Three-fold-Interpenetrated Diamondoid Coordination Frameworks with Torus Links Constructed by Tetranuclear Building Blocks Yun Ling, Lei Zhang,* Jing Li, and Ai Xi Hu School of Chemistry and Chemical Engineering, South China UniVersity of Technology, Guangzhou 510640, P. R. China
CRYSTAL GROWTH & DESIGN 2009 VOL. 9, NO. 5 2043–2046
ReceiVed October 22, 2008; ReVised Manuscript ReceiVed March 22, 2009
ABSTRACT: Two new isostructural coordination polymers, namely, [M(malo)(HFlu)]n (M ) Zn for 1 and Cu for 2, malo ) malonate dianion, HFlu ) fluconazole), have been prepared by a solution diffusion method. The polymers show rare three-dimensional 3-fold interpenetrated dia-f coordination frameworks with (2.2.1) Hopf links and (6.3.3) Torus links. The tetranuclear M4(malo)4 cluster as a secondary building unit becomes the decorated vertex in the dia-f net. Polymer 1 shows an intense fluorescent emission, while polymer 2 shows a quenching phenomenon in the solid state at room temperature. Magnetic susceptibility studies for 2 reveal a ferromagnetic coupling interaction in the anti-syn carboxylate-bridged Cu(II) clusters. Comparable experiments with Ni(II) and Cd(II) resulting in discrete dinuclear structures are also reported. Crystal engineering has been the subject aimed at the production of coordination polymers with controllable fascinating structure and/ or potential applications as functional materials.1 The varieties of steric topologies have attracted considerable attention in recent years for chemists and mathematicians in search of entanglement coordination polymers such as interpenetrated, polycatenated, polythreaded, and polyknotted structures, especially with undiscovered intriguing topologies.2-4 The diamondoid framework, as one of most important topologies in networks, has attracted great attention not only for the robust structural motifs in constructing acentric solid but also for its potential application in nonlinear optics (NLO) since the pioneering work of Ermer5 and in zeolitelike materials.1a,d,2a,3c Recently, diverse secondary building units (SBUs, metal clusters) are now widely used in the synthesis of diamondoid (dia) net and open porous metal-organic frameworks (MOFs),6-8 in which the n-fold interpenetrated dia coordination polymers have been an invariable highlight.9,10 For example, an unusual 12-fold interpenetrated dia net with a longer N,N′-di(4-pyridyl)adipoamide ligand as a spacer has been reported by Hsu et al. recently.10 The carboxylate-bridged tetranuclear clusters always feature distorted tetrahedral geometry,11a,b which is the prerequisite in the construction of the dia net.2a,3c Therefore, a powerful and effective synthetic strategy has been developed by replacing a diamondoid vertex with a carboxylate-bridged tetrahedral cluster to generate artificially as-synthesized fascinating mineral structures and to obtain properties of dia nets as well.9b Along these line, we report two novel intriguing examples in this communication, [M(malo)(HFlu)]n (M ) Zn for 1; Cu for 2, malo ) malonate dianion; HFlu ) fluconazole, 2-(2,4-difluoro-phenyl)-1,3-bis(1,2,4-triazol-1-yl)propan-2-ol), two rare three-dimensional (3-D) 3-fold-interpenetrated dia-f coordination nets constructed by malonate-bridged tetrahedral SBU and flexible fluconazole ligand. Topology analysis reveals the presence of Hopf links and peculiar Torus links (Scheme 1) in the interlocking uninodal nets. Fluorescent and magnetic properties are also reported herein. The two coordination polymers 1 and 2 were obtained by diffusing methanol solution of HFlu to the aqueous solution of M(malo) (Supporting Information). Single crystal X-ray diffraction analysis12 revealed that 1 and 2 are isostructures (Figure 1, Table S1, Supporting Information), so the structural discussions are mainly described for 1. Coordination polymer 1 consists of Zn4(malo)4 SBUs and flexible HFlu ligands in an antigauche conformation (Figure S1, Supporting Information). The Zn(II) ions in 1 are five * Corresponding author. E-mail:
[email protected]. Fax: +86-20-8711 0234.
