/2, -z + 1/2; #5 x - 1, y, z; #6 –x + 5/2, y - 1/2, -z + 1/2; #7 x + 1/2, -y - 1/2, z + 1/2; #8
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–x + 3, -y - 1, -z + 1.
Fig. 2. (a) View of the 3D framework formed by the [Zn5(OH)2]8+ clusters and the btec anions. (b) View of the 3D framework formed by the [Zn5(OH)2]8+ clusters, btec 10
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anions and 3,3'-tmbpt ligands.
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(42·6)(44·62)2(426·627·82).
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Fig. 3. (a) View of the 3D (3,4,11)-connected framework with a Schläfli symbol of
Fig. 4. Solid state excitation (left) and emission (right) spectra of compound 1 at room temperature.
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Graphical abstract
A novel coordination polymer with (3,4,11)-connected structure has been prepared
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gap have also been studied.
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under hydrothermal condition, where its photoluminescent property and optical band
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Highlights 1. Compound 1 displays a highly connected structure. 2. The N-donor ligand is multidentate. 3. The photoluminescent property of the compound has been studied. 4. The optical band gap of the compound has been studied.
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S1387-7003(15)30070-8 doi: 10.1016/j.inoche.2015.08.026 INOCHE 6096
To appear in:
Inorganic Chemistry Communications
Received date: Revised date: Accepted date:
13 May 2015 24 June 2015 29 August 2015
Please cite this article as: Wei-Qiu Kan, Shi-Zheng Wen, Yu-He Kan, Hua-You Hu, Lin Yang, Dan Li, Synthesis, structure and properties of a novel 3D pentanuclear [Zn5 (OH)2 ]8 + cluster-based (3,4,11)-connected coordination polymer, Inorganic Chemistry Communications (2015), doi: 10.1016/j.inoche.2015.08.026
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, structure and properties of a novel 3D pentanuclear
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[Zn5(OH)2]8+ cluster-based (3,4,11)-connected coordination polymer
Wei-Qiu Kana, Shi-Zheng Wena,b,*, Yu-He Kana, Hua-You Hua, Lin Yanga, Dan
Jiangsu Province Key Laboratory for Chemistry of Low-Dimensional Materials,
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a
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Lia
School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huaian a
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223300, People’s Republic of China
Huaian Key Laboratory of Functional Materials for Informatics, School of Physics
and Electronic Electrical Engineering, Huaiyin Normal University, Huaian 223300,
PT
* Correspondence author
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People’s Republic of China
E-mail: [email protected] (S. Wen)
CE
Tel : +86 517 83525663
AC
Fax: +86 517 83525663
ABSTRACT
A novel coordination polymer based on the multidentate N-donor ligand 1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole (3,3'-tmbpt) and 1,2,4,5-benzenetetracarboxylate anion (btec), namely, [Zn5(3,3'-tmbpt)(btec)2(OH)2] (1), has been synthesized hydrothermally. Compound 1 displays a rare 3D (3,4,11)-connected framework based on a [Zn5(OH)2]8+ cluster. The optical band gap and photoluminescent property of compound 1 have been studied.
Keywords: Pentanuclear cluster; highly connected; coordination polymer; optical band gap; photoluminescence 1
ACCEPTED MANUSCRIPT
Coordination polymers (CPs) have provoked significant interest in recent years because of their diverse structures and various applications in the fields of sensors
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[1,2], catalysts [3,4], nonlinear optics [5,6], and so on. Out of the large number of CPs, highly connected structures (the number of connections ≥ 8) have attracted particular
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attention because of their robust framework stabilities and remarkable surface areas [7-10]. However, the design and synthesis of highly connected structures remains a
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challenge because of the limited coordination number of single metal ion and the steric hindrance of the organic ligands.
and
multidentate
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Our previous work demonstrated that the combination of polycarboxylate anions N-donor
ligands
1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(pyridyl)-1,2,4-triazole (tmbpt) can construct CPs with highly connected structures [11-14]. The polycarboxylate anions can chelate
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metal ions into metal clusters, which can increase the connectivity number of the nodes in the structure. The multidentate N-donor ligands tmbpt can extend the metal
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clusters into highly connected structures.
