A catenated strut in a catenated metal-organic framework

Article abstract of DOI:10.1002/anie.201003221

MIMs meet MOFs: Mechanically interlocked molecules (MIMs), in the form of donor-acceptor [2]catenane-containing struts of exceptional length, have been incorporated into a three-dimensional catenated metal-organic framework (MOF) at precise locations and with uniform relative orientations. Catenation is expressed simultaneously within the struts and the framework. (Figure Equotion Present)

Full text of DOI:10.1002/anie.201003221

Angewandte
Chemie
DOI: 10.1002/anie.201003221
Metal–Organic Frameworks
A Catenated Strut in a Catenated Metal–Organic Framework**
Qiaowei Li, Chi-Hau Sue, Subhadeep Basu, Alexander K. Shveyd, Wenyu Zhang, Gokhan Barin,
Lei Fang, Amy A. Sarjeant, J. Fraser Stoddart,* and Omar M. Yaghi*
The integration of mechanically interlocked molecules
(MIMs)[1] into metal–organic frameworks (MOFs)[2] provides
a way of coupling[3] the workings[4] and addressability[5] of the
former to the robustness and modularity of the latter. When
MIMs are covalently linked to MOFs in such a well-defined
fashion, the incoherent translational motion, which is
observed in solution for the MIM progenitors, is eliminated.
Although we have already shown that struts (2 nm in length)
bearing components of MIMs, such as crown ethers,[6]
pseudorotaxanes,[7] and catenanes,[8] can be reticulated into
open MOFs,[9] when we attempted to build MOFs with three-
dimensional structures incorporating catenane struts at this
length scale, the only structure obtained[9b] was a two-dimen-
sional one. Herein, we report the synthesis of a strut of
exceptional length (3.3 nm) and describe its assembly into a
three-dimensional MOF structure with vast openness, allow-
ing bulky MIMs to be anchored at precise locations and with
uniform relative orientations throughout the framework as a
whole.
total of 7524 atoms (ignoring anions and solvent molecules)
including those present in the 36 donor–acceptor [2]cate-
nanes. While CATDC constitutes the longest link to be
employed in MOF chemistry to date, the new extended
structure is unique in so far as catenation is expressed
simultaneously within the struts and the framework.
The synthesis of the extended strut CATDC, wherein 1,5-
naphthoparaphenylene[36]crown-10 (NPP36C10) is grafted
into its midriff by a modular synthetic protocol,[10] prior to
being catenated with
a cyclobis(paraquat-p-phenylene)
(CBPQT4+) ring,[11] is illustrated in Figure 1. I2-NPP36C10
was reacted in DMF employing Sonogashira coupling[12]
conditions, with the substituted acetylene derivatives 1 (R =
Me) and 2 (R = tBu) to give, respectively, the struts CEME
and CEBU.[13] De-esterification of CEME (base-promoted)
and CEBU (acid-catalyzed) both afforded the same CEDC
strut terminated by carboxyl groups. Although catenation
with the well-established precursors of the CBPQT4+ ring,
followed by counterion exchange, yielded the required
CATDC for MOF preparation, this compound exhibited
low solubility in most polar organic solvents and was there-
fore difficult to characterize. Consequently, CEME was also
subjected to catenation under exactly the same conditions to
yield the dimethyl diester CATME, which was fully charac-
Specifically, a catenated dicarboxylic acid (CATDC) strut
was joined to copper(I) to give a catenated three-dimensional
MOF, namely MOF-1030, in which each unit cell contains a
[*] Dr. Q. Li,[$] [+] Dr. W. Zhang, Prof. O. M. Yaghi
Department of Chemistry and Biochemistry
University of California, Los Angeles
1
terized by H NMR spectroscopy in solution and by X-ray
crystallography in the solid state (see Supporting Informa-
tion).
