In Situ Obtained Cu(II) Compound with Coexistence of Polycatenation

Dec 8, 2008 - Graduate University of the Chinese Academy of Sciences. ... Entangled Two-Dimensional Coordination Networks: A General Survey...
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In Situ Obtained Cu(II) Compound with Coexistence of Polycatenation and Polythreading Xin-Yi Cao,†,‡ Qi-Pu Lin,† Ye-Yan Qin,† Jian Zhang,† Zhao-Ji Li,† Jian-Kai Cheng,† and Yuan-Gen Yao*,†

CRYSTAL GROWTH & DESIGN 2009 VOL. 9, NO. 1 20–23

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China, and Graduate UniVersity of the Chinese Academy of Sciences, Beijing 100039, China ReceiVed August 25, 2008; ReVised Manuscript ReceiVed NoVember 11, 2008

ABSTRACT: The present study describes the preparation and characterization of the first example of metal-organic frameworks (MOFs) with the coexistence of polycatenation and polythreading involving chemically and structurally different two-dimensional square grids [Cu(II)2(5-HIPA)2(4,4′-bipy)2(H2O)2]n (A, 5-HIPA ) 5-hydroxyisophthalato) and irregular layers [Cu(II)3(5-HIPA)2(2-PyC)2(4,4′-bipy)2(H2O)4]n (B) in a unique three-dimensional framework [(A)(B)] · 6.5nH2O (1) with the in situ generated pyridine-2-carboxylate (2-PyC) ligand.

Introduction. Crystal engineering of metal-organic frameworks (MOFs) is of current interest not only for their potential applications in microelectronics, nonlinear optics, zeolite-like materials for molecular selection, ion exchange, and catalysis, but also for their intriguing variety of architectures and topologies.1 Particularly attractive are the novel types of supramolecular entanglements observed in parallel or inclined interpenetrating networks and the elucidation of the factors resulting in such periodic entanglements.2 So far, a variety of remarkable entangled systems of MOFs have been documented, which include polycatenane or polyrotaxane species, interweaved arrays of polymeric chains or helixes, polythreaded networks and interlocking topologies of the same or different motifs and/or dimensionality.3 According to Carlucci, Ciani, and Proserpio,3,4 polycatenation can be described as a type of entanglement in which the component motifs have lower dimensionality than that of the resulting architectures, and each individual motif is catenated only with the surrounding ones not with all the others. Although the 2D f 3D (increase of dimensionality) parallel or inclined catenation of layers is not very unusual, the polycatenation of different sheets is extremely rare in both inorganic and coordination polymer chemistry.2-5 Polythreaded structures are characterized by the presence of closed loops, as well as of elements that can thread through the loops, and can be considered as extended periodic analogues of molecular rotaxanes and pseudorotaxanes. A few interesting coordination polymers exhibiting polythreaded network architectures have been reported.6 However, the entanglement of distinct networks with coexistent polycatenation and polythreading has not been observed so far. Furthermore, research on such entanglements based on in situ generated building unit has seldom been reported. We report herein the first example of MOFs with the coexistence of polycatenation and polythreading involving chemically and structurally different 2D square grids [Cu(II)2(5-HIPA)2(4,4′-bipy)2(H2O)2]n (A, 5-HIPA ) 5-hydroxyisophthalato) and irregular layers [Cu(II)3(5-HIPA)2(2PyC)2(4,4′-bipy)2(H2O)4]n (B) in a unique 3D framework [(A)(B)] · 6.5nH2O (1) with the in situ generated pyridine-2-carboxylate (2PyC) ligand. In addition, a novel copper(I) chain polymer [Cu(I)2(5HIPA)(4,4′-bipy)2(H2O)]n · 2nH2O (2) has also been obtained simultaneously as a reductive product (Scheme 1). Hydrothermal reaction of Cu(NO3)2 · 3H2O, P-2mo-BDCME (5(pyridin-2-ylmethoxy)-isophthalic acid dimethyl ester) or P-2moBDCEE (5-(pyridin-2-ylmethoxy)-isophthalic acid diethyl ester), 4,4′-bipyridine (4,4′-bipy), and H2O at 170 °C for 60 h yielded a * To whom correspondence should be addressed. E-mail: [email protected]. † Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences. ‡ Graduate University of the Chinese Academy of Sciences.

