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Two novel 2D metal–organic frameworks based on biphenyl-2,2′,6,6′-tetracarboxylic acid: Synthesis, structures and luminescent properties
Inorganic Chemistry Communications 16 (2012) 92–94
Contents lists available at SciVerse ScienceDirect
Inorganic Chemistry Communications journal homepage: www.elsevier.com/locate/inoche
Two novel 2D metal–organic frameworks based on biphenyl-2,2′,6,6′-tetracarboxylic acid: Synthesis, structures and luminescent properties Zhi Yang a, Jia Liu b, Xiao-Qiang Liang b, Yuan Jiang b, Ting Zhang b, Bing Han a, Fu-Xing Sun b,⁎, Lei Liu a,⁎ a b
Teaching and Research Center of Chemistry of College of Chemistry,Jilin University,Changchun 130021, China State Key laboratory of Inorganic Synthesis & Preparative Chemistry, Jilin University, Changchun 130012, China
a r t i c l e
i n f o
Article history: Received 23 September 2011 Accepted 1 December 2011 Available online 8 December 2011 Keywords: Biphenyl-2,2′,6,6′-tetracarboxylic acid Luminescent properties
a b s t r a c t Two novel metal–organic frameworks (MOFs) assembled from H4BPTC, {[Co2(BPTC)(H2O)4(DMF)2]2H2O} 1, {[Mn2(BPTC)(H2O)4(DMF)2]2H2O} 2, (H4BPTC = biphenyl-2,2′,6,6′-tetracarboxylic acid, DMF = N,Ndimethylformamide) have been obtained under hydrothermal conditions, and structurally characterized by single-crystal X-ray diffraction. The results reveal that compounds 1 and 2 are isostructural except the different metal centers, exhibiting a 2D layer structure with 4–4 net. 1 and 2 are also characterized by elemental analysis, IR spectra, TGA analysis and PXRD. The luminescent properties of 1 and 2 in solid state are discussed. © 2011 Elsevier B.V. All rights reserved.
The field of metal–organic coordination polymers continues to move forward at an explosive pace driven, not only by their potential applications in gas storage, ion-exchange, magnetism, ferroelectrics, catalysis, nonlinear optics, and molecular sensing [1–6], but also their esthetic architectures and fascinating topologies, such as rectangular grids, brick walls, herringbones, ladders, rings, boxes, diamondoids, and honeycombs [7–10]. To establish these molecular structures multicarboxylate ligands have been proven to be excellent candidates owing to their diversified coordination modes and interesting structures [11]. In the construction of novel metal–organic frameworks (MOFs), polycarboxylate ligands, such as biphenyl-3,3′,4,4′-tetracarboxylic acid [11–20], biphenyl-3,3′,5,5′-tetracarboxylic acid [21–24], biphenyl2,3′,3,4′-tetracarboxylic acid [25], biphenyl-2,2′,4,4′-tetracarboxylic acid [26,27], biphenyl-2,5,2′,5′-tetracarboxylic acid [28], and biphenyl2,2′,6,6′-tetracarboxylic acid [29–34] have been used. Nevertheless, we are more curious about biphenyl-2,2′,6,6′-tetracarboxylic acid (H4BPTC), which is chosen to prepare novel coordination polymers in view of its following characteristics: (1) it can be regarded not only as hydrogenbonding acceptors but also as hydrogen-bonding donors, depending upon the number of deprotonated carboxylic groups [11]; (2) as a rotatable ligand, two phenyl rings can rotate around the C\C single bond, which could increase the potential possibility to form helical and chiral structures [35,36] (Scheme 1). With the above considerations in mind, we chose H4BPTC as ligand and synthesized two novel MOFs,{[Co2(BPTC)(H2O)4(DMF)2] 2H2O} 1 and {[Mn2(BPTC)(H2O)4(DMF)2]2H2O} 2 under hydrothermal conditions. To the best of our knowledge, no examples of 2D
⁎ Corresponding authors. E-mail address: [email protected] (F.-X. Sun). 1387-7003/$ – see front matter © 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2011.12.003
MOFs have been made only by the ligand H4BPTC. In addition, the photoluminescent properties of compounds 1 and 2 have been investigated in solid state. Single-crystal X-ray analysis reveals that compounds 1 and 2 are isostructural except the different metal centers. These compounds are self-assembled from the H4BPTC with Co (II) and Mn (II). Hence, only the structure of compound 1 is described in detail here. The Xray diffraction studies indicate that compound 1 crystallizes in monoclinic crystal system, space group C2/c. In the asymmetric unit of 1, there are one Co (II) atom, one half H4BPTC ligand, one terminal DMF, two terminal water, and one solvated water. As shown in Fig. 1, two Co (II) atoms have different coordination environments. Co1 has an octahedral coordination sphere, being surrounded by six oxygen atoms: two from H4BPTC ligands, two from terminal water and two from terminal DMF. Co2 is coordinated by four oxygen atoms from terminal water and two oxygen atoms from H4BPTC ligands. The ligands link the Co1 (II) ions to form 1D linear chain
Scheme 1. Structure of H4BPTC.