607 Charles E. Young Drive East, Los Angeles, CA 90095 (USA)
Fax: (+1)310-206-5891
E-mail: yaghi@chem.ucla.edu
Homepage: http://yaghi.chem.ucla.edu
C.-H. Sue,[+] Dr. S. Basu, A. K. Shveyd, G. Barin, L. Fang,
The crystal structure of CATME[13] is illustrated in
Figure 2. In CATME, the NPP36C10 ring is endowed with
planar chirality[14–16] as a consequence of the two pairs of para-
oriented substituents on the hydroquinone ring. Racemiza-
tion of the enantiomers is prevented on account of the lack of
rotation of the central hydroquinone ring as a consequence of
the length of the rigid strut. The planar chirality, which was
revealed (see the Supporting Information, Figure S2) using a
chiral shift reagent,[17] was confirmed by the existence of equal
amounts of (R) and (S) enantiomers in the unit cell of
CATME. In the solid state, the mechanically-interlocked
components in the pendant [2]catenanes, namely the
CBPQT4+ and NPP36C10 rings, adopt a geometry similar to
that reported previously in the literature.[18] The linear rigid
strut spans a distance of 32.9 ꢀ in length between the two
carboxylate carbon atoms. Overall, the incorporation of the
pendant [2]catenane and the rigid strut renders CATDC, with
its 120 non-hydrogen atoms (excluding counterions) and M =
1595.82 gmolÀ1, the pinnacle in terms of complexity and size
of links exploited in MOF synthesis to date.
Dr. A. A. Sarjeant, Prof. J. F. Stoddart
Department of Chemistry, Northwestern University
2145 Sheridan Road, Evanston, IL 60208 (USA)
Fax: (+1)847-491-1009
E-mail: stoddart@northwestern.edu
Homepage: http://stoddart.northwestern.edu
C.-H. Sue[+]
Department of Electrical Engineering
University of California, Los Angeles
420 Westwood Plaza, Los Angeles, CA 90095 (USA)
[$] Current address: Department of Chemistry, Fudan University,
Shanghai 200433(P. R. China)
[+] These authors contributed equally to this work.
[**] This work was supported at the University of California, Los Angeles
by the US Department of Defense (DTRA: HDTRA1-08-10023), and
at Northwestern University by the Non-equilibrium Energy Center
(NERC) which is an Energy Frontier Research Center (EFRC) funded
by the U.S. Department of Energy, Office of Basic Energy Sciences
under Award Number DE-SC0000989.
MOF-1030 (Figure 3a) can be prepared from CATDC
with Cu(NO3)2·2.5H2O employing reaction conditions (see
Experimental Section) identical to those used[9b] in the
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201003221.
Angew. Chem. Int. Ed. 2010, 49, 6751 –6755
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6751

Communications
the strut cause the p-conju-
gated system in the back-
bone to deteriorate, making
the phenylene ring at one
end (ring 1) almost perpen-
dicular to the other phenyl-
ene rings (Figure 3a).
From a topological point
ꢀ
of view, Cu(C C)(COO)2
serves as a secondary build-
ing unit (SBU) with square-
planar geometry. The points
of extension of this square
planar joint are two carbon
atoms from the carboxylates
and two carbon atoms con-
nected to the acetylenic
bond (Figure 3b). Mean-
while, strut CATDC can be
divided into two different
types of ditopic links, with
lengths of 22.6 and 16.4 ꢀ,
corresponding to the distan-
ces between copper atoms
Figure 1. Catenated strut synthesis. CATME and CATDC were synthesized by the catenation of the CBPQT4+
ring around the 1,5-dioxynaphthalene unit in CEME and CEDC. CEDC was obtained from the de-esterification
of CEBU (in TFA/MeCN) or CEME (in KOH/MeOH/CH2Cl2). Structural formulae defining the graphical
representations are illustrated at the bottom.