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In this work, we report a (3,4,11)-connected CP synthesized by the assembly of 1,2,4,5-benzenetetracarboxylate
anion
(btec,
scheme
(3,3'-tmbpt,
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1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(3-pyridyl)-1,2,4-triazole
S1),
scheme 1) and Zn(II) ion under hydrothermal condition [15]. This compound has been characterized by single-crystal X-ray diffraction analysis [16], infrared spectra (IR), elemental analysis and thermogravimetric analysis (TGA). The optical band gap and photoluminescent property of the compound have also been studied.
Scheme 1. The structures of H4btec and 3,3'-tmbpt.
Compound 1 displays a rare 3D (3,4,11)-connected framework based on a [Zn5(OH)2]8+ cluster. As shown in Fig. 1, the asymmetric unit of 1 consists of five Zn(II) ions, one 3,3'-tmbpt ligand, two btec anions and two hydroxyl groups. Zn1, Zn2 and Zn3 are six-coordinated in distorted octahedral coordination geometries, but 2
ACCEPTED MANUSCRIPT their coordination environments are different. Zn1 is coordinated by two nitrogen atoms from two different 3,3'-tmbpt ligands and four oxygen atoms from two individual btec anions and one hydroxyl group. Zn2 is coordinated by six oxygen
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atoms from four different btec anions and two hydroxyl groups. However, Zn3 is coordinated by one nitrogen atom from one 3,3'-tmbpt ligand and five oxygen atoms
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from three distinct btec anions and one hydroxyl group. Zn4 is four-coordinated by four oxygen atoms from three different btec anions and one hydroxyl group. Zn5 is
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five-coordinated by five oxygen atoms from four distinct btec anions and one hydroxyl group. The Zn-N bond lengths range from 2.146(7) to 2.240(7) Å, and the
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Zn-O distances are in the range of 1.941(5)-2.339(5) Å. The Zn-N and Zn-O bond lengths are in the normal ranges as other Zn(II)-containing CPs [17,18]. Zn1 to Zn5 are connected by two hydroxyl groups to generate a pentanuclear [Zn5(OH)2]8+ cluster.
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Each [Zn5(OH)2]8+ cluster is surrounded by eleven organic ligands (three 3,3'-tmbpt ligands and eight btec anions), each 3,3'-tmbpt ligand is connected to three
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[Zn5(OH)2]8+ clusters, and each btec anion is linked by four [Zn5(OH)2]8+ clusters. In this way, the [Zn5(OH)2]8+ clusters are connected by the btec anions to form a 3D
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framework containing large channels with the dimension of about 11.6 ×11.6 Å2 (Fig. 2a and Fig. S2). The 3,3'-tmbpt ligands, which are located in the channels in pairs,
2b).
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link the Zn(II) ions in tridentate modes to form a complicated 3D framework (Fig.
Fig. 1. View of the coordination environments of Zn(II) ions. Symmetry codes: #1 x 1/2, -y + 1/2, z + 1/2; #2 –x + 5/2, y + 1/2, -z + 1/2; #3 –x + 3, -y, -z + 1; #4 –x + 7/2, y 1/2, -z + 1/2; #5 x - 1, y, z; #6 –x + 5/2, y - 1/2, -z + 1/2; #7 x + 1/2, -y - 1/2, z + 1/2; #8 –x + 3, -y - 1, -z + 1. Fig. 2. (a) View of the 3D framework formed by the [Zn5(OH)2]8+ clusters and the btec anions. (b) View of the 3D framework formed by the [Zn5(OH)2]8+ clusters, btec anions and 3,3'-tmbpt ligands.