Scheme 1. (a) (6.3.2) Borromean Links and (b) (6.3.3) Torus Links
coordinated with distorted square-pyramidal geometry (τ ) 0.355 based on τ ) |β - R|/60).13 The M-O and M-N distances fall in the range of 2.004-2.071 Å (1.940-2.033 Å for 2) and 2.075-2.126 Å (1.984-2.225 Å for 2) (Table S2, Supporting Information), respectively, while for 2, O2A (A: 5/4 - y, -3/4 + x, 1/4 - z) is weakly coordinated to Cu1 with a Cu1-O2A distance of 2.706 Å due to the large John-Teller effect. The M · · · M distances connected by malo2- ligands in the tetrahedral SBU are 4.595 Å for 1 and 4.571 Å for 2. Each tetrahedral SBU is further connected by every two HFlu ligands from four vertexes of the SBU to generate an infinite 3-D coordination polymeric net. The M · · · M distances connected by two HFlu ligands are 10.339 Å for 1 and 10.441 Å for 2, respectively. Topology analyses reveal a rare 4.142 net according to the short vertex symbol and 4.14(12).14(12) net according to the long vertex symbol (OLEX) (regarding the metal ions as nodes and bridge ligands as linkers, Figure 2a), which is characteristic of the dia-f net.14 As far as we know, this is the first example of dia-f net constructed by carboxylate-bridged tetranuclear clusters as SBU.15 It is worth noting that the tetrahedral SBU, four metal ions occupying the vertex in the tetrahedron, makes itself possible to act as a vertex of the uninodal net in dia-f topology. Polymers 1 and 2 represent open porous frameworks at first sight along both a and b axes (Figure 1b). However, the dia net is one of the four nets naturally interpenetrated.3a,c,6b Structural analyses reveal that three independent dia-f nets mutually interpenetrate leaving no accessible cavities for other guests in 1 and 2, which is confirmed by the fact that no absorption is observed in the N2 absorption experiment at 77 K, although the void space (nonframework volume per unit cell) is 5.7% calculated via PLATON analysis. Further structural analyses reveal each six-membered (one tetrahedral SBU as one member) chair ring in the 3-fold dia-f net is totally crossed by 12 other rings forming 12 Hopf links and (6.3.3)
10.1021/cg801188r CCC: $40.75 2009 American Chemical Society Published on Web 04/16/2009
2044
Crystal Growth & Design, Vol. 9, No. 5, 2009
Communications
Figure 1. (a) dia-f net with tetrahedral Zn4(malo)4 SBUs as the diamondoid vertexes (Zn ions are drawn based on the crystal coordinates). (b) A view of open porous structure.
Torus links were sheltered among them (Figure 2a). Torus links differ from Borromean links in that cleavage one of three rings could not make them wholly fall apart, but generates a new Hopf link.2d In 1 and 2, the decorated dia-f topology has without doubt exhibited higher net undulation, which rightly matches the requirement to construct the (6.3.3) Torus link. The hydrogen bonding interactions consisting of a hydroxyl group of HFlu and uncoordinated acetate-O atom in 1 and 2 further establish the 3-fold interpenetrated reticular structure (Table S3, Supporting Information). In addition, the 3-fold interpenetrated dia-f nets exhibit a triintertwist right and left handed alternating helical array along the c axis when taking the SBU as a linkage (helical pitch 26.0 Å) of the four neighboring helices array (Figure 2b). Therefore, 1 and 2 feature 3-D helical interlocked dia-f nets with Hopf links and Torus links, which are stabilized by hydrogen bond interactions. As mentioned above, the tetrahedral SBU in the uninodal net is the basic and most important part for presentation of the dia-f net. In order to investigate the influence of node types (coordination geometry of metal ion) on the tetrahedral SBU, comparable experiments were carried out under similar reaction conditions with generally six-coordinated metal ions, namely, Ni(II), Cd(II), while generated discrete dinuclear structure with malo acted as a terminal chelating ligand (Figure S2, Supporting Information). The structural
analyses confirm the conclusion that the regular octahedron is hardly present in the tetranuclear tetrahedral metal-carboxylate cluster because the malonate-bridged M · · · M distances generally fall in the range of 4.52-5.51 Å,11 longer than the sum of two M-O bond distances bridged by a carboxylate-O atom in the regular octahedron. However, the octahedral Cu(II) clusters in the tetrahedral SBUs could be formed due to the longer Cu-O distance at the axial positions. Therefore, 1 and 2 are a node-induced SBUbased 3-D coordination net. The solid-state spectra of 1 and 2 at room temperature are shown in Figure 3. Excited at λ ) 262 nm (based on HFlu), sample 1 shows an intense emission peak at 288 nm, while 2 shows a quenching phenomenon, which may be attributed to the intramolecular energy transfer because polymer 2 shows a broad absorption band at 220-290 nm at solid state in the UV-vis spectrum. Variable temperature magnetic susceptibility data for a crystalline sample of 2 were obtained on a SQUID susceptometer within the temperature range of 2-300 K at a constant magnetic field of 1 kOe. Magnetic susceptibility has also been fitted based on the isotropic Heisenberg Hamiltonian (eq 1) with square polygon model (Figure S3, Supporting Information) and reveals that the malo2group is responsible for weak ferromagnetic interactions with g ) 2.03(2), J ) 6.7(2) cm-1 and R ) 1.96 × 10-4 (R ) Σ[(χMT)obs -
Communications
Crystal Growth & Design, Vol. 9, No. 5, 2009 2045
Figure 2. (a) 3-fold interpenetrated dia-f nets labeled with three different colors and Torus links (6.3.3) observed in 12 Hopf links. (b) Triple intertwist alternating helical array with magnified right-handed helices in space-filling mode.