synthesis of MOF-1011. Single-crystal X-ray diffraction
reveals that MOF-1030[13] crystallizes in the trigonal space
¯
group R3c, with unit cell parameters a = b = 34.67 ꢀ, and c =
98.98 ꢀ. In MOF-1030, each reduced copper(I) ion is bonded
to two carboxylate groups from two struts and to one
acetylenic bond from a third strut in an h2 fashion (Fig-
ure 3b), after the same coordination as that present in MOF-
1011. A closer examination of the strut in MOF-1030 reveals
that the two carboxylate planes are twisted relative to each
other. The p-alkyne copper(I) coordination and the length of
Figure 3. Assembly of MOF-1030 from square-planar joints and linear
links. a) Crystal structure of MOF-1030. Ring 1 at one end of the
catenane link is almost perpendicular to the other phenylene rings in
the strut. b) Left: Each Cu+ ion is bonded to two carboxylate groups
from two struts and to one acetylenic bond from a third strut in an h2
fashion. Center: This square-planar joint is shown in a ball-and-stick
representation with the Cu+ ion highlighted in orange. Right: The
points of extension of this square planar joint are two carbon atoms
from carboxylates and two carbon atoms connecting to the acetylenic
group. c) Strut CATDC can be divided into two different types of
ditopic links, connecting to square planar joints at both ends.
d) Graphical representation of (a) with squares replacing the inorganic
SBU, and rods replacing the organic links. The twist of Ring 1 results
in neighboring square-planar joints being almost perpendicular to
each other. e) The three-dimensional network with nbo topology was
constructed by using squares and linear links. Organic struts: gray;
crown ethers: red; CBPQT4+: blue; Cu: orange spheres; inorganic
SBUs: orange squares. All hydrogen atoms and anions have been
omitted for clarity.
Figure 2. Crystal structure of CATME. a) ORTEP drawing of CATME,
excluding hydrogen atoms and counterions. All ellipsoids are set at
80% probability. b) Packing of CATME in the solid state, with two
catenanes illustrated by means of a space-filling representation. All the
phenylene rings in the strut backbone are almost co-planar. The planar
chirality of each catenane strut is labeled either (R) or (S). NPP36C10:
red; CBPQT4+: blue; linear strut: black. All hydrogen atoms and anions
have been omitted for clarity.
6752
www.angewandte.org
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2010, 49, 6751 –6755

Angewandte
Chemie
(Figure 3c). The twist of the carboxylate planes in the struts
renders all the neighboring squares more or less perpendic-
ular to each other (Figure 3d), leading to the observed three-
dimensional structure.[19] This unique arrangement means that
MOF-1030 has a network with an nbo topology,[20] assuming
that both links are identical in terms of connectivity (Fig-
ure 3e).
The exceptional length of the struts provides vast open-
ness to accommodate the bulky MIMs in the framework.
Figure 4 illustrates a face in the nbo network of MOF-1030.
Six donor–acceptor [2]catenanes point outward from the six
links of the hexagon at precise locations and with uniform
relative orientations. The (R) and (S) enantiomeric struts are
present in a 1:1 ratio in the crystal structure of MOF-1030.
Considering the slender nature of the strut, it is not
surprising that the backbone of MOF-1030 adopts a catenated
framework (Figure 5a). The two nets are related by an
inversion operation, and the closest copper atoms in two
different nets are separated by 4.9 ꢀ. Two kinds of p···p
stacking interactions exist (Figure 5b) in the framework:
i) between the CBPQT4+ rings and the framework backbones
within which they are anchored, and ii) between the frame-
work backbones from two catenated nets. p···p stacking
between a CBPQT4+ ring and the neighboring strut backbone
might explain why ring 2 is co-planar with the rings from 3 to
5, while ring 1 is not involved in stacking, and thus can be
twisted, giving rise to the nbo topology network.
Figure 4. One of the hexagonal faces in MOF-1030. Hexagons are
formed with six Cu+ ions as vertices. A ball-and-stick representation of
a hexagonal array of catenanes with six of them inserted into the six
edges. Organic struts: gray; crown ethers: red; CBPQT4+: blue; Cu:
orange. All hydrogen atoms and anions have been omitted for clarity.
