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A 2D brickwall architecture from a double-T-shaped ligand and hybrid coordinatively unsaturated copper: Synthesis, structure, and framework dynamic
Inorganic Chemistry Communications 12 (2009) 157–160
Contents lists available at ScienceDirect
Inorganic Chemistry Communications journal homepage: www.elsevier.com/locate/inoche
A 2D brickwall architecture from a double-T-shaped ligand and hybrid coordinatively unsaturated copper: Synthesis, structure, and framework dynamic Shengjun Deng, Ning Zhang *, Weiming Xiao, Chao Chen * Department of Chemistry, Nanchang University, Xuefu Road, No. 999, Nanchang 330031, PR China
a r t i c l e
i n f o
Article history: Received 12 October 2008 Accepted 2 December 2008 Available online 10 December 2008 Keywords: Coordination polymer Brickwall Double-T-shaped ligand Framework dynamic
a b s t r a c t A double-T-shaped ligand (H4BPTC) as the spacer has been first used to direct the assembly of a 2D coordination polymer with brickwall network topology, [Cu2(BPTC)(Im)4(H2O)(DMF)]n (1) (DMF = N,Ndimethylformamide, H4BPTC = Biphenyl-3,30 ,4,40 -tetracarboxylic acid, Im = imidazole), which exhibits an interesting framework dynamic upon de-/resolvation. Ó 2008 Elsevier B.V. All rights reserved.
The ‘‘node-and-spacer” approach has been the most effective synthetic approach to producing predictable architectures and topologies of coordination networks [1]. By this approach, coordination polymers bearing various aesthetical structures such as tube, brickwall, herringbone, and diamond, have been isolated [2]. Recently, particular attention has been devoted to the use of new suitably-tailored highly symmetrical ligands (spacers) that enable control of the structural motifs and/or introduce peculiar topological features into the solid-state products [2b,3,4]. Among them, T-shaped ligands with high symmetry have been extensively used to construct coordination networks, especially for brickwall, ladder and herringbone [4]. Inspired by above, we have focused on a multidentate ligand, biphenyl-3,30 ,4,40 -tetracarboxylic acid (H4BPTC), featuring a new double-T shape. Compared to T-shaped ligands, H4BPTC possesses similar geometric configuration, more rich coordination sites, and the potential to construct porous frameworks with larger pores owing to its extended length. Herein, we employed H4BPTC as the spacer to successfully construct a 2D brickwall architecture, namely [Cu2(BPTC)(Im)4(H2O)(DMF)]n (1), which exhibits an interesting framework dynamic upon de-/ resolvation. Blue bulk crystals of 1 were prepared in moderate yield (65%) by solvothermal reaction of Cu(OAc)2 H2O, H4BPTC, Im, HNO3, DMF and ethanol at 85 °C for 2 days [5]. The as-synthesized sample is not air-stable and undergoes the slow efflorescence process. Single-crystal X-ray structural analysis [6] reveals that 1 crystallizes in monoclinic, P21/n space group. Each asymmetric unit * Corresponding authors. E-mail addresses: [email protected] (N. Zhang), [email protected] (C. Chen). 1387-7003/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2008.12.002
(Fig. S1) contains two crystallographically independent copper(II) ions, one BPTC ligand, four Im ligands and one coordinated water molecule. It is notable that the two copper(II) ions exhibit unsaturated coordination numbers of 4 and 5, respectively, which is relatively rare among coordination polymers [7] and raises the possibility that 1 might have potential as a catalyst. Cu1 takes a four-coordinated square-planar mode, coordinated by two oxygen atoms from two BPTC ligands (O1 and O6A), and two nitrogen atoms from two Im ligands (N1 and N3). Cu2 adopts a five-coordinated square-pyramidal geometry, coordinated by two oxygen atoms from two BPTC ligands (O3A and O7), two nitrogen atoms from two Im ligands (N5 and N7), living the other one as terminal water oxygen atom (O200). As shown in Scheme 1, each BPTC ligand bridges four copper(II) ions in a l4-fashion to form a 2D brickwall network. Two carboxylate groups of the BPTC ligand extend horizontally and coordinate to two tetracoordinate copper(II) ions, while the other two remaining carboxylate groups extend vertically and coordinate to two pentacoordinate copper(II) ions upwards and downwards, respectively. Consequently, the whole BPTC ligand can be described as a trans double-T-shaped spacer. The simplest cyclic unit of the 2D-network is a rectangular grid with the dimensions 15.261 9.645 Å (based on the separation of the metal ions), consisting of four copper(II) ions and four BPTC ligands (Fig. 1). The tetracoordinate and pentacoordinate copper(II) ions alternately assembly into layers in rows. Furthermore, Im ligands binding to the pentacoordinate copper(II) ions are coplanar with the layer, whereas Im ligands binding to the tetracoordinate copper(II) ions perpendicularly standing up and down the layer. The crystal packing diagram of 1 is shown in Fig. 2. Parallel layers stack in an offset ABAB fashion, separated by Cu–Cu distance of 7.601 Å. The adjacent layers are related by a 21 axis. The stacked 2D
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Scheme 1. Schematic representation for the assembly of a 2D brickwall motif from double-T-shaped ligand (H4BPTC) and node (copper ion) (Blue arrows showing the coordination sites). (For interpretation of the references in color in this figure legend, the reader is referred to the web version of this article.)