M4(malo)4 SBUs and flexible HFlu ligands through a solution diffusion reaction. The topology analyses reveal that the Zn(II)/ Cu(II) ion favors formation of tetrahedral units with a malo ligand as the diamondoid vertex, and that 3-fold interpenetrated dia-f framework within Hopf links and Torus links is further stabilized by hydrogen bond interactions. The property studies show dissimilar fluorescent phenomena for 1 and 2 (an intense emission for 1 vs a quenching phenomenon for 2) and the ferromagnetic coupling interactions between the Cu(II) centers with anti-syn carboxylate bridges in 2.
Acknowledgment. We thank the Key Lab of Enhanced Heat Transfer and Energy Conservation, MOE, South China University of Technology, for partially funding this work. We also thank Dr. Xiao-Lan Yu for use of the SQUID magnetometer.
Figure 3. Emission spectra of 1 and 2 in solid state at room temperature excited with λex ) 262 nm. (1: deep cyan; 2: deep blue).
(χMT)calc]2/Σ(χMT)obs2) (Figure S3, Supporting Information), consistent with the known magnetostructural relationship in the synanti configuration of equatorial-equatorial Cu-O-C-O-Cu skeleton reported previously.11
H ) -2J(S1S2 + S2S3 + S3S4 + S4S1)
(1)
In summary, we present here two novel 3-fold interpenetrated 3D dia-f coordination frameworks constructed by tetrahedral
Supporting Information Available: Crystallographic data in CIF format of 1 and 2, synthesis of 1 and 2, tables for structural data and hydrogen bonds for 1 and 2, the coordination geometry of Zn(II), Ni(II), Cd(II) complexes, magnetic data and the fragment of the magnetic coupling in 2, IR spectra, TG, powder X-ray patterns and crystal photography for 1 and 2. This material is available free of charge via the Internet at http://pubs.acs.org.
References (1) (a) O’Keeffe, M.; Eddaoudi, M.; Li, H.; Reineke, T.; Yaghi, O. M. J. Solid State Chem. 2000, 152, 3–20. (b) Kitagawa, S.; Kitaura, R.; Noro, S. I. Angew. Chem., Int. Ed. 2004, 43, 2334–2375. (c) Siegel, J. S.