In summary, MOF-1030 (Figure 6) constitutes an example
of the ordering of MIMs within a well-defined three-dimen-
sional solid matrix. The catenated MOF-1030 brings the
Figure 5. Catenated framework of MOF-1030. a) A representation of
MOF-1030, which has a catenaned extended structure with the nbo
topology in which the catenanes in the struts are located at precise
locations and with uniform relative orientations. The two nets are
shown in gray and green. Inorganic SBUs: orange squares; crown
ethers: red rings; CBPQT4+: blue square rings. b) In MOF-1030, two
kinds of p···p stacking interactions exist in the frameworks: i) between
CBPQT4+ cyclophanes (blue) and framework backbones (gray), and
ii) between framework backbones from two nets (gray and green).
Copper atoms: orange spheres; crown ethers: red spheres.
Figure 6. Catenated struts in catenated MOF-1030. a) View of MOF-
1030 along the c axis. Crown ethers and CBPQT4+ rings are omitted.
MOF-1030 is a catenated structure with two different frameworks
shown in two different colors (gray and green). b) The framework with
crown ethers represented in red. Hydrogen atoms, anions, and
CBPQT4+ rings are omitted. c) Two interwoven nets, one in gray and
the other in green, with the crown ethers shown in red and the
CBPQT4+ rings in blue and featured in a space-filling manner.
Angew. Chem. Int. Ed. 2010, 49, 6751 –6755
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
6753

Communications
2055 – 2056; d) W. R. Dichtel, J. R. Heath, J. F. Stoddart, Philos.
Trans. R. Soc. London Ser. A 2007, 365, 1607 – 1625.
[5] J. E. Green et al. Nature 2007, 445, 414 – 417; see the Supporting
Information.
prototypically active switching gear and machinery in the
catenated struts to a standstill—at least as far as translational
motion in three-dimensional space is concerned. Compared
to the analogous pendant poly[2]catenanes,[21] MOFs made
from catenated links significantly enhance the order and
coherence of MIMs, with the potential to achieve mechanical
movements in porous solid-state materials and hence ulti-
mately switches organized in three-dimensional arrays for the
next generation of functional materials directed towards
ultrahigh-density electronics applications.
[6] a) C. J. Pedersen, J. Am. Chem. Soc. 1967, 89, 2495 – 2496;
b) C. J. Pedersen, J. Am. Chem. Soc. 1967, 89, 7017 – 7036;
c) E. B. Kyba, K. Koga, L. R. Sousa, M. G. Siegel, D. J. Cram, J.
Am. Chem. Soc. 1973, 95, 2692 – 2693; d) R. C. Helgeson, J. M.
Timko, P. Moreau, S. C. Peacock, J. M. Mayer, D. J. Cram, J. Am.
Chem. Soc. 1974, 96, 6762 – 6763; e) P. R. Ashton, E. J. T.
Chrystal, J. P. Mathias, K. P. Parry, A. M. Z. Slawin, N. Spencer,
J. F. Stoddart, D. J. Williams, Tetrahedron Lett. 1987, 28, 6367 –
6370; f) D. J. Cram, Angew. Chem. 1988, 100, 1041 – 1052;
Angew. Chem. Int. Ed. Engl. 1988, 27, 1009 – 1020; g) T. B.
Gasa, J. M. Spruell, W. R. Dichtel, T. J. Sørensen, D. Philp, J. F.
Experimental Section
MOF-1030: A solid mixture of CATDC (10.00 mg, 4.60 ꢁ 10À3 mmol;
see Supporting Information) and Cu(NO3)2·2.5H2O (20.00 mg, 8.60 ꢁ
10À2 mmol; Aldrich Chemical Co.) was dissolved in DMF (375 mL),
EtOH (375 mL), and H2O (250 mL) in a 4 mL vial. The vial was capped
and placed in an isothermal oven at 858C for 6 days, after which time
it was removed from the oven and allowed to cool to room
temperature. A mixture of green and brown crystals was obtained.
