A Quadruply Stranded Metallohelicate and Its Spontaneous Dimerization into an Interlocked Metallohelicate

Angewandte Chemie International EditionVolume 47, Issue 4 p. 706-710 Communication A Quadruply Stranded Metallohelicate and Its Spontaneous Dimerization into an Interlocked Metallohelicate† Morihiko Fukuda, Morihiko Fukuda Department of Biophysics and Biochemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, JapanSearch for more papers by this authorRyo Sekiya Prof., Ryo Sekiya Prof. [email protected] Department of Life Sciences, Graduate School of Arts and Sciences, The University of Tokyo, 3-8-1 Komaba, Meguro-ku, Tokyo 153-8902, Japan, Fax: (+81) 3-5454-6601 (for R.S.), Fax: (+81) 3-5454-6600 (for R.K.)Search for more papers by this authorReiko Kuroda Prof., Reiko Kuroda Prof. [email protected] Department of Life Sciences, Graduate School of Arts and Sciences, The University of Tokyo, 3-8-1 Komaba, Meguro-ku, Tokyo 153-8902, Japan, Fax: (+81) 3-5454-6601 (for R.S.), Fax: (+81) 3-5454-6600 (for R.K.) Department of Biophysics and Biochemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan Japan Science and Technology Agency, ERATO-SORST, Kuroda Chiromorphology Team, 4-7-6 Komaba, Meguro-ku, Tokyo 153-0041, JapanSearch for more papers by this author Morihiko Fukuda, Morihiko Fukuda Department of Biophysics and Biochemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, JapanSearch for more papers by this authorRyo Sekiya Prof., Ryo Sekiya Prof. [email protected] Department of Life Sciences, Graduate School of Arts and Sciences, The University of Tokyo, 3-8-1 Komaba, Meguro-ku, Tokyo 153-8902, Japan, Fax: (+81) 3-5454-6601 (for R.S.), Fax: (+81) 3-5454-6600 (for R.K.)Search for more papers by this authorReiko Kuroda Prof., Reiko Kuroda Prof. [email protected] Department of Life Sciences, Graduate School of Arts and Sciences, The University of Tokyo, 3-8-1 Komaba, Meguro-ku, Tokyo 153-8902, Japan, Fax: (+81) 3-5454-6601 (for R.S.), Fax: (+81) 3-5454-6600 (for R.K.) Department of Biophysics and Biochemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan Japan Science and Technology Agency, ERATO-SORST, Kuroda Chiromorphology Team, 4-7-6 Komaba, Meguro-ku, Tokyo 153-0041, JapanSearch for more papers by this author First published: 08 January 2008 https://doi.org/10.1002/anie.200703162Citations: 172 † We are grateful to the single-crystal X-ray structure analysis group of the RIGAKU corp. for measurement of the diffraction data of 2. This work was partly supported by a Grant-in-Aid for Scientific Research (17750122) from the Ministry of Education, Culture, Sports, and Technology of Japan. 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 Making up a foursome: Self-assembly of 4,4′-(3-pyridinemethoxy)benzophenone (L) and Pd(NO3)2 resulted in the quantitative formation of a quadruply stranded metallohelicate [Pd2(L)4], which undergoes spontaneous dimerization to an unprecedented chiral interlocked metallohelicate [Pd2(L)4]2 (see X-ray structure; C black, H white, N blue, O red). Supporting Information Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2008/z703162_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article. References 1 1aM. Fujita, M. Tominaga, A. Hori, B. Therrien, Acc. Chem. Res. 2005, 38, 369–378; 1bM. Ruben, J. Rojo, F. J. Romero-Salguero, L. H. Uppadine, J.-M. Lehn, Angew. Chem. 2004, 116, 3728–3747; Angew. Chem. Int. Ed. 2004, 43, 3644–3662. 2 2aG. F. Swiegers, T. J. Malefetse, Coord. Chem. Rev. 2002, 225, 91–121; 2bM. Tominaga, K. Suzuki, M. Kawano, T. Kusukawa, T. Ozeki, S. Sakamoto, K. Yamaguchi, M. Fujita, Angew. Chem. 2004, 116, 5739–5743; Angew. Chem. Int. Ed. 2004, 43, 5621–5625. 3J.-M. Lehn, A. Rigault, J. Siegel, J. Harrowfield, B. Chevrier, D. Moras, Proc. Natl. Acad. Sci. USA 1987, 84, 2565–2569. 4 4aC. Piguet, G. Bernardinelli, G. Hopfgartner, Chem. Rev. 1997, 97, 2005–2062; 4bA. E. Rowan, R. J. M. Nolte, Angew. Chem. 1998, 110, 65–71; Angew. Chem. Int. Ed. 1998, 37, 63–68. 5 5aJ. Gregoliński, J. Lisowski, Angew. Chem. 2006, 118, 6268–6272; Angew. Chem. Int. Ed. 2006, 45, 6122–6126; 5bS. G. Telfer, R. Kuroda, J. Lefebvre, D. B. Leznoff, Inorg. Chem. 2006, 45, 4592–4601; 5cS. G. Telfer, R. Kuroda, Chem. Eur. J. 2005, 11, 57–68; 5dS. G. Telfer, T. Sato, R. Kuroda, Angew. Chem. 2004, 116, 591–594; Angew. Chem. Int. Ed. 2004, 43, 581–584; 5eJ. Hamacek, S. Blanc, M. Elhabiri, E. Leize, A. V. Dorsselaer, C. Piguet, A. M. Albrecht-Gary, J. Am. Chem. Soc. 2003, 125, 1541–1550; 5fR. C. Scarrow, D. L. White, K. N. Raymond, J. Am. Chem. Soc. 1985, 107, 6540–6546. 