large amount of blue (1) and yellow (2) crystals simultaneously7 (Scheme 1). The compositions were confirmed by elemental analysis and IR spectra, and the phase purities of the bulk samples were identified by powder X-ray diffraction. It is noteworthy that the whole reaction procedure includes the in situ hydrolysis of ester, decomposition of ether and redox process of copper(II) ions. Complexes 1 and 2 present the oxidative and reductive phases, respectively. Although many attempts to produce complex 1 by using H25-HIPA and H2-PyC instead of P-2mo-BDCME or P-2moBDCEE as starting materials failed, the reaction presented here is fully reproducible. X-ray single crystals analysis8 of complex 1 revealed that there are two distinct and crystallographically independent polymeric 2D motifs which form 2D inclined catenation (Figure 1). As motif A, a 2D square grid layer [CuII2(5-HIPA)2(4,4′-bipy)2(H2O)2]n consists of one Cu(II) ion, one 5-HIPA2-, one 4,4′-bipy, and one coordinating water molecule in the asymmetry unit. Each Cu1(II) ion is in an octahedral site surrounded by two N atoms from two 4,4′-bipy ligands (Cu-N 2.013 and 2.019 Å) occupying the axial positions, with three O atoms from two 5-HIPA ligands (Cu-O 1.931, 1.949 and 2.599 Å) and one water molecule (Cu-O 2.555 Å) occupying the equatorial positions. Each node (Cu1) of the square net is surrounded by four nodes (Cu1 atoms) which are bridged by 5-HIPA and 4,4′-bipy ligands. Two pyridyl rings of the 4,4′-bipy ligands are twisted by 24.77°. The square grids lie parallel to the crystallographic ac plane with a 9.724 Å period corresponding to two successive grids. The cavities in these 2D grid layers are slightly distorted squares (Cu1 to Cu1 dimension ) 10.303 × 11.079 Å2) with angles of 85.34 and 94.66°. The polymeric motif B of 1 is an unusual 2D irregular layer with intralayer stacking. The 2D network contains two crystallographically distinct copper atoms (Figure 1). Atom Cu2 is square pyramidal coordinated by one N atom from 4,4′-bipy ligand (Cu-N 2.029 Å), one O atom from 5-HIPA ligand (Cu-O 1.922 Å), one N and O atom from 2-PyC ligand (Cu-N 2.013 Å and Cu-O 1.938 Å) in a chelate fashion. A water molecule occupies the remaining apical site (Cu-O 2.507 Å). Atom Cu3 is in an octahedral site surrounded by two water molecules occupying the axial positions (Cu-O 2.614 Å), with two N atoms from two 4,4′-bipy ligands (Cu-N 2.038 Å) and two O atoms from two 5-HIPA ligands (Cu-O 1.922 Å) occupying the equatorial positions. It is interesting to note that atoms Cu2 and Cu3 are linked by 4,4′-bipy and 5-HIPA ligands to form an unusual 2D irregular layer with intralayer stacking. At each Cu2 site, the coordinated 4,4′-bipy ligand and the 2-PyC ligand are stacked up another Cu2 site in the same layer. What is more, the in situ generated 2-PyC ligand is crucial for the formation of the motif B and the whole structure. It not only acts

10.1021/cg800938y CCC: $40.75  2009 American Chemical Society Published on Web 12/08/2008

Communications

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Scheme 1. In situ Hydrothermal Syntheses of Complexes 1 and 2 in One Pot Reaction. View of the Coordination Arrangement of the Copper Atoms in 1 and 2

as a bidentate terminal ligand coordinating with the Cu2 atom, but also as the dangling ligand threading into the square grid of the motif A. The 2D irregular layers lie parallel to the crystallographic bc plane with a 6.826 Å period corresponding to two successive bilayers. In the irregular layered structure, each 4-connected node (Cu3 atom) is surrounded by four 2-connected linkers (Cu2 atoms), and each 2-connected linkers is surrounded by two 4-connected nodes. The architecture of motif B is schematically represented in Figure S4, Supporting Information. It is worth mentioning that the type B sheets have a classical sql topology because the 2-connected linkers are not counted as nodes topologically,9 as illustrated in Figure S4, Supporting Information. As far as we know, it is quite rare to observe distinct coordination polymers, especially with different chemistry, within the same crystal, affording an unusual packing lattice such as polycatenation, polythreading, interlocking and others.10 The most interesting

Figure 1. Two polymeric motifs present in 1 are a square grid A (top) and an irregular layer B (bottom) with intralayer stacking. Hydrogen atoms are omitted for clarity.