Z. Yang et al. / Inorganic Chemistry Communications 16 (2012) 92–94
Fig. 1. Local coordination environments of Co1 and Co2 in 1. All the hydrogen atoms are omitted for clarity. Symmetry codes, a: − x + 2,y, − z + 1/2; b: − x + 2, − y + 2, − z; c: x + 2,y + 1, − z + 1/2; d: − x + 2,y − 1, − z + 1/2.
(Fig. 2(a)), then Co2 (II) ions connect the 1D chains to give a 2D sheet (Fig. 2(b)). After topology analysis, the 2D sheet gives a 4–4 net with a schlafli symbol (4·4·4·4) (Fig. 2(c)). Powder XRD patterns of compounds 1 and 2 and their simulated XRD patterns are shown in supporting information (Fig. S1 and S2). The diffraction peaks on the pattern of as-synthesized sample correspond well in position with those in the simulated pattern, suggesting that the product is pure single phase.
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To characterize the thermal stability of compounds 1 and 2, thermogravimetric analysis (TGA) study was carried out between 40 and 800 °C under nitrogen. The TG curve of compound 1 (Fig. S3) shows the first weight loss of 16.52% from 83 to 190 °C, corresponding to the loss of lattice water molecules and coordinated water molecules (calcd: 15.47%), and followed by a weight loss of 20.45% in the range of 190 to 371 °C consistent with the removal terminal DMF molecules (calcd: 20.92%). The resulting residue remains about 20.45% (calcd: 21.52%) after the complete decomposition of the organic ligands. TGA study of 2 suggests an initial weight loss of 15.47% (calcd: 15.65%) between 83 and 155 °C, corresponding to the mass loss of the terminal water molecules and guest water molecules. Further increase in temperature results in a weight loss of 20.46% (calcd: 21.12%) at 155–364 °C, which could correspond the loss of terminal DMF molecule. The total weight loss is and finished at about 387 °C (Fig. S4). The luminescent properties of compounds 1, 2 and the free ligand H4BPTC have been carried out in the solid state at room temperature under the same situation. As shown in Fig. 3, compounds 1and 2 display the emission maxima at 377 nm when excited at 234 nm. The free ligand exhibits emission maxima at 420 nm upon excitation at 234 nm. Both of the two compounds are blue-shifted with respect to the free ligand H4BPTC, which can likely be assigned to ligandcentered p–p* electronic transitions. In summary, we first obtained two 2D MOFs (compounds 1 and 2) constructed only with the ligand H4BPTC under hydrothermal conditions. Compounds 1 and 2 are isostructural except different metal centers, showing 2D layer structures with 4–4 net. The TGA analysis,
Fig. 2. (a) 1D chain constructed from Co1(II) ions and H4BPTC in Compound 1; (b) 2D layer; (c) schematic representation of the 2D 4,4-c net.
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Z. Yang et al. / Inorganic Chemistry Communications 16 (2012) 92–94
[12]
[13]
[14]
[15]
[16]
[17]
[18] Fig. 3. Solid-state luminescent spectrum of the ligand H4BPTC (a,a'), compound 1(b,b') and compound 2(c,c') at room temperature. [19]
PXRD and luminescent properties of 1 and 2 were also determined in solid state at room temperature. These two compounds demonstrate that the polycarboxylate ligands play important roles in producing novel frameworks and topologies of the coordination complexes.
[20]
[21] [22]
Acknowledgment [23]
We are grateful for the financial support of National Basic Research Program of China (973 Program, grant no. 2012CB821700), Major International (Regional) Joint Research Project of NSFC (grant no. 21120102034) and NSFC (grant no. 20831002).