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ACCEPTED MANUSCRIPT From a topological point of view, each 3,3'-tmbpt ligand can be considered as a 3-connected node, each btec anion can be viewed as a 4-connected node, and each [Zn5(OH)2]8+ cluster can be regarded as a 11-connected node (Fig. S1). Thus, the
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complicated 3D framework can be simplified as a (3,4,11)-connected framework with a Schläfli symbol of (42·6)(44·62)2(426·627·82) (Fig. 3). It should be noted that although
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more and more highly connected frameworks have been reported in recent years, most of the reported ones are based on the even highly connected nodes, and only few
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examples of highly connected frameworks containing odd highly connected nodes,
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such as 11-connected nodes, have been reported [19-23].
Fig. 3. (a) View of the 3D (3,4,11)-connected framework with a Schläfli symbol of
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(42·6)(44·62)2(426·627·82).
CPs containing d10 metal centers have attractive photoluminescent properties
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[24,25]. Therefore, in this work, the solid-state photoluminescent properties of 3,3'-tmbpt, H4btec and compound 1 were studied at room temperature. The emission
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peaks of 3,3'-tmbpt and H4btec are located at 441 nm [12] and 380 nm [26], respectively. These emission peaks may be caused by the π*–n or π*–π transition as
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previously reported [11-13]. When excited at 339 nm, compound 1 shows emission peak at 381 nm (Fig. 4). This emission should originate from the btec anion, because similar peak also appears for the H4btec.
Fig. 4. Solid state excitation (left) and emission (right) spectra of compound 1 at room temperature.
In order to investigate the conductivity of compound 1, diffuse reflection spectrum data for powder samples of 1 were collected to obtain the band gap (Eg). Fig. S3 shows the F versus E plot. The values of F were converted from the reflectivity according to the Kubelka−Munk function: F = (1 − R)2/(2R) (R is the reflectivity at a certain wavelength) [27]. The intersection point between the energy axis at F = 0 and 4
ACCEPTED MANUSCRIPT the line extrapolated from the linear portion of the adsorption edge in the plot can be considered as the band gap [27]. The Eg of compound 1 is 3.87 eV, which is in the
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normal range as observed in other CPs [12,28].
The thermal stability of compound 1 has been studied by TGA. The experiment
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was carried out under N2 atmosphere at a heating rate of 10 °C/min. The TGA curve (Fig. S4) indicated that there was no chemical decomposition up to 370 °C. The
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framework decomposed in the temperature range of 370-558°C. The remaining
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weight is 34.8%, corresponding to the formation of ZnO (observed: 35.0%).
In conclusion, a novel 3D (3,4,11)-connected framework based on the multidentate N-donor ligand 3,3'-tmbpt and the polycarboxylate anion btec has been prepared
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hydrothermally. Compound 1 represents a rare case of CP based on the odd highly connected nodes. In addition, the luminescent spectra indicate that compound 1 emits
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blue light at room temperature. The diffuse reflection spectrum indicates that
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compound 1 may be a potential wide band gap semiconductive material.
Acknowledgments
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This work was supported by the National Science Foundation of China (21401063, 21403081 and 21202058), the Jiangsu Province NSF (Grant Nos. BK20140452 and BK20140453), and Open Fund of Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials (Project No. JSKC13137).
Appendix A. Supplementary material CCDC 1058119 contains the supplementary crystallographic data for this paper. The 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 this article can be found, in the online version, at doi:???
