Role of Temperature on Framework Dimensionality: Supramolecular

Communication pubs.acs.org/crystal

Role of Temperature on Framework Dimensionality: Supramolecular Isomers of Zn3(RCOO)8 Based Metal Organic Frameworks Sanjog S. Nagarkar, Abhijeet K. Chaudhari, and Sujit K. Ghosh* Department of Chemistry, Indian Institute of Science Education and Research (IISER), Pashan, Pune, Maharashtra 411021, India S Supporting Information *

ABSTRACT: Three new anionic metal organic frameworks, [Zn 1 . 5 (FDA) 2 (Me 2 NH 2 )]·xG (1), [Zn 3 (FDA) 4 (Me 2 NH 2 ) 2 ]·xG (2), and [Zn1.5(FDA)2(Me2NH2)]·xG (3) (FDAH2 = 2,5-furandicarboxylic acid, G = guest), were synthesized solvothermally via a temperature tuning strategy. Compound 1, synthesized at 90 °C, has a two-dimensional (2D) sheet structure, while 2 and 3, synthesized at 120 and 160 °C, respectively, have three-dimensional (3D) structures. Compound 2 has alternating hydrophobic and hydrophilic channels with pore dimensions ∼4.3 × 4.4 Å2 and ∼5.6 × 6.2 Å2, respectively. Compound 3 has only one type of pore with dimensions of ∼5.3 × 6.2 Å2. All three compounds have eight connected Zn3(RCOO)8 nodes as building units and are anionic, with dimethyl ammonium cations present inside the channels to balance charge. Compounds 1, 2, and 3 are supramolecular isomers with general formula [Zn1.5(FDA)2(Me2NH2)]n.

C

dimensionality of supramolecular isomers where no coordinated solvents are present will provide another new approach along the same line but has not been studied systematically. Herein we report three anionic porous MOFs synthesized solvothermally using Zn(II), FDA (FDAH2 = 2,5-furandicarboxylic acid) (1:1), and DMF at different reaction temperatures. [Zn1.5(FDA)2(Me2NH2)]·xG (1) is a 2D sheet structure, [Zn3(FDA)4(Me2NH2)2]·xG (2) is a 3D framework with alternating hydrophilic and hydrophobic channels, and [Zn1.5(FDA)2(Me2NH2)]·xG (3) is a 3D framework synthesized at 90, 120, and 160 °C, respectively. Compounds 1, 2, and 3 are supramolecular isomers with general formula [Zn1.5(FDA)2(Me2NH2)]n. To the best of our knowledge, this is a first example where simultaneous control over dimensionality and supramolecular isomerism is achieved via a temperature tuning strategy. The reaction at 90 °C yielded compound 1, having 2D anionic sheet structure running parallel to the ab plane (Figure.1). The asymmetric unit contains two types of Zn centers (Zn1 and Zn2 with full and half occupancy, respectively), two FDA ligands, and one dimethyl ammonium (DMA) cation. The Zn1 has a distorted octahedral geometry, and Zn2 has a perfect octahedral geometry and is sitting at the crystallographic centrosymmetric position, leading to a trinuclear cluster of three zinc ions (Zn1−Zn2−Zn1′). Zn1 and Zn2 are bridged by two monodentate bridging carboxylates and share a common vertex. Hexacoordination of Zn1 is completed by oxygens from two carboxylate groups via a bidentate coordination mode. This trimeric cluster unit with

onsiderable efforts have been devoted to the synthesis of metal organic frameworks (MOFs) or porous coordination polymers (PCPs) due to their potential application in catalysis, gas/solvent storage and separation, magnetism, ion exchange, drug delivery, luminescence, and the synthesis of compounds with new network topologies and novel architectures.1−15 The controlled synthesis of MOF for desired applications is still a great challenge, as the superstructure determines the properties associated with the materials. The supramolecular isomerism is receiving great attention in crystal engineering, as the isomers show the differential response to several physical properties, owing to their crystal packing, and thus, they are good candidates for smart functional materials.16,17d But the formation energy differences between the isomers are very less; hence, the prediction and control over particular structure becomes more difficult.17 It has been shown previously that solvent,18 pH,19 counteranion,20 concentration,21 template used,22 and reaction temperature23 are the factors which determine the overall structure of the material, and thus, the control over the solvothermally obtained product is very difficult. Understanding the role of the above factors in a self-assembly process is very important for the synthesis of target materials. The temperature is one of the important factors which governs the overall structure of the material. The temperature-tuning strategy is gaining interest, as the material with the novel topology, different dimensionality, and unique properties can be made with the same precursor and building unit. Systematic studies on the effect of temperature on the dimensionality of MOFs are very rare24 and was first explained by Cheetam et al.,25 where the effect of reaction temperature has been demonstrated by thermal desolvation and subsequent changes in the coordination environment. The effect of temperature on the structural © 2012 American Chemical Society