[24]
Appendix A. Supplementary material
[25]
Supplementary data to this article can be found online at doi:10. 1016/j.inoche.2011.12.003.
[26]
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Contents lists available at SciVerse ScienceDirect
Inorganic Chemistry Communications journal homepage: www.elsevier.com/locate/inoche
Two novel 2D metal–organic frameworks based on biphenyl-2,2′,6,6′-tetracarboxylic acid: Synthesis, structures and luminescent properties Zhi Yang a, Jia Liu b, Xiao-Qiang Liang b, Yuan Jiang b, Ting Zhang b, Bing Han a, Fu-Xing Sun b,⁎, Lei Liu a,⁎ a b
Teaching and Research Center of Chemistry of College of Chemistry,Jilin University,Changchun 130021, China State Key laboratory of Inorganic Synthesis & Preparative Chemistry, Jilin University, Changchun 130012, China
a r t i c l e
i n f o
Article history: Received 23 September 2011 Accepted 1 December 2011 Available online 8 December 2011 Keywords: Biphenyl-2,2′,6,6′-tetracarboxylic acid Luminescent properties
a b s t r a c t Two novel metal–organic frameworks (MOFs) assembled from H4BPTC, {[Co2(BPTC)(H2O)4(DMF)2]2H2O} 1, {[Mn2(BPTC)(H2O)4(DMF)2]2H2O} 2, (H4BPTC = biphenyl-2,2′,6,6′-tetracarboxylic acid, DMF = N,Ndimethylformamide) have been obtained under hydrothermal conditions, and structurally characterized by single-crystal X-ray diffraction. The results reveal that compounds 1 and 2 are isostructural except the different metal centers, exhibiting a 2D layer structure with 4–4 net. 1 and 2 are also characterized by elemental analysis, IR spectra, TGA analysis and PXRD. The luminescent properties of 1 and 2 in solid state are discussed. © 2011 Elsevier B.V. All rights reserved.
The field of metal–organic coordination polymers continues to move forward at an explosive pace driven, not only by their potential applications in gas storage, ion-exchange, magnetism, ferroelectrics, catalysis, nonlinear optics, and molecular sensing [1–6], but also their esthetic architectures and fascinating topologies, such as rectangular grids, brick walls, herringbones, ladders, rings, boxes, diamondoids, and honeycombs [7–10]. To establish these molecular structures multicarboxylate ligands have been proven to be excellent candidates owing to their diversified coordination modes and interesting structures [11]. In the construction of novel metal–organic frameworks (MOFs), polycarboxylate ligands, such as biphenyl-3,3′,4,4′-tetracarboxylic acid [11–20], biphenyl-3,3′,5,5′-tetracarboxylic acid [21–24], biphenyl2,3′,3,4′-tetracarboxylic acid [25], biphenyl-2,2′,4,4′-tetracarboxylic acid [26,27], biphenyl-2,5,2′,5′-tetracarboxylic acid [28], and biphenyl2,2′,6,6′-tetracarboxylic acid [29–34] have been used. Nevertheless, we are more curious about biphenyl-2,2′,6,6′-tetracarboxylic acid (H4BPTC), which is chosen to prepare novel coordination polymers in view of its following characteristics: (1) it can be regarded not only as hydrogenbonding acceptors but also as hydrogen-bonding donors, depending upon the number of deprotonated carboxylic groups [11]; (2) as a rotatable ligand, two phenyl rings can rotate around the C\C single bond, which could increase the potential possibility to form helical and chiral structures [35,36] (Scheme 1). With the above considerations in mind, we chose H4BPTC as ligand and synthesized two novel MOFs,{[Co2(BPTC)(H2O)4(DMF)2] 2H2O} 1 and {[Mn2(BPTC)(H2O)4(DMF)2]2H2O} 2 under hydrothermal conditions. To the best of our knowledge, no examples of 2D
⁎ Corresponding authors. E-mail address: [email protected] (F.-X. Sun). 1387-7003/$ – see front matter © 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2011.12.003
MOFs have been made only by the ligand H4BPTC. In addition, the photoluminescent properties of compounds 1 and 2 have been investigated in solid state. Single-crystal X-ray analysis reveals that compounds 1 and 2 are isostructural except the different metal centers. These compounds are self-assembled from the H4BPTC with Co (II) and Mn (II). Hence, only the structure of compound 1 is described in detail here. The Xray diffraction studies indicate that compound 1 crystallizes in monoclinic crystal system, space group C2/c. In the asymmetric unit of 1, there are one Co (II) atom, one half H4BPTC ligand, one terminal DMF, two terminal water, and one solvated water. As shown in Fig. 1, two Co (II) atoms have different coordination environments. Co1 has an octahedral coordination sphere, being surrounded by six oxygen atoms: two from H4BPTC ligands, two from terminal water and two from terminal DMF. Co2 is coordinated by four oxygen atoms from terminal water and two oxygen atoms from H4BPTC ligands. The ligands link the Co1 (II) ions to form 1D linear chain
Scheme 1. Structure of H4BPTC.