2046
(2)
(3)
(4)
(5) (6)
(7)
(8)
Crystal Growth & Design, Vol. 9, No. 5, 2009
Science 2004, 304, 1256–1258. (d) Ockwig, N. W.; DelgadoFriederichs, O.; O’Keeffee, M.; Yaghi, O. M. Acc. Chem. Res. 2005, 38, 176–182. (e) Rosi, N. L.; Kim, J.; Eddaoudi, M.; Chen, B. L.; O’Keeffe, M.; Yaghi, O. M. J. Am. Chem. Soc. 2005, 127, 1504– 1518. (a) Batten, S. R.; Robson, R. Angew. Chem., Int. Ed. 1998, 37, 1461– 1494. (b) Batten, S. R. CrystEngComm 2001, 18, 1–7. (c) Carlucci, L.; Ciani, G.; Proserpio, D. M. Coord. Chem. ReV. 2003, 246, 247– 289. (d) Carlucci, L.; Ciani, G.; Proserpio, D. M. CrystEngComm 2003, 5, 269–279. (e) Blatov, V. A.; Carlucci, L.; Ciani, G.; Proserpio, D. M. CrystEngComm 2004, 6, 377–395. (a) Bonneau, C.; Delgado-Friedrichs, O.; O’Keeffe, M.; Yaghi, O. M. Acta Crystallogr. A 2004, A60, 517–520. (b) Delgado-Friedrichs, O.; Foster, M. D.; O’Keeffe, M.; Proserpio, D. M.; Treacy, M. M. J.; Yaghi, O. M. J. Solid State Chem. 2005, 178, 2533–2554. (c) Tiekink, E. R. T.; Vittal, J. J., Eds.; Frontiers in Crystal Engineering; John Wiley & Sons, Ltd.: San Francisco, 2006; pp 157-194. (a) Lv, X. Q.; Pan, M.; He, J. R.; Cai, Y. P.; Kang, B. S.; Su, C. Y. CrystEngComm 2006, 8, 827–829. (b) Liantonio, R.; Metrangolo, P.; Meyer, F.; Pilati, T.; Navarrin, W.; Resnati, G. Chem. Commun. 2006, 1819–1821. (c) Zhang, X. L.; Guo, C. P.; Yang, Q. Y.; Wang, W.; Liu, W. S.; Kang, B. S.; Su, C. Y. Chem. Commun. 2007, 4242– 4244. (d) Li, J. R.; Song, L.; Du, S. W. Inorg. Chem. Commun. 2007, 10, 358–361. (e) Yang, E. C.; Zhao, H. K.; Ding, B.; Wang, X. G.; Zhao, X. J. Cryst. Growth Des. 2007, 7, 2009–2015. (f) Zhang, J.; Yao, Y. G.; Bu, X. H. Chem. Mater. 2007, 29, 5083–5089. (g) Metrangolo, P.; Meyer, F.; Pilati, T.; Proserpio, D. M.; Resnati, G. Chem.sEur. J. 2007, 13, 5765–5772. (a) Ermer, O.; Eling, A. Angew. Chem., Int. Ed. 1988, 27, 829–833. (b) Ermer, O. J. Am. Chem. Soc. 1988, 110, 3747–3754. (a) Yaghi, O. M.; Li, H. L.; Davis, C.; Richardson, D.; Groy, T. L. Acc. Chem. Res. 1998, 31, 474–484. (b) Yaghi, O. M.; O’Keeffe, M.; Ockwig, N. W.; Chae, H. K.; Eddaoudi, M.; Kim, J. Nature (London) 2003, 423, 705–714. (a) Konar, S.; Zangrando, E.; Drew, M. G. B.; Ribas, J.; Chaudhuri, N. R. Dalton Trans. 2004, 260–266. (b) Yang, J.; Ma, J. F.; Liu, Y. Y.; Li, S. L.; Zheng, G. L. Eur. J. Inorg. Chem. 2005, 217, 4–2180. (c) Kumar, D. K.; Jose, D. A.; Das, A.; Dastidar, P. Inorg. Chem. 2005, 44, 6933–6935. (a) Jones, K. M. E.; Mahmoudkhani, A. H.; Chandler, B. D.; Shimizu, G. K. H. CrystEngComm 2006, 8, 303–305. (b) Taylor, J. M.; Mahmoudkhani, A. H.; Shimizu, G. K. H. Angew. Chem., Int. Ed. 2007, 46, 795–798. (c) Sarkar, M.; Biradha, K. Cryst. Growth Des. 2007, 7, 1318–1331. (d) Wang, X. L.; Qin, C.; Wang, E. B.; Su, Z. M. Chem. Commun. 2007, 4245–4247. (e) Martin, D. P.; Braverman, M. A.; LaDuca, R. L. Cryst. Growth Des. 2007, 7, 2609–2619. (f) Lee, H. Y.; Park, J.; Lah, M. S.; Hong, J. I. Cryst. Growth Des. 2008,
