Title: Infinite Secondary Building Units and Forbidden Catenation in Metal-Organic Frameworks The National Science Foundation support to M.O'K. (DMR- 9804817) and O.M.Y. (DMR-9980469) is gratefully acknowledged.
Abstract: Angewandte Chemie International EditionVolume 41, Issue 2 p. 284-287 Communication Infinite Secondary Building Units and Forbidden Catenation in Metal-Organic Frameworks Nathaniel L. Rosi, Nathaniel L. Rosi Materials Design and Discovery Group Department of Chemistry University of Michigan Ann Arbor, MI 48109-1055, USA, Fax: (+1) 734-615-9751Search for more papers by this authorMohamed Eddaoudi Dr., Mohamed Eddaoudi Dr. Materials Design and Discovery Group Department of Chemistry University of Michigan Ann Arbor, MI 48109-1055, USA, Fax: (+1) 734-615-9751Search for more papers by this authorJaheon Kim Dr., Jaheon Kim Dr. Materials Design and Discovery Group Department of Chemistry University of Michigan Ann Arbor, MI 48109-1055, USA, Fax: (+1) 734-615-9751Search for more papers by this authorMichael O'Keeffe Prof., Michael O'Keeffe Prof. Department of Chemistry and Biochemistry Arizona State University Tempe, AZ 85287-1604, USASearch for more papers by this authorOmar M. Yaghi Prof., Omar M. Yaghi Prof. [email protected] Materials Design and Discovery Group Department of Chemistry University of Michigan Ann Arbor, MI 48109-1055, USA, Fax: (+1) 734-615-9751Search for more papers by this author Nathaniel L. Rosi, Nathaniel L. Rosi Materials Design and Discovery Group Department of Chemistry University of Michigan Ann Arbor, MI 48109-1055, USA, Fax: (+1) 734-615-9751Search for more papers by this authorMohamed Eddaoudi Dr., Mohamed Eddaoudi Dr. Materials Design and Discovery Group Department of Chemistry University of Michigan Ann Arbor, MI 48109-1055, USA, Fax: (+1) 734-615-9751Search for more papers by this authorJaheon Kim Dr., Jaheon Kim Dr. Materials Design and Discovery Group Department of Chemistry University of Michigan Ann Arbor, MI 48109-1055, USA, Fax: (+1) 734-615-9751Search for more papers by this authorMichael O'Keeffe Prof., Michael O'Keeffe Prof. Department of Chemistry and Biochemistry Arizona State University Tempe, AZ 85287-1604, USASearch for more papers by this authorOmar M. Yaghi Prof., Omar M. Yaghi Prof. [email protected] Materials Design and Discovery Group Department of Chemistry University of Michigan Ann Arbor, MI 48109-1055, USA, Fax: (+1) 734-615-9751Search for more papers by this author First published: 18 January 2002 https://doi.org/10.1002/1521-3773(20020118)41:2<284::AID-ANIE284>3.0.CO;2-MCitations: 283 The National Science Foundation support to M.O'K. (DMR- 9804817) and O.M.Y. (DMR-9980469) is gratefully acknowledged. Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract Interlinked Zn-O-C infinite secondary building units (SBUs) form the basis of the novel metal-organic frameworks (MOFs) [Zn3(OH2)(X)2]⋅4 DEF⋅2 H2O (MOF-69A: X=4,4′-biphenyldicarboxylate; MOF-69B: X=2,6-naphthalenedicarboxylate; DEF=N,N′-diethylformamide). The nature of the infinite SBUs results in frameworks (structure of MOF-69A depicted) wherein catenation is forbidden. References 1 Interpenetration, maximal displacement of catenated frameworks. For example see: 1a S. R. Batten, R. Robson, Angew. Chem. 1998, 110, 1558–1595; Angew. Chem. Int. Ed. 1998, 37, 1460–1494; 1b K. A. Hirsch, S. R. Wilson, J. S. Moore, Chem. Eur. J. 1997, 3, 765; 1c T. M. Reineke, M. Eddaoudi, D. Moler, M. O'Keeffe, O. M. Yaghi, J. Am. Chem. Soc. 2000, 122, 4843. Interweaving, minimal displacement of catenated frameworks. For example: 1d B. Chen, M. Eddaoudi, S. T. Hyde, M. O'Keeffe, O. M. Yaghi, Science 2001, 291, 1021. 2 2a O. M. Yaghi, H. Li, C. Davis, D. Richardson, T. L. Groy, Acc. Chem. Res. 1998, 31, 474; 2b L. R. MacGillivray, S. Subramanian, M. J. Zaworotko, Chem. Commun. 1994, 1325; 2c S. Kitagawa, M. Kondo, Bull. Chem. Soc. Jpn. 1998, 71, 1739–1753; 2d C. Klein, E. Graf, M. W. Hossieni, De Cian, New J. Chem. 2001, 25, 207–209; 2e O. R. Evans, Z. Wang, R. G. Xiong, B. M. Foxman, W. Lin, Inorg. Chem., 1999, 38, 2969–2973; 2f L. Carlucci, G. Ciani, P. Macchi, D. M. Proserpio, S. Rizzato, Chem. Eur. J. 1999, 5, 237–243. 3 M. Eddaoudi, D. B. Moler, H. Li, B. Chen, T. M. Reineke, M. O′Keeffe, O. M. Yaghi, Acc. Chem. Res. 2001, 34, 319–330. 4 H. Li, M. Eddaoudi, M. O'Keeffe, O. M. Yaghi, Nature 1999, 402, 276–279. 5 X-ray structure data: Siemens SMART CCD diffractometer, ω scans, graphite-monochromated MoKα radiation, SAINT for data integration, SADABS for absorption correction, XPREP for correction of Lorentz and polarization effects, and structure solution with direct methods (teXsan[17] for MOF-69A, SHELX-TL[18] for MOF-69B). 