structural feature of 1 is that there are two chemically and structurally distinct coordination frameworks, 2D square grids and irregular layer with intralayer stacking in the lattice. Also of further importance, analysis of the crystal packing of 1 reveals that it represents an unprecedented entanglement for such two motifs; that is, the two types of sheets are polycatenated in a diagonal-parallel inclined fashion with the square windows of the A-type nets enclosing the 4,4′-bipy and 2-PyC rods of the B-type nets (Figure 2). Clearly, each square mesh of the A-type nets is not only catenated by one irregular layer of type B, but also threaded by one 2-PyC rod of the B-type net (Figure 3). Each single curled square mesh of B layer is catenanted with two different parallel A layers. The two sets of layers cross at a 90 degree angle. Each individual square layer of type A is catenated with an infinite number of the parallel irregular layers of type B, and vice versa. Being both sql nets we can adopt the further nomenclature proposed by Moulton and Zaworotko and call the inclined catenation of the d-p (diagonal-parallel) type when the full simplification is used.5a This fascinating supramolecular system could be considered as a new 3-D polycatenated and polythreaded architecture. The overall architecture is schematically represented in Figure 4. As a subgroup of entanglement supramolecular system, polycatenation, especially those involving distinct sheets, is still rarely documented, although a few intriguing examples have been designed with potential applications as functional materials.5 Known examples include a polycatenated 1D ladder that give a 2D or 3D array,11 2D simple12 or multilayers13 that result in 3D architectures, and the more complex cases involving motifs of different dimensionality.14 On the other hand, polythreaded structures containing finite components are, at present, still rare.6 The few species known include polythreaded 0D rings with side arms that give 1D15a or 2D15b arrays, as well as molecular ladders with dangling arms that result in (1D f 2D)15c or (1D f 3D)15d polythreaded arrays. Higher dimensional

Figure 2. The polycatenation of square grid A (yellow) with irregular layer B (purple) view along the a and b directions, respectively.

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Communications of 1 indicates two main weight losses. The first one from 45 to 167 °C corresponds to the loss of six and one-half lattice water molecules and six aqua ligands. The observed weight loss of 10.15% is in agreement with the calculated one (10.55%). The second weight loss of 68.16% (theoretical one is 70.8%) from 239 to 900 °C corresponds to the decomposition of the organic groups. The TGA curve of 2 indicates three main weight losses. The first one from 77 to 113 °C corresponds to the loss of two lattice water molecules. The second one from 113 to 156 °C corresponds to the loss of one aqua ligands. The observed weight loss of 7.88% is in agreement with the calculated one (8.02%). The final weight loss of 68.34% (theoretical one is 70.74%) from 239 to 900 °C corresponds to the decomposition of the organic groups. X-ray powder diffraction profiles for complexes 1 and 2 were illustrated in Figure S7, Supporting Information. In summary, we have synthesized and characterized a new 3D copper MOF with extraordinary structural features. The results reported here first reveal another type of entanglement architecture: coexistence of polycatenation and polythreading involving chemically and structurally distinct sheets.

Figure 3. Coexistence of catenated and threaded units in the polycatenated structure. Aqua ligands and H atoms are omitted for clarity.

Acknowledgment. This work was supported by the State Key Basic R&D Plan of China (2007CB815302), The CAS (KJCX2YW-M05), the NSF (E0620005) of Fujian Province (FP), the Major Special Foundation of FP (2005HZ1027), (2005HZ01-1), and Fund of FP Key Laboratory of Nanomaterials (2006L2005). Supporting Information Available: Syntheses of P-2mo-BDCME, P-2mo-BDCEE, 1 and 2; IR spectra of P-2mo-BDCME, P-2moBDCEE, 1 and 2; 2D and 3D structural diagram of 2; TGA and XRPD diagrams for complexes 1 and 2. This information is available free of charge via the Internet at http://pubs.acs.org.

References

Figure 4. Schematic view of the overall entanglement of 1.

polythreaded coordination networks as periodic analogues of the molecular rotaxanes or pseudorotaxanes are achieved by Du et al. (1D + 2D f 3D)16 and Wang et al. (2D f 3D).17 However, the entanglement of distinct networks with coexistent polycatenation and polythreading has not been reported up to now. Remarkably, complex 1 represents the first 2D + 2D f 3D entangled system with the coexistence of polycatenation and polythreading involving chemically and structurally distinct sheets. Additional investigation for this structure indicates that O-H · · · O hydrogen bonds can be detected between two different motifs in 1, involving the carboxylate oxygens, the lattice aqua and water ligand, which further stabilize this framework. X-ray crystallography8 of complex 2 has shown that it exists as a linear chain [Cu1-bipy1-Cu2-bipy2-Cu1]n with 5-HIPA2- and water molecule as terminal ligands (Scheme 1). Both copper(I) atoms display a T-shaped trigonal geometry, but with different coordinating environments. The two pyridine rings in the independent 4,4′bipy ligands are twisted by 14.75° and 23.67°, respectively. Worth mentioning here is that these adjacent chains are linked with each other by O5-H · · · O4 (O5 · · · O4 2.554 Å) strong hydrogen bonds to form 2D layers which are further connected to each other through π-π interactions of 4,4′-bipy ligands to complete the final 3D architecture (Figure S5, Supporting Information), as reflected by the less than 3.70 Å intermolecular contacts. Thermogravimetric analyses (TGA) of complexes 1 and 2 were performed (Figure S6, Supporting Information). The TGA curve

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