layers are held together via strong interlayer hydrogen bond interactions between free carbonyl oxygen atoms of BPTC ligands in one layer and amine hydrogen atoms of the pendant Im ligands in a neighboring layer, resulting in a 3D network. The pendant Im ligands on adjacent layers are mutually interdigitated along the a axis, which leaves the channels running parallel to the a and b axes (Fig. 2 and Fig. S2), and free water and DMF molecules are stabilized in the channels by hydrogen bonds (Table S3).
2D-network materials have the potential to provide dynamic porous materials as they can adopt changes caused by external stimuli [8]. To investigate if the material is robust upon guest removal or exchange, its de-/resolvation was studied according to the thermal gravimetric analysis (TGA) results and X-ray powder diffraction (XRPD) patterns. The XRPD pattern of the as-prepared solid shows slightly different peak positions and intensities as compared with the simulated one from single-crystal X-ray diffrac-
Fig. 1. View of the 2D brickwall network structure of 1 (all the hydrogen atoms are omitted for clarity).
Fig. 2. (a) The ABAB molecular packing of 2D layers (red and blue balls representation of H2O and DMF, dashed lines representation of hydrogen bonds) and (b) Schematic representation for the offset packing of the adjacent layers in 1 down c axis. (For interpretation of the references in color in this figure legend, the reader is referred to the web version of this article.)
S. Deng et al. / Inorganic Chemistry Communications 12 (2009) 157–160
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Appendix A. Supplementary material CCDC 703849 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/data_request/cif. Supplementary data associated with this article can be found, in the online version, at doi:10.1016/ j.inoche.2008.12.002. References
Fig. 3. XRPD patterns: (a) simulated from single-crystal X-ray data, (b) assynthesized solid, (c) desolvated solid at 130 °C, (d) after resolvation of solid c, (e) desolvated solid at 160 °C and (d) after resolvation of solid e.
tion data of 1 (Fig. 3), implying a slight change in the layer distance resulted from efflorescence. TGA of 1 indicates that all guest molecules are removed by 120 °C and the framework decomposes above 150 °C (Fig. S3). So we heated the as-prepared solid at 130 °C in air for 24 h to completely lose the guest molecules. As shown in Fig. 3, the black-blue solid residue has almost featureless XRPD pattern, which indicates that it is very low crystalline or amorphous, resulting from the loss of guest molecules and probable collapse of the open frameworks [9]. However, when the desolvated solid was immersed in the mixture of DMF/ethanol (2:1, v/v) at room temperature for 3 days, the material recovered the original structure, as confirmed by comparing its XRPD pattern to the asprepared one (Fig. 3). The line and characteristic peaks widths of the resolvated solid increases significantly as compared to the asprepared solid, which is probably explained that some degradation might occur [9c]. In order to get more insight into the framework dynamic, another solid repeated above experiments at 160 °C. Interestingly, the de-/resolvation behavior is also partially reversible although the important characteristic peaks intensities of XRPD pattern of resolvation solid are weakened, and only few similar coordination polymers have been reported [10]. These facts clearly indicate that the de-/resolvation is reversible for the material, and the porous framework shows framework dynamic upon de-/resolvation. This type of reversible dynamic frameworks responding to guest molecules might find application in molecular separation or sensors [11]. In summary, using a double-T-shaped ligand, we have constructed the first 2D coordination polymer with brickwall network topology, which shows a framework dynamic driven by desolvation and resolvation. The structure reported here reveals an exciting new route to the construction of 2D brickwall architectures. Toward the successful design and synthesis of 2D molecular brickwall, we think that double-T-shaped ligands, as T-shaped spacers, might be suitable and promising for the construction of compounds with novel structures such as ladder, brickwall, herringbone and basket.
