A Face-to-Face Dimer of Au3 Superatoms Supported by Interlocked Tridentate Scaffolds Formed in Au18S2(SR)12
Taro Shigeta
Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 1130033 Japan
Search for more papers by this authorDr. Shinjiro Takano
Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 1130033 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Tatsuya Tsukuda
Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 1130033 Japan
Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, 1-30 Goryo-Ohara, Nishikyo-ku, Kyoto, 6158245 Japan
Search for more papers by this authorTaro Shigeta
Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 1130033 Japan
Search for more papers by this authorDr. Shinjiro Takano
Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 1130033 Japan
Search for more papers by this authorCorresponding Author
Prof. Dr. Tatsuya Tsukuda
Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 1130033 Japan
Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, 1-30 Goryo-Ohara, Nishikyo-ku, Kyoto, 6158245 Japan
Search for more papers by this authorGraphical Abstract
Au18S2(SR)12, a new gold cluster that can be viewed as an interlocked dimer of Au9S(SR)6 cages, was synthesized using a bulky thiol ligand. Theoretical calculation demonstrated that the Au6 core can be interpreted as a face-to-face dimer of Au3 superatoms.
Abstract
A new sulfur-containing gold cluster, Au18S2(STipb)12, was serendipitously obtained using the bulky thiol, 2,4,6-triisopropylbenzyl mercaptan (TipbSH), as protecting ligands. Single-crystal X-ray diffraction analysis revealed that Au18S2(STipb)12 has a deformed octahedral Au6 core clutched by two tridentate S[Au2(STipb)2]3 units in an interlocked manner. Based on density functional theory calculations, we propose that the Au6 core with two electrons is better viewed as a face-to-face dimer of Au3(1e) superatoms rather than an electronically closed Au6(2e) superatom. In situ formation of the sulfide anions (S2−) via C-S bond breakage is ascribed to the steric repulsion between the TipbS ligands.
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References
- 1R. Jin, C. Zhen, M. Zhou, Y. Chen, Chem. Rev. 2016, 116, 10346–10413.
- 2I. Chakraborty, T. Pradeep, Chem. Rev. 2017, 117, 8208–8271.
- 3H. Hirai, S. Ito, S. Takano, K. Koyasu, T. Tsukuda, Chem. Sci. 2020, 11, 12233–12248.
- 4M. Walter, J. Akola, O. Lopez-Acevedo, P. D. Jadzinsky, G. Calero, C. J. Ackerson, R. L. Whetten, H. Grönbeck, H. Häkkinen, Proc. Natl. Acad. Sci. USA 2008, 105, 9157–9162.
- 5S. Takano, T. Tsukuda, J. Am. Chem. Soc. 2021, 143, 1683–1698.
- 6T. Omoda, S. Takano, T. Tsukuda, Small 2021, 17, 2001439.
- 7L. Cheng, C. Ren, X. Zhang, J. Yang, Nanoscale 2013, 5, 1475–1478.
- 8J. Nishigaki, K. Koyasu, T. Tsukuda, Chem. Rec. 2014, 14, 897–909.
- 9T. Dainese, S. Antonello, S. Bogialli, W. Fei, A. Venzo, F. Maran, ACS Nano 2018, 12, 7057–7066.
- 10E. Ito, S. Takano, T. Nakamura, T. Tsukuda, Angew. Chem. Int. Ed. 2021, 60, 645–649; Angew. Chem. 2021, 133, 655–659.
- 11M. Brust, M. Walker, D. Bethell, D. J. Schiffrin, R. Whyman, J. Chem. Soc. Chem. Commun. 1994, 801–802.
- 12Y. Pei, P. Wang, Z. Ma, L. Xiong, Acc. Chem. Res. 2019, 52, 23–33.
- 13H. Häkkinen, Nat. Chem. 2012, 4, 443–455.
- 14T. Higaki, C. Zeng, Y. Chen, E. Hussain, R. Jin, CrystEngComm 2016, 18, 6979–6986.
- 15S. Hossain, Y. Imai, D. Suzuki, W. Choi, Z. Chen, T. Suzuki, M. Yoshioka, T. Kawawaki, D. Lee, Y. Negishi, Nanoscale 2019, 11, 22089–22098.
- 16T. Omoda, S. Takano, S. Yamazoe, K. Koyasu, Y. Negishi, T. Tsukuda, J. Phys. Chem. C 2018, 122, 13199–13204.
- 17D. Crasto, S. Malola, G. Brosofsky, A. Dass, H. Häkkinen, J. Am. Chem. Soc. 2014, 136, 5000–5005.