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ACCEPTED MANUSCRIPT B.L.Chen, A Rare Uninodal 9-Connected Metal−Organic Framework with Permanent Porosity, Cryst. Growth Des. 10 (2010) 2372-2375. [11] W.Q. Kan, J. Yang, Y.Y. Liu, J.F. Ma, A series of coordination polymers based on a
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[15] A mixture of 3,3'-tmbpt (0.03 g, 0.1 mmol), Zn(CH3COO)2·2H2O (0.066 g, 0.3
mmol), H4btec (0.038 g, 0.15 mmol), NaOH (0.024 g, 0.6 mmol) and water (8 mL)
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was placed in a Teflon reactor. The mixture was heated at 130 °C for 3 days. After cooling to ambient temperature, colorless crystals of 1 were obtained in a 62% yield. Anal. calcd for C35H18Zn5N8O18, (Mr = 1165.42): C, 36.07; H, 1.56; N, 9.61. Found: C, 36.19; H, 1.66; N, 9.52%. IR data (KBr, cm−1): 3447 (m), 1609 (s), 1538 (m), 1488 (m), 1424 (s), 1368 (s), 1318 (m), 1276 (w), 1197 (w), 1134 (m), 1040 (w), 875 (w), 820 (w), 754 (w), 700 (w), 676 (w), 616 (w), 544 (w), 519 (w). [16] Crystallographic diffraction data for compound 1 was recorded on an Oxford
Diffraction Gemini R CCD with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) at 293 K. Absorption correction was applied using multi-scan technique. The hydrogen atoms on C atoms were generated geometrically and refined using a riding model with d(C-H) = 0.93-0.97 Å and Uiso = 1.2Ueq (C). The hydrogen atoms of hydroxyl groups were located from different Fourier maps and 7
ACCEPTED MANUSCRIPT refined as riding atoms with d(O-H) = 0.76-0.90 Å and Uiso = 1.5Ueq (O). Crystal data for 1: C35H18Zn5N8O18, M = 1165.42, monoclinic, space group P21/n, T = 293(2) K, a = 15.0988(6) Å, b = 15.5888(5) Å, c = 17.1086(7) Å, β = 112.926(5)°,
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V = 3708.8(2) Å3, Z = 4, Dc = 2.087 g·cm−3, a total of 15084 reflections were collected, 6770 of which were unique (Rint = 0.0566), final R1 = 0.0663 for I>2σ(I),
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wR2 = 0.1514 for all data, GOOF = 1.069.
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ACCEPTED MANUSCRIPT on blue emitters with small singlet–triplet splitting and ambipolar transport property, Adv. Funct. Mater. 23 (2013) 2672–2680. [25] G. De Santis, L. Fabbrizzi, M. Licchelli, A. Poggi, A. Taglietti, Molecular
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(HDBU)4[δ-Mo8O26], J. Solid State Chem. 179 (2006) 3615-3627. [28] J. Guo, J.F. Ma, B. Liu, W.Q. Kan, J. Yang, A Series of 2D and 3D Metal-Organic
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Figure captions
Fig. 1. View of the coordination environments of Zn(II) ions. Symmetry codes: #1 x -
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1/2, -y + 1/2, z + 1/2; #2 –x + 5/2, y + 1/2, -z + 1/2; #3 –x + 3, -y, -z + 1; #4 –x + 7/2, y 1/2, -z + 1/2; #5 x - 1, y, z; #6 –x + 5/2, y - 1/2, -z + 1/2; #7 x + 1/2, -y - 1/2, z + 1/2; #8
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–x + 3, -y - 1, -z + 1.
Fig. 2. (a) View of the 3D framework formed by the [Zn5(OH)2]8+ clusters and the btec anions. (b) View of the 3D framework formed by the [Zn5(OH)2]8+ clusters, btec 10
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anions and 3,3'-tmbpt ligands.
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(42·6)(44·62)2(426·627·82).
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Fig. 3. (a) View of the 3D (3,4,11)-connected framework with a Schläfli symbol of
Fig. 4. Solid state excitation (left) and emission (right) spectra of compound 1 at room temperature.
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Graphical abstract
A novel coordination polymer with (3,4,11)-connected structure has been prepared
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gap have also been studied.
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under hydrothermal condition, where its photoluminescent property and optical band
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ACCEPTED MANUSCRIPT
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Highlights 1. Compound 1 displays a highly connected structure. 2. The N-donor ligand is multidentate. 3. The photoluminescent property of the compound has been studied. 4. The optical band gap of the compound has been studied.
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