6 6aD. A. McMorran, P. J. Steel, Angew. Chem. 1998, 110, 3495–3497; Angew. Chem. Int. Ed. 1998, 37, 3295–3297; 6bL. J. Barbour, G. W. Orr, J. L. Atwood, Nature 1998, 393, 671–673; 6cH. Amouri, L. Mimassi, M. N. Rager, B. E. Mann, C. Guyard-Duhayon, L. Raehm, Angew. Chem. 2005, 117, 4619–4622; Angew. Chem. Int. Ed. 2005, 44, 4543–4546; 6dJ. Xu, K. N. Raymond, Angew. Chem. 2006, 118, 6630–6635; Angew. Chem. Int. Ed. 2006, 45, 6480–6485. 7M. Fujita, N. Fujita, K. Ogura, K. Yamaguchi, Nature 1999, 400, 52–55. 8J. J. P. Stewart, MOPAC 2007, http://openmopac.net/. 9See the Supporting Information for details. 10Crystal data for L1 (C25H20N2O3): Mr=198.2, colorless crystal, crystal dimensions 0.40×0.40×0.25 mm3, orthorhombic, space group Pbcn (no. 60), Z=8, ρcalcd=1.39 g cm−3, F(000)=831.9, 2θmax=55.8° were a=7.1974(5), b=6.4495(5), c=40.935(3) Å, and V=1900.16(2) Å3. The intensity data were collected on a Bruker SMART APEX CCD diffractometer (MoKα radiation, λ=0.71073 Å) at 103 K. A total of 10 678 reflections were collected of which 2243 reflections were independent (Rint=0.0254). The crystal structure was solved by direct methods using the SHELXS-97 program[18] and refined by successive differential Fourier syntheses and full-matrix least-squares procedures using the SHELXL-97 program.[19] Anisotropic thermal factors were applied to all non-hydrogen atoms. All hydrogen atoms were generated geometrically. The structure was refined to final R1=0.047 for 2032 data [I>2σ(I)] with 137 parameters, wR2=0.113 for all data, GOF=1.088, and residual electron density max/min=0.357/−0.264 e Å−3.. 11Crystallization of 1 from DMF or DMSO solutions gave only crystals of 2. We have reasoned that during crystallization, 1 was gradually converted into the thermodynamically more stable 2. See text for details. 12A. K. Rappe, K. S. Colwell, C. J. Casewit, Inorg. Chem. 1993, 32, 3438–3450. 13As [D6]DMSO freezes at 291 K, we used [D6]DMSO/[D4]MeOD (1:1) mixed solutions for the measurement of the variable-temperature NMR spectra of 1 and 2. Splitting of the He signal of 1 was not observed at the lowest possible temperature for the solvent. 14The possibility of L1 having C2v symmetry with a planar conformation in the complexes and a box shape for 1 was pointed out by one of the referees. PM6 calculations suggested that benzophenone with a planar conformation has a higher heat of formation than the other conformations because of the steric repulsion between hydrogen atoms of neighboring phenyl rings. 15Crystal data for 2 (Pd(C25H20N2O3)2(DMF)): Mr=972.4, colorless crystal, crystal dimensions 0.11×0.10×0.04 mm3, tetragonal, space group P4/n (no. 85), Z=8, ρcalcd=0.90 g cm−3, F(000)=4015.4, 2θmax=54.4° were a=20.8580(8), b=20.8580(8), c=33.150(2) Å, and V=14 421.1(1) Å3. The intensity data were collected on a Rigaku Saturn-724 CCD diffractometer (MoKα radiation, λ=0.71073 Å) at 103 K. A total of 145 124 reflections were collected of which 16 491 reflections were independent (Rint=0.0791). The crystal structure was solved by direct methods using the SIR-2004 program[20] and refined by successive differential Fourier syntheses and full-matrix least-squares procedures using the SHELXL-97 program.[19] Anisotropic thermal factors were applied to all non-hydrogen atoms. All hydrogen atoms were generated geometrically. The structure was refined to final R1=0.124 for 11 715 data [I>2σ(I)] with 592 parameters, wR2=0.388 for all data, GOF=1.391, and residual electron density max/min=1.485/−1.636 e Å−3. The diffuse electron density arising from the disordered and unidentified moieties was treated with the SQUEEZE routine within the PLATON software package.[17] The final ρcalcd, F(000), and Mr values reflect known contents only. Statistical prior to treatment of data with SQUEEZE were R1=0.203 [I>2σ(I)], wR2=0.538 for all data, and GOF=2.111. CCDC 652008 (L1) and 652007 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. 16The highly disordered state of the incorporated molecules meant that none of them could be located, and hence in the final refinement, the electron density within the cages was treated with the SQUEEZE routine in the PLATON program package.[17] 17A. L. Spek, PLATON, University of Glasgow, Glasgow (Scotland), 1998. 18G. M. Sheldrick, SHELXS-97: Program for X-ray Crystal Structure Solution, University of Göttingen, Göttingen (Germany), 1997. 19G. M. Sheldrick, SHELXL-97: Program for X-ray Crystal Structure Refinement, University of Göttingen, Göttingen (Germany), 1997. 20M. C. Burla, R. Caliandro, M. Camalli, B, Carrozzini, G. L. Cascararo, L. De Caro, C. Giacovazzo, G. Polidori, R. Spagna, SIR-2004: A program for automatic solution and refinement of crystal structures. Citing Literature Volume47, Issue4January 11, 2008Pages 706-710 ReferencesRelatedInformation