After decanting mother liquor, DMF (1.0 mL) and CHBr3 (1.0 mL)
was added to the vial. Because of the density difference of the two
types of crystals, the brown crystals float to the top of the solution,
while the green crystals stay at the bottom. Crystals of MOF-1030,
which is the brown compound, were collected and rinsed with DMF
(4 ꢁ 1.0 mL).
ˇ
Stoddart, P. Kuzmic, Chem. Eur. J. 2009, 15, 106 – 116; h) C. J.
Bruns, S. Basu, J. F. Stoddart, Tetrahedron Lett. 2010, 51, 983 –
986.
[7] a) P.-L. Anelli, P. R. Ashton, N. Spencer, A. M. Z. Slawin, J. F.
Stoddart, D. J. Williams, Angew. Chem. 1991, 103, 1052 – 1054;
Angew. Chem. Int. Ed. Engl. 1991, 30, 1036 – 1039; b) P. R.
Ashton, D. Philp, N. Spencer, J. F. Stoddart, J. Chem. Soc. Chem.
Commun. 1991, 1677 – 1679.
[8] a) G. Schill, Catenanes, Rotaxanes and Knots, Academic Press,
New York, 1971; b) P. R. Ashton, T. T. Goodnow, A. E. Kaifer,
M. V. Reddington, A. M. Z. Slawin, N. Spencer, J. F. Stoddart, C.
Vicent, D. J. Williams, Angew. Chem. 1989, 101, 1404 – 1408;
Angew. Chem. Int. Ed. Engl. 1989, 28, 1396 – 1399; c) C. A.
Hunter, J. Am. Chem. Soc. 1992, 114, 5303 – 5311; d) C. O.
Dietrich-Buchecker, B. Frommberger, I. Lꢄer, J.-P. Sauvage, F.
Vꢅgtle, Angew. Chem. 1993, 105, 1526 – 1529; Angew. Chem. Int.
Ed. Engl. 1993, 32, 1434 – 1437; e) D. B. Amabilino, P. R. Ashton,
A. S. Reder, N. Spencer, J. F. Stoddart, Angew. Chem. 1994, 106,
450 – 453; Angew. Chem. Int. Ed. Engl. 1994, 33, 433 – 437; f) T. J.
Kidd, D. A. Leigh, A. J. Wilson, J. Am. Chem. Soc. 1999, 121,
Received: May 27, 2010
Published online: August 16, 2010
Keywords: catenanes · chirality · crystal growth ·
.
mechanically interlocked molecules · metal–organic frameworks
ˇ
´
1599 – 1600; g) O. S. Miljanic, J. F. Stoddart, Proc. Natl. Acad.
Sci. USA 2007, 104, 12966 – 12970; h) J. M. Spruell, W. F.
Paxton, J.-C. Olsen, D. Benꢆtez, E. Tkatchouk, C. L. Stern, A.
Trabolsi, D. C. Friedman, W. A. Goddard III, J. F. Stoddart, J.
Am. Chem. Soc. 2009, 131, 11571 – 11580.
[1] a) D. B. Amabilino, J. F. Stoddart, Chem. Rev. 1995, 95, 2725 –
2828; b) M. C. T. Fyfe, J. F. Stoddart, Acc. Chem. Res. 1997, 30,
393 – 401; c) J.-P. Sauvage, C. Dietrich-Buchecker, Molecular
Catenanes, Rotaxanes and Knots: A Journey through the World of
Molecular Topology, Wiley-VCH, Weinheim, 1999; d) J. F.
Stoddart, Chem. Soc. Rev. 2009, 38, 1802 – 1820.
[2] a) H. Li, M. Eddaoudi, M. OꢂKeeffe, O. M. Yaghi, Nature 1999,
402, 276 – 279; b) M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J.