Received: December 9, 2011 Revised: January 6, 2012 Published: January 6, 2012 572

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Figure 1. Temperature dependent synthesis of porous compounds 1−3, and the changes in coordination environment of trimeric Zn units. (Color code: zinc, yellow; carbon, gray; oxygen, red. Hydrogen atoms and disordered solvents, and extra framework cations are omitted for clarity.).

connected Zn3(RCOO)8 nodes give rise to two types of channels along the a axis: one is hydrophobic, and the other one is hydrophilic. The hydrophobic channels have dimensions of ∼4.3 × 4.4 Å2 and are lined with the hydrocarbon part of the aromatic furan rings (Figure 2). The channel contains hydrogen

eight FDA ligands forms an eight connected Zn3(RCOO)8 node (Figure S2 of the Supporting Information). Each trinuclear cluster is connected with four such clusters by a pair of FDA ligands on each side and extending the 2D net in the ab plane. These 2D nets arrange one above the other, forming a pseudo-3D structure. The two extra-framework DMA cations and disordered solvents are present inside the pore formed between the four trimeric units. The PLATON26 analysis revealed that the porous structure was composed of large voids of 1035.8 Å3 that represent 45.2% per unit cell volume. The same reaction, when performed at 120 °C, gave compound 2, having a biporus 3D structure (Figure 1). The basic structure of compound 2 is similar to that of compound 1, but one of the carboxylate oxygens of one 2D sheet of compound 2 is now coordinated to the next 2D layer, leading to a 3D structure. Compound 2 contains two types of Zn trimeric units (Zn1−Zn3−Zn1′ and Zn2−Zn4−Zn2′). Interestingly, with increasing reaction temperature for compounds 1 and 2 from 90 to 120 °C, the distorted octahedral Zn (Zn1 and 1′) of the trimeric unit of compound 1 is now transformed to tetrahedral (Zn1 and 1′) in one unit and distorted trigonal bipyramidal (tbp) geometry (Zn2) in another unit in compound 2 (Figures 3 and S1). The Zn2 (Zn2′) and Zn4 are connected by (η1,μ2) bridging monodentate carboxylate oxygen. The remaining coordination of Zn2 with distorted trigonal bipyramidal coordination geometry is completed by the bidentate coordination mode of carboxylate, forming one type of trimeric unit. The Zn1 (Zn1) and Zn3 have similar coordination environments, only μ2 bridging carboxylate becomes bidentate bridging, and thus, the vertex sharing polyhedrons are now separated. The coordination environment of Zn1 is completed by monodentate carboxylate forming another trimeric unit. These two types of trimeric units are connected by eight FDA ligands, respectively, which connect other trimeric units, forming a 3D structure (Figures S3 and S4 of the Supporting Information). These two types of eight

Figure 2. Perspective view of the biporous framework of compound 2 with hydrophobic hydrophilic channels.

bonded DMF molecules arranged in such a way that the methyl groups will direct toward the hydrophobic walls (Figure S12). The hydrophilic channels have dimensions ∼5.6 × 6.2 Å2 and are decorated with furan oxygen and free carboxylic oxygen from monodentate coordination of furan carboxylates (Figure 2). These channels also contain hydrogen bonded DMF molecules but are arranged in such a way that the carbonyl oxygens will direct toward the hydrophilic walls (Figure S12). The PLATON26 analysis revealed that the 3D porous structure was composed of large voids of 2191.9 Å3 that represent 45.8% per unit cell volume. 573

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Figure 3. Comparison of Zn3(RCOO)8 eight connected nodes: (a) compound 1; (b and c) compound 2; (d) compound 3.