- 18C. Liu, T. Li, G. Li, K. Nobusada, C. Zeng, G. Pang, N. L. Rosi, R. Jin, Angew. Chem. Int. Ed. 2015, 54, 9826–9829; Angew. Chem. 2015, 127, 9964–9967.
- 19T. C. Jones, L. Sementa, M. Stener, K. J. Gagnon, V. D. Thanthirige, G. Ramakrishna, A. Fortunelli, A. Dass, J. Phys. Chem. C 2017, 121, 10865–10869.
- 20T. Higaki, C. Liu, M. Zhou, T.-Y. Luo, N. L. Rosi, R. Jin, J. Am. Chem. Soc. 2017, 139, 9994–10001.
- 21J. Nishigaki, R. Tsunoyama, H. Tsunoyama, N. Ichikuni, S. Yamazoe, Y. Negishi, M. Ito, T. Matsuo, K. Tamao, T. Tsukuda, J. Am. Chem. Soc. 2012, 134, 14295–14297.
- 22J. Nishigaki, S. Yamazoe, S. Kohara, A. Fujiwara, W. Kurashige, Y. Negishi, T. Tsukuda, Chem. Commun. 2014, 50, 839–841.
- 23T. Omoda, S. Takano, T. Tsukuda, Chem. Lett. 2019, 48, 885–887.
- 24Deposition Number 2067702 contains the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service www.ccdc.cam.ac.uk/structures.
- 25J. B. Tracy, M. C. Crowe, J. F. Parker, O. Hampe, C. A. Fields-Zinna, A. Dass, R. W. Murray, J. Am. Chem. Soc. 2007, 129, 16209–16215.
- 26M. Fujita, N. Fujita, K. Ogura, K. Yamaguchi, Nature 1999, 400, 52–55.
- 27M. R. Wiseman, P. A. Marsh, P. T. Bishop, B. J. Brisdon, M. F. Mahon, J. Am. Chem. Soc. 2000, 122, 12598–12599.
- 28S. S.-Y. Chui, R. Chen, C.-M. Che, Angew. Chem. Int. Ed. 2006, 45, 1621–1624; Angew. Chem. 2006, 118, 1651–1654.
- 29A. Das, T. Li, G. Li, K. Nobusada, C. Zeng, N. L. Rosi, R. Jin, Nanoscale 2014, 6, 6458–6462.
- 30F. Demartin, M. Manassero, L. Naldini, R. Ruggeri, M. Sansoni, J. Chem. Soc. Chem. Commun. 1981, 222–223.
- 31J. W. A. van der Velden, J. J. Bour, R. Pet, W. P. Bosman, J. H. Noordik, Inorg. Chem. 1983, 22, 3112–3115.
- 32E. Zeller, H. Beruda, H. Schmidbaur, Inorg. Chem. 1993, 32, 3203–3204.
- 33Y. Yang, P. R. Sharp, J. Am. Chem. Soc. 1994, 116, 6983–6984.
- 34M. J. Calhorda, O. Crespo, M. C. Gimeno, P. G. Jones, A. Laguna, J. M. López-de-Luzuriaga, J. L. Perez, M. A. Ramón, L. F. Veiros, Inorg. Chem. 2000, 39, 4280–4285.
- 35D. Zhang, J. Dou, D. Li, D. Wang, J. Coord. Chem. 2007, 60, 825–831.
- 36A. Das, C. Liu, H. Y. Byun, K. Nobusada, S. Zhao, N. Rosi, R. Jin, Angew. Chem. Int. Ed. 2015, 54, 3140–3144; Angew. Chem. 2015, 127, 3183–3187.
- 37S. Chen, S. Wang, J. Zhong, Y. Song, J. Zhang, H. Sheng, Y. Pei, M. Zhu, Angew. Chem. Int. Ed. 2015, 54, 3145–3149; Angew. Chem. 2015, 127, 3188–3192.
- 38Y. Negishi, K. Nobusada, T. Tsukuda, J. Am. Chem. Soc. 2005, 127, 5261–5270.
- 39Q. Yao, Y. Yu, X. Yuan, Y. Yu, J. Xie, J. Y. Lee, Small 2013, 9, 2696–2701.
- 40R. Itteboina, U. D. Madhuri, P. Ghosal, M. Kannan, T. K. Sau, T. Tsukuda, S. Bhardwaj, J. Phys. Chem. A 2018, 122, 1228–1234.