Wachter, M. OꢂKeeffe, O. M. Yaghi, Science 2002, 295, 469 – 472;
c) O. M. Yaghi, M. OꢂKeeffe, N. W. Ockwig, H. K. Chae, M.
Eddaoudi, J. Kim, Nature 2003, 423, 705 – 714; d) H. K. Chae,
D. Y. Siberio-Pꢃrez, J. Kim, Y. Go, M. Eddaoudi, A. J. Matzger,
M. OꢂKeeffe, O. M. Yaghi, Nature 2004, 427, 523 – 527; e) S.
Kitagawa, R. Kitaura, S. Noro, Angew. Chem. 2004, 116, 2388 –
ˇ
´
[9] a) Q. Li, W. Zhang, O. S. Miljanic, C.-H. Sue, C. Knobler, Y.-L.
Zhao, L. Liu, J. F. Stoddart, O. M. Yaghi, Science 2009, 325, 855 –
ˇ
´
859; b) Q. Li, W. Zhang, O. S. Miljanic, C. B. Knobler, J. F.
Stoddart, O. M. Yaghi, Chem. Commun. 2010, 46, 380 – 382; c) C.
Valente, E. Choi, M. E. Belowich, C. J. Doonan, Q. Li, T. B.
Gasa, Y. Y. Botros, O. M. Yaghi, J. F. Stoddart, Chem. Commun.
2010, 46, 4911 – 4913.
ˇ
´
[10] Y.-L. Zhao, L. Liu, W. Zhang, C.-H. Sue, Q. Li, O. S. Miljanic,
O. M. Yaghi, J. F. Stoddart, Chem. Eur. J. 2009, 15, 13356 –
13380.
[11] a) B. Odell, M. V. Reddington, A. M. Z. Slawin, N. Spencer, J. F.
Stoddart, D. J. Williams, Angew. Chem. 1988, 100, 1605 – 1608;
Angew. Chem. Int. Ed. Engl. 1988, 27, 1547 – 1550; b) M.
Asakawa, W. Dehaen, G. L’abbꢃ, S. Menzer, J. Nouwen, F. M.
Raymo, J. F. Stoddart, D. J. Williams, J. Org. Chem. 1996, 61,
9591 – 9595; c) C.-H. Sue, S. Basu, A. C. Fahrenbach, A. K.
Shveyd, S. K. Dey, Y. Y. Botros, J. F. Stoddart, Chem. Sci. 2010, 1,
119 – 125.
ˇ
2430; Angew. Chem. Int. Ed. 2004, 43, 2334 – 2375; f) M. Dinca ,
A. Dailly, Y. Liu, C. M. Brown, D. A. Neumann, J. R. Long, J.
Am. Chem. Soc. 2006, 128, 16876 – 16883; g) C.-D. Wu, A. Hu,
L. Zhang, W. Lin, J. Am. Chem. Soc. 2005, 127, 8940 – 8941;
h) K. L. Mulfort, J. T. Hupp, J. Am. Chem. Soc. 2007, 129, 9604 –
ˇ
9605; i) L. J. Murray, M. Dinca, J. R. Long, Chem. Soc. Rev. 2009,
38, 1294 – 1314; j) J.-R. Li, R. J. Kuppler, H.-C. Zhou, Chem. Soc.
Rev. 2009, 38, 1477 – 1504.
[12] a) K. Sonogashira, Y. Tohda, N. Hagihara, Tetrahedron Lett.
1975, 16, 4467 – 4470; b) S. Takahashi, Y. Kuroyama, K. Sonoga-
shira, N. Hagihara, Synthesis 1980, 627 – 630.
[3] H. Deng, M. A. Olson, J. F. Stoddart, O. M. Yaghi, Nature Chem.
2010, 2, 439 – 443.
[13] Crystallographic data for CEBU: C78H81N2O14, Mr = 1270.45,
´
[4] a) C. P. Collier, E. W. Wong, M. Belohradsky, F. M. Raymo, J. F.
