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for 438 Å when the temperature is lowered to 100 K. Such
Notes and references
DOI: 10.1039/C6CC04912E
slight contraction makes the channel dimension (ca. 3.8
Å , diagonal 5.3 Å) even closer to the kinetic diameters for N
3.64 Å), as shown in Fig. 5a. Interestingly, on the contrary, the
diameter of the rod (measured by CdCd separation distance
in ab plane) increases (Fig. 5b). We observe that the rod
geometry in the room-temperature phase is close to the 8-fold
BC helix above (Fig. 1d), while in the low-temperature phase it
deviates more drastically from 8-fold symmetry. In the net
wuy with optimized symmetry there are two types of
3.8
1
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2
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II
tetrahedra (Fig. 2d), whereas in ROD-1 there is only one Cd .
3
41, 1230444.
4
(a) B.-Q. Song, X.-L. Wang, Y.-T. Zhang, X.-S. Wu, H.-S. Liu, K.-
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Table 1 Comparison of selected structural parameters for ROD-1 at various conditions.
ROD-1-
93K
ROD-1-100K
ROD-1-CO
100K
2
-
ROD-1-N
100K
2
-
,
d
e
2
5
6
7
8
A. K. Inge, M. Kꢀppen, J. Su, M. Feyand, H. Xu, X. Zou, M.
O’Keeffe and N. Stock, J. Am. Chem. Soc., 2016, 138, 1970.
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a = b (Å)
c (Å)
24.5830(4)
10.8704(3)
6569.2(2)
2494.3
24.0666(7)
10.5856(11)
6131.2(7)
2361.3
24.6108(3)
10.76785(17)
6522.0(14)
2394.8
24.0290(5)
10.5501(3)
6091.5(3)
2334.3
3
a
V (Å )
2
b
A (m /g)
,
Void (%) c
37.8
33.0
37.1
32.7
a
b
Space group: tetragonal I4
1
/a. See Table S1 in ESI† for detailed data. Connolly
Coxeter, Regular Complex Polytopes, Cambridge University
Press, 1st ed. 1974, 2nd ed. 1991; (c) J. D. Bernal, Nature,
c
d
surface area (probe radius 1.0 Å). Void volume defined by Connolly surface.
After N adsorption
adsorption (77 K) and then determined at 100 K. e After CO
193 K) and then determined at 100 K.
2
2
1
960, 185, 68.
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(
9
1
After N
see Table 1). This can well explain the abnormal retention as
desorption isotherm at 77 K (Fig. 4a),
considering the matching size of adsorbent/adsorbate. In
comparison, the unit cell of the CO -adsorbed phase is similar
to that of the room-temperature phase. Unfortunately, we
were not able to determine the locations of the CO guests
2
adsorption the unit cell is even smaller at 100 K
E. Luijten and S. Granick, Science, 2011, 331, 199; (c) Y. Zhu, J.
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(
observed in the N
2
1
1
2
2
experimentally. In order to interpret the unusual phenomenon
of increasing enthalpy and decreasing entropy change upon
F. Deng, J.-P. Zhang and X.-M. Chen, Nat. Commun., 2013,
534; (d) H.-L. Zhou, Y.-B. Zhang, J.-P. Zhang and X.-M. Chen,
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4,
2
CO loading (Fig. 4b inset), we have performed preliminary
2
grand canonical Monte Carlo (GCMC) simulations (see the
6
Computational Section in ESI†).13a As expected, the adsorbed 12 (a) O. Delgado-Friedrichs and M. O’Keeffe, Acta Crystallogr.
A, 2003, 59, 351; (b) V. A. Blatov, A. P. Shevchenko and D. M.
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CO
ROD-1 statistically (Fig. S6a in ESI†). A snapshot at the lowest
energy clearly shows the cooperative CO -CO interactions
shortest distance 2.948 Å) within the channels (Fig. S6b in
2
molecules are found to reside in the ultramicropores of
1
3 (a) S. Nandi, P. D. Luna, T. D. Daff, J. Rother, M. Liu, W.
Buchanan, A. I. Hawari, T. K. Woo and R. Vaidhyanathan, Sci.
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2
(
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ESI†).
Burd, A. J. Cairns, R. Luebke, K. Forrest, T. Pham, S. Ma, B.
There are a number of rod MOFs with helical SBUs,2a,6,16
Space, L. Wojtas, M. Eddaoudi and M. J. Zaworotko, Nature,
2
013, 495, 80; (c) S. Xiang, Y. He, Z. Zhang, H. Wu, W. Zhou, R.
including the frequently studied MOF-74/CPO-27 and MOF-76,
but their topological descriptions remained unsolved because
the underlying geometrical pattern, i.e. aperiodic helices of
face-sharing polyhedra, was not identified prior to this work.
The present work provides a unique deconstruction method
inspired by the Boerdijk-Coxeter helix. Furthermore, ROD-1
exhibits unit cell changes responding to temperature variation
and gas adsorption, which deserves to be studied in depth and
is the topic of an ongoing work.
This work was financially supported by the National Basic
Research Program of China (973 Program, Nos. 2012CB821706
and 2013CB834803), and the National Natural Science
Foundation of China (Nos. 91222202 and 21171114). We thank
Wei Chen and Dong Luo for helps on some data analysis.
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1
4
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