5a Data collection for MOF-69A: A colorless columnar crystal was analyzed: approximate dimensions: 0.30×0.090×0.080 mm at −120 °C, monoclinic, space group C2/c (no. 15) with a=23.1179(11), b=20.9192(5), c=12.0021(5) Å, β=111.627(2)°, V=5395.7(4) Å3, Z=4, ρcalcd=1.417 g cm−3, μ(MoKα)=13.90 cm−1, F(000)=2400, 3530 unique reflections within 2θmax=43.9°, Tmax=0.87, Tmin=0.57. The zinc atoms were refined anisotropically, while the rest were refined isotropically. Hydrogen atoms were included in predicted positions for the ligand and the ordered DEF molecule but not refined. The final cycle of full-matrix least-squares refinement was based on 1339 observed reflections (I>2.50σ(I)) and 171 variable parameters and refined to convergence R1=0.060 and Rw (all data)=0.066. The maximum and minimum peaks on the final difference Fourier map corresponded to 0.64 and −0.55 e− Å−3, respectively. While a hydrogen-bonded DEF molecule was defined well, the other DEF guest molecule was not modeled suitably due to the severe disorder around a mirror plane. 5b Data collection for MOF-69B: A colorless needle crystal was analyzed: approximate dimensions: 0.12×0.020×0.020 mm at −115 °C, monoclinic, space group C2/c (no. 15) with a=20.1658(15), b=18.5518(14), c=12.1580(9) Å, β=95.331(1)°, V=4528.8(6) Å3, Z=4, ρcalcd=1.612 g cm−3, and μ(MoKα)=16.54 cm−1, F(000)=2288, 4647 unique reflections within 2θmax=52.86°, Tmax=0.97, Tmin=0.75. All non-hydrogen atoms were refined anisotropically. The hydrogen atoms of the ndc ligand and the six methyl hydrogen atoms in a DEF molecule were generated with idealized geometries. The hydrogen atoms in both the hydroxy group and the DEF molecule were found in the electron density map and their positional parameters were refined. The final cycle of full-matrix least-squares refinement was based on 2282 observed reflections (I>2.00σ(I)) and 294 variable parameters and refined to convergence R1=0.0587 and Rw=0.1855. The maximum and minimum peaks on the final difference Fourier map corresponded to 0.854 and −0.761 e− Å−3, respectively. 5c All crystal structures in this report may be viewed and manipulated on the web: http://www.umich.edu/∼yaghigrp/structures.html Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication nos. CCDC-170965 (MOF-69A) and CCDC-170966 (MOF-69B). Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: (+44) 1223-336-033; e-mail: [email protected]). 6 6a J. Tao, M. L. Tong, J. X. Shi, X. M. Chen, S. W. Ng, Chem. Commun. 2000, 2043; 6b W. Clegg, D. R. Harbron, C. D. Homan, P. A. Hunt, I. R. Little, B. P. Straughan, Inorg. Chim. Acta. 1991, 186, 51; 6c J. Hermann, A. Erxleben, Inorg. Chim. Acta. 2000, 304, 125. 7 J. S. Seo, D. Whang, H. Lee, S. I. Jun, J. Oh, Y. J. Jeon, K. Kim, Nature 2000, 404, 982. 8 Van der Waals radii of C (1.70 Å) and O (1.40 Å) were employed in determination of distance parameters. A. Bondi, J. Phys. Chem. 1964, 68, 441–451. 9 9a M. O'Keeffe, M. Eddaoudi, H. Li, T. M. Reineke, O. M. Yaghi, J. Solid State Chem. 2000, 152, 3–20; 9b M. O'Keeffe, B. G. Hyde, Crystal Structures. I. Patterns and symmetry, Mineralogical Society of America, Washington, DC, 1996. 10 Other structures types such as the B net in CaB6 can be adapted to the same strategy. Here, linking octahedral SBUs with both short and long links, of the proper length ratio, that have been designed to lie along perpendicular planes would yield frameworks that do not catenate. This is well-represented in the structure of [Zn(4,4′-bpy)2(SiF6)n]n⋅x DMF (4,4′-bpy=4,4′-bipyridine: S. Subramanian, M. Zaworotko, Angew. Chem. 1995, 107, 2295–2297; Angew. Chem. Int. Ed. Engl. 1995, 34, 2127–2129. 11 Calculated free volumes were obtained by using Cerius2 software. 12 Elemental analysis for the exchange products of [Zn3(OH)2(bpdc)2]⋅(G)g; G=guest. Guests: (C6H6)3.5: calcd: C 59.81, H 3.99, N 0.00; found: C 60.16, H 3.76, N 0.00. (CHCl3)3.5: calcd: C 33.53, H 1.92, N 0.00; found: C 33.35, H 1.78, N 0.00. (iC3H7OH)0.5: calcd: C 44.48, H 2.63, N 0.00; found: C 44.78, H 2.56, N 0.00. (C4H8O)2: calcd: C 47.88, H 3.77, N 0.00; found: C 48.01, H 3.73, N 0.00. (CH3C6H5)3.75: calcd: C 61.70, H 4.58, N 0.00; found: C 61.69, H 4.70, N 0.00. Similar results were obtained with MOF-69B. 13 M. Eddaoudi, H. Li, O. M. Yaghi, J. Am. Chem. Soc. 2000, 122, 1391–1397. Citing Literature Volume41, Issue2January 18, 2002Pages 284-287 ReferencesRelatedInformation