10.1002/chem.201905390
Chemistry - A European Journal
FULL PAPER
oligomers which serve as hosts for fullerenes C60 and C70. The
inclusion of fullerenes was observed by single crystal X-ray
diffractometry, NMR, and was validated using computations.
These metallacycles are robust and show no sign of
decomposition. Although computations on such large systems
are challenging, we were able to model the C60/C70
encapsulated metallacycles and even predict spectroscopic data,
which are in strong agreement with the experimental results.
Electrostatic potential maps reveal that the positive charges of
the cavity cores can be tuned by the peripheral halide co-ligands.
These computations help to provide a deeper understanding of
host-guest interaction in these metallacycles. Similar
computations will no doubt be useful for the rational design of
host molecules with other cargo. In the future, these complexes
could serve as container molecules transporting important
cargo.[2f, 21]
Liepold, J. Abedin, E. D. Buckhouse, J. A. Frank, M. J.
Young, T. Douglas, Nano Lett. 2009, 9, 4520-4526; (e) S.
van Dun, C. Ottmann, L. G. Milroy, L. Brunsveld, J. Am.
Chem. Soc. 2017, 139, 13960-13968; (f) M. J. Webber, R.
Langer, Chem. Soc. Rev. 2017, 46, 6600-6620; (g) X. Yan,
T. R. Cook, P. Wang, F. Huang, P. J. Stang, Nat. Chem.
2015, 7, 342-348.
[3] (a) R. Chakrabarty, P. S. Mukherjee, P. J. Stang, Chem.
Rev. 2011, 111, 6810-6918; (b) M. Zhang, H. Xu, M. Wang,
M. L. Saha, Z. Zhou, X. Yan, H. Wang, X. Li, F. Huang, N.
She, P. J. Stang, Inorg. Chem. 2017, 56, 12498-12504.
[4] (a) J. Langer, B. Maitland, S. Grams, A. Ciucka, J. Pahl, H.
Elsen, S. Harder, Angew. Chem. Int. Ed. 2017, 56, 5021-
5025; (b) I. M. Müller, D. Möller, K. Föcker, Chem. Eur. J.
2005, 11, 3318-3324; (c) I. M. Müller, R. Robson, Angew.
Chem. Int. Ed. 2000, 39, 4357-4359; (d) N. Sahiner, S.
Butun Sengel, M. Yildiz, J. Coord. Chem. 2017, 70, 3619-
3632; (e) A. J. Tasiopoulos, A. Vinslava, W. Wernsdorfer,
K. A. Abboud, G. Christou, Angew. Chem. Int. Ed. 2004,
116, 2169-2173.
CCDC numbers: 1830922 (3), 1830936 (5-Cl), 1830997 (6),
1851696 (7), 1831512 (8), 1831515 (C60⊂9), 1831516 (C70⊂9)
[5] (a) A. Baniodeh, N. Magnani, Y. Lan, G. Buth, C. E. Anson,
J. Richter, M. Affronte, J. Schnack, A. K. Powell, npj
Quantum Mater. 2018, 3, 1-6; (b) W. Brenner, T. K.
Ronson, J. R. Nitschke, J. Am. Chem. Soc. 2017, 139, 75-
78; (c) E. Huerta, E. Cequier, J. de Mendoza, Chem.
Commun. 2007, 5016-5018; (d) G. F. Whitehead, F. Moro,
G. A. Timco, W. Wernsdorfer, S. J. Teat, R. E. Winpenny,
Angew. Chem. Int. Ed. 2013, 52, 9932-9935.
[6] (a) T. B. Karpishin, T. D. P. Stack, K. N. Raymond, Journal
of the American Chemical Society 1993, 115, 182-192; (b)
R. W. Saalfrank, A. Stark, K. Peters, H. G. von Schnering,
Angew. Chem. Int. Ed. 1988, 27, 851-853; (c) P. J. Stang,
B. Olenyuk, D. C. Muddiman, R. D. Smith, Organometallics
1997, 16, 3094-3096.
[7] (a) R. A. Bilbeisi, T. K. Ronson, J. R. Nitschke, Angew.
Chem. Int. Ed. 2013, 125, 9197-9200; (b) J. L. Bolliger, A.
M. Belenguer, J. R. Nitschke, Angew. Chem. Int. Ed. 2013,
52, 7958-7962; (c) M. Kawano, Y. Kobayashi, T. Ozeki, M.
Fujita, J. Am. Chem. Soc. 2006, 128, 6558-6559; (d) T.