Communications
(9)
(10) (11)
(12)
(13) (14)
(15)
8, 587–591. (g) Mondal, R.; Bhunia, M. K.; Dhara, K. CrystEngComm 2008, 10, 1167–1174. (h) Wang, G. H.; Li, Z. G.; Jia, H. Q.; Hu, N. H.; Xu, J. W. Cryst. Growth Des. 2008, 8, 1932–1939. (i) O’Keeffe, M. Acta Crystallogr., Sect. A 2008, A64, 425–429. (j) Furukawa, H.; Kim, J.; Ockwig, N. W.; O’Keeffe, M.; Yaghi, O. M. J. Am. Chem. Soc. 2008, 130, 11650–11661. (a) Wang, X. S.; Zhao, H.; Qu, Z. R.; Ye, Q.; Zhang, J.; Xiong, R. G.; You, X. Z.; Fun, H. K. Inorg. Chem. 2003, 42, 5786–5788. (b) Fang, Q. R.; Zhu, G. S.; Jin, Z.; Xue, M.; Wei, X.; Wang, D. J.; Qiu, S. L. Cryst. Growth Des. 2007, 7, 1035–1037. (c) Liang, K.; Zheng, H. G.; Song, Y. L.; Li, Y. Z.; Xin, X. Q. Cryst. Growth Des. 2007, 7, 373– 376. Hsu, Y. F.; Lin, C. H.; Chen, J. D.; Wang, J. C. Cryst. Growth Des. 2008, 8, 1094–1096. (a) Dey, S. K.; Bag, B.; Abdul Malik, K. M.; EI Fallah, M. S.; Ribas, J.; Mitra, S. Inorg. Chem. 2003, 42, 4029–4035. (b) Konar, S.; Mukherjee, P. S.; Drew, M. G. B.; Ribas, J.; Chaudhuri, N. R. Inorg. Chem. 2003, 42, 2545–2552. (c) Zang, S.; Su, Y.; Li, Y. Z.; Zhu, H. Z.; Meng, Q. J. Inorg. Chem. Commun. 2006, 9, 337–340. (d) Baldoma´, R.; Monfort, M.; Ribas, J.; Solans, X.; Maestro, M. A. Inorg. Chem. 2006, 45, 8144–8155. (e) Biswas, C.; Mukherjee, P.; Drew, M. G. B.; Go´mez-Garcı´a, C. J.; Clemente-Juan, J. M.; Ghosh, A. Inorg. Chem. 2007, 46, 10771–10780. Crystal data for 1 and 2: C16H14F2N6O5Zn, M ) 473.70, tetragonal, space group I41/a, a ) 30.1922(9), b ) 30.1922(9), c ) 8.6557(3) Å, V ) 7890.3(4) Å3, Z ) 16, Dc ) 1.595 g · cm-3, F(000) ) 3840, GOF ) 1.033, R1 ) 0.0324 and wR2 ) 0.0742 for 1. C16H14CuF2N6O5, Mr ) 471.87 tetragonal, space group I41/a, a ) 30.0837(16), b ) 30.0837(16), c ) 8.6670(9) Å, V ) 7843.9(10) Å3, Z ) 16, Dc ) 1.598 g · cm-3, F(000) ) 3824, GOF ) 1.044, R1 ) 0.0273 and wR2 ) 0.0714 for 2. Addison, A. W.; Rao, T. N. J. J. Chem. Soc., Dalton Trans. 1984, 1349–1356. (a) Wells, A. F. Three-Dimensional Nets and Polyhedra; WileyInterscience: New York, 1977. (b) Delgado Friedrichs, O.; O’Keeffe, M.; Yaghi, O. M. Acta Crystallogr., Sect. A 2003, A59, 22–27. (c) O’Keeffe, M.; Peskov, M. A.; Ramsden, S. J.; Yaghi, O. M. Acc. Chem. Res. 2008, 41, 1782–1789. (a) Schier, A.; Wallis, J. M.; Mu¨eller, G.; Schmidbaur, H. Angew. Chem. 1986, 98, 742–744. (b) Zhang, J.-P.; Lin, Y.-Y.; Zhang, W.X.; Chen, X.-M. J. Am. Chem. Soc. 2005, 127 (41), 14162–14163. (c) Xie, Y.-M.; Zhao, Z.-G.; Wu, X.-Y.; Zhang, Q.-S.; Chen, L.-J.; Wang, F.; Chen, S.-C.; Lu, C.-Z. J. Solid State Chem. 2008, 181, 3322–3326.
CG801188R