Acknowledgement This work was supported by the National Natural Science Foundation of China (No. 20701018) and the Natural Science Foundation of Jiangxi Province (No. 2007GZH2755).
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Contents lists available at ScienceDirect
Inorganic Chemistry Communications journal homepage: www.elsevier.com/locate/inoche
A 2D brickwall architecture from a double-T-shaped ligand and hybrid coordinatively unsaturated copper: Synthesis, structure, and framework dynamic Shengjun Deng, Ning Zhang *, Weiming Xiao, Chao Chen * Department of Chemistry, Nanchang University, Xuefu Road, No. 999, Nanchang 330031, PR China
a r t i c l e
i n f o
Article history: Received 12 October 2008 Accepted 2 December 2008 Available online 10 December 2008 Keywords: Coordination polymer Brickwall Double-T-shaped ligand Framework dynamic
a b s t r a c t A double-T-shaped ligand (H4BPTC) as the spacer has been first used to direct the assembly of a 2D coordination polymer with brickwall network topology, [Cu2(BPTC)(Im)4(H2O)(DMF)]n (1) (DMF = N,Ndimethylformamide, H4BPTC = Biphenyl-3,30 ,4,40 -tetracarboxylic acid, Im = imidazole), which exhibits an interesting framework dynamic upon de-/resolvation. Ó 2008 Elsevier B.V. All rights reserved.
The ‘‘node-and-spacer” approach has been the most effective synthetic approach to producing predictable architectures and topologies of coordination networks [1]. By this approach, coordination polymers bearing various aesthetical structures such as tube, brickwall, herringbone, and diamond, have been isolated [2]. Recently, particular attention has been devoted to the use of new suitably-tailored highly symmetrical ligands (spacers) that enable control of the structural motifs and/or introduce peculiar topological features into the solid-state products [2b,3,4]. Among them, T-shaped ligands with high symmetry have been extensively used to construct coordination networks, especially for brickwall, ladder and herringbone [4]. Inspired by above, we have focused on a multidentate ligand, biphenyl-3,30 ,4,40 -tetracarboxylic acid (H4BPTC), featuring a new double-T shape. Compared to T-shaped ligands, H4BPTC possesses similar geometric configuration, more rich coordination sites, and the potential to construct porous frameworks with larger pores owing to its extended length. Herein, we employed H4BPTC as the spacer to successfully construct a 2D brickwall architecture, namely [Cu2(BPTC)(Im)4(H2O)(DMF)]n (1), which exhibits an interesting framework dynamic upon de-/ resolvation. Blue bulk crystals of 1 were prepared in moderate yield (65%) by solvothermal reaction of Cu(OAc)2 H2O, H4BPTC, Im, HNO3, DMF and ethanol at 85 °C for 2 days [5]. The as-synthesized sample is not air-stable and undergoes the slow efflorescence process. Single-crystal X-ray structural analysis [6] reveals that 1 crystallizes in monoclinic, P21/n space group. Each asymmetric unit * Corresponding authors. E-mail addresses: [email protected] (N. Zhang), [email protected] (C. Chen). 1387-7003/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.inoche.2008.12.002
(Fig. S1) contains two crystallographically independent copper(II) ions, one BPTC ligand, four Im ligands and one coordinated water molecule. It is notable that the two copper(II) ions exhibit unsaturated coordination numbers of 4 and 5, respectively, which is relatively rare among coordination polymers [7] and raises the possibility that 1 might have potential as a catalyst. Cu1 takes a four-coordinated square-planar mode, coordinated by two oxygen atoms from two BPTC ligands (O1 and O6A), and two nitrogen atoms from two Im ligands (N1 and N3). Cu2 adopts a five-coordinated square-pyramidal geometry, coordinated by two oxygen atoms from two BPTC ligands (O3A and O7), two nitrogen atoms from two Im ligands (N5 and N7), living the other one as terminal water oxygen atom (O200). As shown in Scheme 1, each BPTC ligand bridges four copper(II) ions in a l4-fashion to form a 2D brickwall network. Two carboxylate groups of the BPTC ligand extend horizontally and coordinate to two tetracoordinate copper(II) ions, while the other two remaining carboxylate groups extend vertically and coordinate to two pentacoordinate copper(II) ions upwards and downwards, respectively. Consequently, the whole BPTC ligand can be described as a trans double-T-shaped spacer. The simplest cyclic unit of the 2D-network is a rectangular grid with the dimensions 15.261 9.645 Å (based on the separation of the metal ions), consisting of four copper(II) ions and four BPTC ligands (Fig. 1). The tetracoordinate and pentacoordinate copper(II) ions alternately assembly into layers in rows. Furthermore, Im ligands binding to the pentacoordinate copper(II) ions are coplanar with the layer, whereas Im ligands binding to the tetracoordinate copper(II) ions perpendicularly standing up and down the layer. The crystal packing diagram of 1 is shown in Fig. 2. Parallel layers stack in an offset ABAB fashion, separated by Cu–Cu distance of 7.601 Å. The adjacent layers are related by a 21 axis. The stacked 2D
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Scheme 1. Schematic representation for the assembly of a 2D brickwall motif from double-T-shaped ligand (H4BPTC) and node (copper ion) (Blue arrows showing the coordination sites). (For interpretation of the references in color in this figure legend, the reader is referred to the web version of this article.)