¯
triclinic, space group P1, a = 10.8058(17), b = 11.873(3), c =
Stoddart, P. J. Kuekes, R. S. Williams, J. R. Heath, Science 1999,
285, 391 – 394; b) C. P. Collier, G. Mattersteig, E. W. Wong, Y.
Luo, K. Beverly, J. Sampaio, F. M. Raymo, J. F. Stoddart, J. R.
Heath, Science 2000, 289, 1172 – 1175; c) A. H. Flood, J. F.
Stoddart, D. W. Steuerman, J. R. Heath, Science 2004, 306,
27.000(5) ꢀ, a = 92.247(16), b = 90.886(13), g = 91.194(14)8,
V= 3460.3(11) ꢀ3,
D , l = 1.54178 ꢀ, Z = 2,
calcd = 1.219 gcmÀ3
R1 [I > 2s(I)] = 0.0815, wR2 (all data) = 0.2222, GOF = 1.013.
Crystallographic data for CATME: C124H124N14O14P4F24, Mr =
6754
www.angewandte.org
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2010, 49, 6751 –6755

Angewandte
Chemie
¯
2614.25, triclinic, space group P1, a = 12.9773(2), b = 13.7430(3),
plane. Here we only consider the first chiral plane, since the
c = 35.9341(6) ꢀ,
a = 79.1720(10),
b = 87.2080(10),
g =
l =
naphthalene plane is able to rotate freely.
80.0320(10)8, V= 6198.7(2) ꢀ3,
D
calcd = 1.401 gcmÀ3
,
[16] The (R) and (S) enantiomer assignments of similar systems in
our previous publications (Figures 5–8 in Ref. [10] and Figure 1
in Ref. [9b]) were incorrectly placed.
1.54178 ꢀ, Z = 2, R1 [I > 2s(I)] = 0.0491, wR2 (all data) =
0.1617, GOF = 1.074. Single crystal data for MOF-1030 after
SQUEEZE:
group
C
102H88Cu1N4O14, Mr = 1657.30, trigonal, space
¯
R3c, a = b = 34.6678(5), c = 98.979(3) ꢀ, V=
[17] W. H. Pirkle, D. L. Sikkenga, M. S. Pavlin, J. Org. Chem. 1977,
42, 384 – 387.
103021(4) ꢀ3, Dcalcd = 0.962 gcmÀ3, l = 1.54178 ꢀ, Z = 36, R1
[I > 2s(I)] = 0.0980, wR2 (all data) = 0.3054, GOF = 1.027.
CCDC 778456–778459 contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
[18] P. R. Ashton et al., J. Chem. Soc. Chem. Commun. 1991, 634 –
639; see also the Supporting Information.
[19] M. Eddaoudi, J. Kim, M. OꢂKeeffe, O. M. Yaghi, J. Am. Chem.
Soc. 2002, 124, 376 – 377.
[20] M. OꢂKeeffe, M. A. Peskov, S. J. Ramsden, O. M. Yaghi, Acc.
Chem. Res. 2008, 41, 1782 – 1789.
[14] V. Prelog, G. Helmchen, Angew. Chem. 1982, 94, 614 – 631;
Angew. Chem. Int. Ed. Engl. 1982, 21, 567 – 583.
[15] There are actually two chiral planes in the NPP36C10 moiety.
One is the hydroquinone and the other is the naphthalene unit
[21] a) C. Hamers, F. M. Raymo, J. F. Stoddart, Eur. J. Org. Chem.
1998, 10, 2109 – 2117; b) D. L. Simone, T. M. Swager, J. Am.
Chem. Soc. 2000, 122, 9300 – 9301; c) L. Fang, M. A. Olson, J. F.
Stoddart, Chem. Soc. Rev. 2010, 39, 17 – 29.
Angew. Chem. Int. Ed. 2010, 49, 6751 –6755
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
6755