10.1002/anie.201912911
Angewandte Chemie International Edition
COMMUNICATION
which is consistent that the removal of the coordinating ligand
leads to facile shifting of the individual sheets. The flexibility of the
organosilicon linker may further disrupt crystalline packing in the
absence of a directing solvent. Reintroduction of a coordinating
polar solvent molecule restores the crystallinity, suggesting that
ligand coordination and solvent polarity are important for ordering
the MOF layers. These reversible conversions further confirm the
structural integrity of each 2D sheet.
In summary, we have demonstrated the use of oligosilyl
moieties to generate a new class of chemically-responsive MOFs
composed of Cu paddlewheel nodes and SinMe2n(PhCO2H)2
linkers. Uniquely, Cu(lin-Sin) MOFs can achieve multiple
crystalline and amorphous states, offering new opportunities
beyond binary “on-off” applications. We postulate the identity and
polarity of the encapsulated solvent directs the stacking
arrangements of the 2D MOF layers. Structural characterization
of the various crystalline and amorphous MOF phases is under
active experimental and computational investigation. The high
degree of reversibility with these structural changes and the
availability of multiple stable states are attractive for molecular
sensing (e.g. alcohols, nitroaromatics, etc.) and memory storage
applications among others. The modularity and diversity of these
MOFs pave the way for a unique class of hybrid oligosilyl
materials which take advantage of the unique chemical properties
of oligosilanes.
13280–13283.
[7]
A. Halder, D. Ghoshal, CrystEngComm 2018, 20, 1322–
1345.
[8]
H. Tan, Q. Chen, Y. Sheng, X. Li, H. Liu, CrystEngComm
2018, 20, 6828–6833.
[9]
J.-W. Xiu, G.-E. Wang, M.-S. Yao, C.-C. Yang, C.-H. Lin, G.
Xu, Chem. Commun. 2017, 53, 2479–2482.
R. M. P. Colodrero, K. E. Papathanasiou, N.
Stavgianoudaki, P. Olivera-Pastor, E. R. Losilla, M. A. G.
Aranda, L. León-Reina, J. Sanz, I. Sobrados, D.
Choquesillo-Lazarte, et al., Chem. Mater. 2012, 24, 3780–
3792.
[10]
[11]
[12]
R. D. Miller, J. Michl, Chem. Rev. 1989, 89, 1359–1410.
J. Koe, M. Fujiki, in Organosilicon Compd., Elsevier, 2017,
pp. 219–300.
[13]
[14]
R. S. Klausen, J. R. Widawsky, M. L. Steigerwald, L.
Venkataraman, C. Nuckolls, J. Am. Chem. Soc. 2012, 134,
4541–4544.
T. A. Su, H. Li, R. S. Klausen, N. T. Kim, M. Neupane, J. L.
Leighton, M. L. Steigerwald, L. Venkataraman, C. Nuckolls,
Acc. Chem. Res. 2017, 50, 1088–1095.
[15]
[16]
J. Zhou, S. K. Surampudi, A. E. Bragg, R. S. Klausen,
Chem. - A Eur. J. 2016, 22, 6204–6207.
S. Surampudi, M.-L. Yeh, M. A. Siegler, J. F. M. Hardigree,
T. A. Kasl, H. E. Katz, R. S. Klausen, Chem. Sci. 2015, 6,
1905–1909.
CCDC 1893669, 1893670, and 1893671 contain the supplementary
crystallographic data for this paper. These data are provided free of charge
by The Cambridge Crystallographic Data Centre.
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
J. B. Lambert, Z. Liu, C. Liu, Organometallics 2008, 27,
1464–1469.
R. P. Davies, R. J. Less, P. D. Lickiss, K. Robertson, a J.
P. White, Inorg. Chem. 2008, 47, 9958–9964.
R. P. Davies, R. Less, P. D. Lickiss, K. Robertson, A. J. P.
White, Cryst. Growth Des. 2010, 10, 4571–4581.
I. Timokhin, J. Baguña Torres, A. J. P. White, P. D. Lickiss,
C. Pettinari, R. P. Davies, Dalt. Trans. 2013, 42, 13806.
M. Xu, S.-S. Yang, Z.-Y. Gu, Chem. - A Eur. J. 2018, 24,
15131–15142.
Acknowledgements
We thank the Department of Chemistry and Johns Hopkins
University for instrumentation support, graduate student support,
and start-up funding. D.A.B also thanks the Department of
Chemistry for a Harry and Cleio Research Fellowship. R.S.K.
thanks the Alfred P. Sloan Foundation for a Sloan Research
Fellowship. We would also like to thank Mr. Hector Vivanco and
Prof. Tyrel McQueen for assistance with PXRD.
W. Zhao, J. Peng, W. Wang, S. Liu, Q. Zhao, W. Huang,
Coord. Chem. Rev. 2018, 377, 44–63.
M. G. Campbell, D. Sheberla, S. F. Liu, T. M. Swager, M.
Dincă, Angew. Chemie Int. Ed. 2015, 54, 4349–4352.
K. Wada, K. Sakaushi, S. Sasaki, H. Nishihara, Angew.
Chemie Int. Ed. 2018, 57, 8886–8890.
Keywords: Metal-Organic Frameworks • Silanes • 2D Materials
• Structural Interconversion • Phase Change
J. Huang, Y. Li, R.-K. Huang, C.-T. He, L. Gong, Q. Hu, L.
Wang, Y.-T. Xu, X.-Y. Tian, S.-Y. Liu, et al., Angew.
Chemie Int. Ed. 2018, 57, 4632–4636.
[1]
A. Schneemann, V. Bon, I. Schwedler, I. Senkovska, S.
Kaskel, R. A. Fischer, Chem. Soc. Rev. 2014, 43, 6062–
6096.
[26]
[27]
J. Michl, R. West, Acc. Chem. Res. 2000, 33, 821–823.
J. C. Giordan, J. H. Moore, J. Am. Chem. Soc. 1983, 105,
6541–6544.
[2]
[3]
[4]
[5]
[6]
Z. Chang, D.-H. Yang, J. Xu, T.-L. Hu, X.-H. Bu, Adv.
Mater. 2015, 27, 5432–5441.
M. Nihei, L. Han, H. Oshio, J. Am. Chem. Soc. 2007, 129,
5312–5313.
[28]
H. Sakurai, M. Ichinose, M. Kira, T. G. Traylor, Chem. Lett.
1984, 13, 1383–1384.
E. Coronado, G. Mínguez Espallargas, Chem. Soc. Rev.
2013, 42, 1525–1539.
[29]
[30]
A. L. Smith, Spectrochim. Acta 1960, 16, 87–105.
N. Koji, Infrared Absorption Spectroscopy - Practical,
Holden-Day, San Francisco, California, 1964.
F. Verpoort, T. Haemers, P. Roose, J. P. Maes, Appl.
Spectrosc. 1999, 53, 1528–1534.
R. A. Heintz, H. Zhao, X. Ouyang, G. Grandinetti, J.
Cowen, K. R. Dunbar, Inorg. Chem. 1999, 38, 144–156.
B. J. Furlong, M. J. Katz, J. Am. Chem. Soc. 2017, 139,
[31]
This article is protected by copyright. All rights reserved.