Kusukawa, M. Fujita, J. Am. Chem. Soc. 2002, 124,
13576-13582; (e) P. Mal, B. Breiner, K. Rissanen, J. R.
Nitschke, Science 2009, 324, 1697-1699; (f) W. J. Ramsay,
T. K. Ronson, J. K. Clegg, J. R. Nitschke, Angew. Chem.
Int. Ed. 2013, 52, 13439-13443; (g) R. W. Saalfrank, A.
Stark, K. Peters, H. G. von Schnering, Angew. Chem. Int.
Ed. 1988, 27, 851-853.
Acknowledgement
We gratefully acknowledge the International Research
Training Group 1628 SeleCa "Selectivity in Chemo- and Bio-
gemeinschaft) for funding this work. Furthermore we like to
thank Dr. Khai Nghi Truong from the group of Prof. Dr. Ulli
Englert (RWTH Aachen University) and Manuela Winter from the
group of Prof. Dr. Roland A. Fischer (Ruhr-Universität Bochum)
for collection single crystal X-ray diffraction data, Rachida
Bomahrat and Dr. Gerhard Fink for NMR spectroscopic
measurements.
We are grateful to the Alexander von Humboldt Foundation
for support of A.E. We thank Prof. Dr. John A. Gladysz (Texas
A&M University) and the U.S. National Science Foundation
(CHE-1566601, 1664866) for financial support. We thank Prof.
Dr. Michael B. Hall and Dr. Lisa M. Pérez (Texas A&M
University) for fruitful discussions and the Laboratory for
Molecular Simulation. We thank the Texas A&M High
Performance Research Computing Facility for computational
resources. We thank Prof. Dr. Steven E. Wheeler (University of
Georgia) for providing scripts to generate ESP plots.
[8] J.-M. Lehn, Angew. Chem. Int. Ed. 1988, 27, 89-112.
[9] M. J. Langton, C. J. Serpell, P. D. Beer, Angew. Chem. Int.
Ed. 2016, 55, 1974-1987.
[10] T. Auletta, M. R. de Jong, A. Mulder, F. C. van Veggel, J.
Huskens, D. N. Reinhoudt, S. Zou, S. Zapotoczny, H.
Schonherr, G. J. Vancso, L. Kuipers, J. Am. Chem. Soc.
2004, 126, 1577-1584.
Conflict of interest
The authors declare no conflict of interest.
[11] S. I. Kawano, T. Fukushima, K. Tanaka, Angew. Chem. Int.
Ed. 2018, 57, 14827-14831.
[12] (a) K. Jelfs, R. L. Greenaway, L. Turcani, M. Miklitz,
ChemRxviv 2019,
Keywords: cage compounds • fullerenes • host-guest-systems •
self assembly • DFT calculations
DOI: 10.26434/chemrxiv.9757862.v9757861; (b) Y. Xu, M.
von Delius, Angew. Chem. Int. Ed. 2019, accepted article,
DOI: 10.1002/anie.201906069.
[1] T. R. Cook, P. J. Stang, Chem. Rev. 2015, 115, 7001-7045.
[2] (a) Y. Cai, H. Shen, J. Zhan, M. Lin, L. Dai, C. Ren, Y. Shi,
J. Liu, J. Gao, Z. Yang, J. Am. Chem. Soc. 2017, 139,
2876-2879; (b) I. V. Grishagin, J. B. Pollock, S. Kushal, T.
R. Cook, P. J. Stang, B. Z. Olenyuk, Proc. Natl. Acad. Sci.
USA 2014, 111, 18448-18453; (c) X. Li, J. Tsibouklis, T.
Weng, B. Zhang, G. Yin, G. Feng, Y. Cui, I. N. Savina, L. I.
Mikhalovska, S. R. Sandeman, C. A. Howel, S. V.
Mikhalovsky, J. Drug. Target. 2017, 25, 17-28; (d) L. O.
[13] (a) I. M. Müller, R. Robson, F. Separovic, Angew. Chem.
Int. Ed. 2001, 40, 4385-4386; (b) I. M. Müller, S. Spillmann,
H. Franck, R. Pietschnig, Chem. Eur. J. 2004, 10, 2207-
2213; (c) I. M. Müller, D. Möller, Angew. Chem. Int. Ed.
2005, 44, 2969-2973; (d) C. von Eßen, C. R. Göb, I. M.
Oppel, in Guanidines as Reagents and Catalysts II, 2015,
pp. 75-94.
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