Z. Yang et al. / Inorganic Chemistry Communications 16 (2012) 92–94
Fig. 1. Local coordination environments of Co1 and Co2 in 1. All the hydrogen atoms are omitted for clarity. Symmetry codes, a: − x + 2,y, − z + 1/2; b: − x + 2, − y + 2, − z; c: x + 2,y + 1, − z + 1/2; d: − x + 2,y − 1, − z + 1/2.
(Fig. 2(a)), then Co2 (II) ions connect the 1D chains to give a 2D sheet (Fig. 2(b)). After topology analysis, the 2D sheet gives a 4–4 net with a schlafli symbol (4·4·4·4) (Fig. 2(c)). Powder XRD patterns of compounds 1 and 2 and their simulated XRD patterns are shown in supporting information (Fig. S1 and S2). The diffraction peaks on the pattern of as-synthesized sample correspond well in position with those in the simulated pattern, suggesting that the product is pure single phase.
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To characterize the thermal stability of compounds 1 and 2, thermogravimetric analysis (TGA) study was carried out between 40 and 800 °C under nitrogen. The TG curve of compound 1 (Fig. S3) shows the first weight loss of 16.52% from 83 to 190 °C, corresponding to the loss of lattice water molecules and coordinated water molecules (calcd: 15.47%), and followed by a weight loss of 20.45% in the range of 190 to 371 °C consistent with the removal terminal DMF molecules (calcd: 20.92%). The resulting residue remains about 20.45% (calcd: 21.52%) after the complete decomposition of the organic ligands. TGA study of 2 suggests an initial weight loss of 15.47% (calcd: 15.65%) between 83 and 155 °C, corresponding to the mass loss of the terminal water molecules and guest water molecules. Further increase in temperature results in a weight loss of 20.46% (calcd: 21.12%) at 155–364 °C, which could correspond the loss of terminal DMF molecule. The total weight loss is and finished at about 387 °C (Fig. S4). The luminescent properties of compounds 1, 2 and the free ligand H4BPTC have been carried out in the solid state at room temperature under the same situation. As shown in Fig. 3, compounds 1and 2 display the emission maxima at 377 nm when excited at 234 nm. The free ligand exhibits emission maxima at 420 nm upon excitation at 234 nm. Both of the two compounds are blue-shifted with respect to the free ligand H4BPTC, which can likely be assigned to ligandcentered p–p* electronic transitions. In summary, we first obtained two 2D MOFs (compounds 1 and 2) constructed only with the ligand H4BPTC under hydrothermal conditions. Compounds 1 and 2 are isostructural except different metal centers, showing 2D layer structures with 4–4 net. The TGA analysis,
Fig. 2. (a) 1D chain constructed from Co1(II) ions and H4BPTC in Compound 1; (b) 2D layer; (c) schematic representation of the 2D 4,4-c net.
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Z. Yang et al. / Inorganic Chemistry Communications 16 (2012) 92–94
[12]
[13]
[14]
[15]
[16]
[17]
[18] Fig. 3. Solid-state luminescent spectrum of the ligand H4BPTC (a,a'), compound 1(b,b') and compound 2(c,c') at room temperature. [19]
PXRD and luminescent properties of 1 and 2 were also determined in solid state at room temperature. These two compounds demonstrate that the polycarboxylate ligands play important roles in producing novel frameworks and topologies of the coordination complexes.
[20]
[21] [22]
Acknowledgment [23]
We are grateful for the financial support of National Basic Research Program of China (973 Program, grant no. 2012CB821700), Major International (Regional) Joint Research Project of NSFC (grant no. 21120102034) and NSFC (grant no. 20831002).
[24]
Appendix A. Supplementary material
[25]
Supplementary data to this article can be found online at doi:10. 1016/j.inoche.2011.12.003.
[26]
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