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Redox‐Mediated Self‐Organization of Metallosupramolecular Architectures Composed of D ‐Penicillaminato Cu I 8 Cu II 6 Clusters: Drastic Structural Change by Subtle pH Changes

2010; Wiley; Volume: 16; Issue: 48 Linguagem: Inglês

10.1002/chem.201002780

1521-3765

Nobuto Yoshinari, Kazuhiro Tatsumi, A. Igashira-Kamiyama, Takumi Konno,

Nanocluster Synthesis and Applications

Chemistry – A European JournalVolume 16, Issue 48 p. 14252-14255 Communication Redox-Mediated Self-Organization of Metallosupramolecular Architectures Composed of D-Penicillaminato CuI8CuII6 Clusters: Drastic Structural Change by Subtle pH Changes Dr. Nobuto Yoshinari, Dr. Nobuto Yoshinari Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043 (Japan), Fax: (+81) 6-6850-5765Search for more papers by this authorKazuhiro Tatsumi, Kazuhiro Tatsumi Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043 (Japan), Fax: (+81) 6-6850-5765Search for more papers by this authorDr. Asako Igashira-Kamiyama, Dr. Asako Igashira-Kamiyama Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043 (Japan), Fax: (+81) 6-6850-5765Search for more papers by this authorProf. Takumi Konno, Corresponding Author Prof. Takumi Konno [email protected] Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043 (Japan), Fax: (+81) 6-6850-5765Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043 (Japan), Fax: (+81) 6-6850-5765Search for more papers by this author Dr. Nobuto Yoshinari, Dr. Nobuto Yoshinari Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043 (Japan), Fax: (+81) 6-6850-5765Search for more papers by this authorKazuhiro Tatsumi, Kazuhiro Tatsumi Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043 (Japan), Fax: (+81) 6-6850-5765Search for more papers by this authorDr. Asako Igashira-Kamiyama, Dr. Asako Igashira-Kamiyama Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043 (Japan), Fax: (+81) 6-6850-5765Search for more papers by this authorProf. Takumi Konno, Corresponding Author Prof. Takumi Konno [email protected] Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043 (Japan), Fax: (+81) 6-6850-5765Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043 (Japan), Fax: (+81) 6-6850-5765Search for more papers by this author First published: 29 November 2010 https://doi.org/10.1002/chem.201002780Citations: 17Read 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 Graphical Abstract pH-dependent architecture: Cluster-based metallosupramolecular compounds, which are composed of [CuI6CuII8(D-pen)12Cl]5− (D-H2pen=D-penicillamine) cluster anions linked by Co2+ and/or K+ cations through D-pen carboxylate groups, were spontaneously synthesized by simple treatment of K[CoIII(D-pen)2] with CuICl in potassium acetate buffer solutions, accompanied by the redox between CoIII and CuI mediated by thiolate. References 1 1aS. G. Murray, F. R. Hartley, Chem. Rev. 1981, 81, 365– 414; 1bB. Krebs, G. Henkel, Angew. Chem. 1991, 103, 785– 804; Angew. Chem. Int. Ed. Engl. 1991, 30, 769– 788; 1cD. W. Stephan, T. T. Nadasdi, Coord. Chem. Rev. 1996, 147, 147– 208. 2 2aA. C. Marr, D. J. E. Spencer, M. Schröder, Coord. Chem. Rev. 2001, 219–221, 1055– 1074; 2bT. Konno, Bull. Chem. Soc. Jpn. 2004, 77, 627– 649; 2cM. W. Degroot, J. F. Corrigan in Comprehensive Coordination Chemistry II—From biology to Nanotechnology; Vol. 7, (Eds.: ), Elsevier, Oxford, 2004; pp. 57– 123; 2dP. V. Rao, S. Bhaduri, J. Jiang, R. H. Holm, Inorg. Chem. 2004, 43, 5833– 5849; 2eZ.-N. Chen, N. Zhao, Y. Fan, J. Ni, Coord. Chem. Rev. 2009, 253, 1– 20; 2fS. Canaguier, L. Vaccaro, V. Artero, R. Ostermann, J. Pécaut, M. J. Field, M. Fontecave, Chem. Eur. J. 2009, 15, 9350– 9364. 3 3aT. Konno, K. Okamoto, J. Hidaka, Inorg. Chem. 1992, 31, 3875– 3876; 3bY. Miyashita, Y. Yamada, K. Fujisawa, T. Konno, K. Kanamori, K. Okamoto, J. Chem. Soc. Dalton Trans. 2000, 981– 987; 3cA. Igashira-Kamiyama, J. Fujioka, S. Mitsunaga, M. Nakano, T. Kawamoto, T. Konno, Chem. Eur. J. 2008, 14, 9512– 9515. 4K. Okamoto, K. Wakayama, H. Einaga, S. Yamada, J. Hidaka, Bull. Chem. Soc. Jpn. 1983, 56, 165– 170. 5See the Supporting Information. 6K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, 5th ed., Wiley Interscience, Chichester, 1997. 7 7aP. J. M. W. L. Birker, H. C. Freeman, J. Chem. Soc. Chem. Commun. 1976, 312– 313; 7bP. J. M. W. L. Birker, H. C. Freeman, J. Am. Chem. Soc. 1977, 99, 6890– 6899. 8Magnetic susceptibility data for 1 were recorded in the temperature range of 2–300 K.[5] The χMT value at 300 K (10.46 cm3 K mol−1) is much larger than the spin-only value of 7.88 cm3 K mol−1 for the magnetically diluted 6 CuII and 3 high-spin CoII centers with the g value of 2.0. On lowering the temperature, the χMT values continuously decrease due to the presence of large magnetic anisotropy of CoII centers, which prevented the further analysis of the magnetic behavior of 1. 9A similar octameric cubic structure was found in Tl5[CuI8CuII6(D-pen)12], but the encapsulation of cationic species inside the cube was not observed for this compound. 10The pK (i=1–12) values for [CuI8CuII6(D-pen)12Cl]5− were calculated from the analysis of the titration curve of 1 with aqueous HCl, assuming that the difference between pK and pK is constant (C). The most reliable values obtained from this analysis is pK=4.35 and C=0.54 with the final agreement factor R=2.1×10−4. In addition, the molar fractions of [Cu14(D-Hpen)n(D-pen)12−nCl](5−n)− (n=0–12) at each pH were evaluated based on the calculated pK values. The distribution diagram of the deprotonated and protonated species in the pH range of 4.0–7.0 indicates that the fully deprotonated form is dominant when the solution pH is larger than 5.0, while the deprotonated and protonated species coexist comparably at pH 4.5.[5] 11The use of a more acidic buffer solution (pH 6.5) gave a colorless powder that contains organic species. 12 12aS. Kitagawa, S. Noro in Comprehensive Coordination Chemistry II—From biology to Nanotechnology; Vol. 7, (Eds.: ), Elsevier, Oxford., 2004; pp. 231– 261; 12bM. Fujita, M. Tominaga, A. Hori, B. Therrien, Acc. Chem. Res. 2005, 38, 369– 378; 12cR. Ganguly, B. Sreenivasulu, J. J. Vittal, Coord. Chem. Rev. 2008, 252, 1027– 1050; 12dS. J. Dalgarno, N. P. Power, J. L. Atwood, Coord. Chem. Rev. 2008, 252, 825– 841. Citing Literature Supporting Information Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Filename Description chem_201002780_sm_miscellaneous_information.pdf399.7 KB miscellaneous_information 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. Volume16, Issue48December 27, 2010Pages 14252-14255 ReferencesRelatedInformation