Table 1. Data for Three Compounds Synthesized in the Series27−29 compd

synthesis temp

formula

dimensionality

coordination geometry of trimeric Zn centers

pore types

1 2 3

90 °C 120 °C 160 °C

[Zn1.5(FDA)2(Me2NH2)]·xG [Zn3(FDA)4(Me2NH2)2]·xG [Zn1.5(FDA)2(Me2NH2)]·xG

2D 3D 3D

Oh (d)−Oh−Oh (d) tbp (d)−Oh−tbp (d) and Td−Oh−Td Td−Oh−Td

porous biporous porous

very similar PXRD and IR patterns (Figure S23), although compounds 1 and 2 have different structures. This indicates that compound 2 loses solvent molecules and transforms to stable phase similar to which air-dried compound 1 transforms. The above results clearly show the role of reaction temperature to change the lower dimensional structure to denser higher dimensions via one intermediate structure in Zn3(RCOO)8 based supramolecular isomers (Table 1). This type of systematic study on the role of different reaction parameters such as temperature may give us control over the desirable structure of MOFs, which is very important for design of functional materials. Unfortunately, the exact mechanisms by which these parameters affect the structures are not well understood yet. We could not check the porous properties of these above compounds, as compounds are losing solvents at room temperature and changing structure, so the phase purities of the bulk phases are difficult to confirm from powder X-ray diffraction data and elemental analysis. In conclusion, we have synthesized three anionic MOFs having general formula [Zn1.5(FDA)2(Me2NH2)] from the same starting materials by a solvothermal technique. The dimensionality control was obtained by a temperature tuning strategy which is attributed to the changes in the local environment around the Zn centers with increasing temperature. To the best of our knowledge, this is the first time we have shown the simultaneous control over dimensionality with supramolecular isomerism on MOFs.

It is now clear that the coordination number of the central Zn remains octahedral while adjacent Zn centers in the trimeric unit decrease from six (compound 1) to five and four (compound 2) with increasing temperature. This result motivated us to check if by increasing temperature we can get another phase with only one type of trimeric Zn unit having a central octahedral and an adjacent tetrahedral Zn center. The reaction at 160 °C yielded compound 3, having a 3D structure (Figure 1). The asymmetric unit contains two types of Zn centers. Zn1 have tetrahedral geometry with full occupancy while Zn2 have octahedral geometry with half occupancy similar to the Zn1−Zn3−Zn1′ unit in compound 2. The only change is the bidentate bridging carboxylate in compound 2 now becomes monodentate μ2-O bridging; thus, the free polyhedra again become vertex sharing in compound 3 (Figures 3 and S1). The trimeric units are connected by four FDA ligands in bc plane to form a 2D sheet. Adjacent 2D sheets are connected at the trimeric units from both the sides by a pair of FDA ligands, leading to a 3D framework. The 3D framework has 1D channels with dimensions ∼5.3 × 6.2 Å2 and is occupied by disordered DMF molecules and DMA cations. The PLATON26 analysis revealed that the 3D porous structure was composed of large voids of 2521.4 Å3 that represent 54.4% per unit cell volume. Interestingly, in total we observed a 2D structure (1) forming at lower temperature (90 °C) and a higher symmetrical monoporous 3D structure forming at higher temperature (160 °C) with one intermediate lower symmetrical biporous 3D structure forming at intermediate temperature (120 °C). On air drying, all three compounds lose disordered solvent molecules and transform to new unknown phases. But to our surprise we observed that the air-dried phases of compounds 1 and 2 have

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ASSOCIATED CONTENT

S Supporting Information *

X-ray crystallographic data of compounds 1−3 in cif format, table of selected bond angles and bond lengths, and figures. 574

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AUTHOR INFORMATION

Corresponding Author

*Telephone: +91-20-2590 8086. Fax: +91-20-2590 8186. Email: [email protected].

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ACKNOWLEDGMENTS We thank Director, Prof. K. N. Ganesh and IISER Pune for encouragement and research facilities. S.K.G. is grateful to DAE (Project No. 2011/20/37C/06/BRNS) for financial support.

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= 0.0347 and wR2 = 0.1171 for 18291 independent reflections [I > 2σ(I)]. CCDC-856831. (28) Crystal data for compound 2: C28H24N2O20Zn3, Mr = 904.60, triclinic, space group P1̅, a = 12.7693 (10) Å, b = 12.7842 (9) Å, c = 14.7758 (11) Å, V = 2191.9 (3) Å3, Z = 2, Fcalcd = 1.371 mg/m3, final R1 = 0.0312 and wR2 = 0.0958 for 11299 independent reflections [I > 2σ(I)]. CCDC-856832. (29) Crystal data for compound 3: C14H12NO10Zn1.5, Mr = 452.30, monoclinic, space group P21/c, a = 9.426 (5) Å, b = 15.424 (5) Å, c = 17.359 (5) Å, V = 2521.4(17) Å3, Z = 4, Fcalcd = 1.191 m g /m3, final R1 = 0.1038 and wR2 = 0.3523 for 6457 independent reflections [I > 2σ(I)]. CCDC-856833.

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