layers are held together via strong interlayer hydrogen bond interactions between free carbonyl oxygen atoms of BPTC ligands in one layer and amine hydrogen atoms of the pendant Im ligands in a neighboring layer, resulting in a 3D network. The pendant Im ligands on adjacent layers are mutually interdigitated along the a axis, which leaves the channels running parallel to the a and b axes (Fig. 2 and Fig. S2), and free water and DMF molecules are stabilized in the channels by hydrogen bonds (Table S3).
2D-network materials have the potential to provide dynamic porous materials as they can adopt changes caused by external stimuli [8]. To investigate if the material is robust upon guest removal or exchange, its de-/resolvation was studied according to the thermal gravimetric analysis (TGA) results and X-ray powder diffraction (XRPD) patterns. The XRPD pattern of the as-prepared solid shows slightly different peak positions and intensities as compared with the simulated one from single-crystal X-ray diffrac-
Fig. 1. View of the 2D brickwall network structure of 1 (all the hydrogen atoms are omitted for clarity).
Fig. 2. (a) The ABAB molecular packing of 2D layers (red and blue balls representation of H2O and DMF, dashed lines representation of hydrogen bonds) and (b) Schematic representation for the offset packing of the adjacent layers in 1 down c axis. (For interpretation of the references in color in this figure legend, the reader is referred to the web version of this article.)
S. Deng et al. / Inorganic Chemistry Communications 12 (2009) 157–160
159
Appendix A. Supplementary material CCDC 703849 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/data_request/cif. Supplementary data associated with this article can be found, in the online version, at doi:10.1016/ j.inoche.2008.12.002. References
Fig. 3. XRPD patterns: (a) simulated from single-crystal X-ray data, (b) assynthesized solid, (c) desolvated solid at 130 °C, (d) after resolvation of solid c, (e) desolvated solid at 160 °C and (d) after resolvation of solid e.
tion data of 1 (Fig. 3), implying a slight change in the layer distance resulted from efflorescence. TGA of 1 indicates that all guest molecules are removed by 120 °C and the framework decomposes above 150 °C (Fig. S3). So we heated the as-prepared solid at 130 °C in air for 24 h to completely lose the guest molecules. As shown in Fig. 3, the black-blue solid residue has almost featureless XRPD pattern, which indicates that it is very low crystalline or amorphous, resulting from the loss of guest molecules and probable collapse of the open frameworks [9]. However, when the desolvated solid was immersed in the mixture of DMF/ethanol (2:1, v/v) at room temperature for 3 days, the material recovered the original structure, as confirmed by comparing its XRPD pattern to the asprepared one (Fig. 3). The line and characteristic peaks widths of the resolvated solid increases significantly as compared to the asprepared solid, which is probably explained that some degradation might occur [9c]. In order to get more insight into the framework dynamic, another solid repeated above experiments at 160 °C. Interestingly, the de-/resolvation behavior is also partially reversible although the important characteristic peaks intensities of XRPD pattern of resolvation solid are weakened, and only few similar coordination polymers have been reported [10]. These facts clearly indicate that the de-/resolvation is reversible for the material, and the porous framework shows framework dynamic upon de-/resolvation. This type of reversible dynamic frameworks responding to guest molecules might find application in molecular separation or sensors [11]. In summary, using a double-T-shaped ligand, we have constructed the first 2D coordination polymer with brickwall network topology, which shows a framework dynamic driven by desolvation and resolvation. The structure reported here reveals an exciting new route to the construction of 2D brickwall architectures. Toward the successful design and synthesis of 2D molecular brickwall, we think that double-T-shaped ligands, as T-shaped spacers, might be suitable and promising for the construction of compounds with novel structures such as ladder, brickwall, herringbone and basket.
Acknowledgement This work was supported by the National Natural Science Foundation of China (No. 20701018) and the Natural Science Foundation of Jiangxi Province (No. 2007GZH2755).
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