ChemComm

View Article Online

COMMUNICATION View Journal | View Issue

Two-step crystal engineering of porous nets from

Published on 22 July 2013. Downloaded by Florida International University on 20/08/2013 18:17:53.

Cite this: Chem. Commun., 2013,

[Cr3(l3-O)(RCO2)6] and [Cu3(l3-Cl)(RNH2)6Cl6]
49, 8154
molecular building blocks†
Received 1st June 2013,
Accepted 17th July 2013 Sameh K. Elsaidi,zab Mona H. Mohamed,zab Lukasz Wojtas,a Amy J. Cairns,c
DOI: 10.1039/c3cc44133d
Mohamed Eddaoudiac and Michael J. Zaworotko*a

www.rsc.org/chemcomm

Two porous nets have been prepared via a 2-step crystal engineer- linking the vertices of [M3(m3-O)(RCO2)6] moieties by linear
ing approach that links decorated trigonal prismatic [Cr3(l3-O)- ligands. However, the inherent flexibility of the [M3(m3-O)-
(CO2)6] and [Cu3(l3-Cl)(RNH2)6Cl6] molecular building blocks, (CO2)6] cluster facilitates shrinkage upon removal of the guest,
MBBs. tp-PMBB-5-acs-1 is a rare example of a rigid acs underlying as exemplified by the MIL-88 class of compounds, which
net whereas tp-PMBB-6-stp-1, an stp underlying net, exhibits free undergo variations of the unit cell volume from 70 to
NH2 groups in its channels and a relatively high isosteric heat of 230%.22–26 Nevertheless, flexibility in MOMs might be useful
adsorption for CO2. for some other applications as exemplified by recent reports on
applications of MIL-88.27,28 Prevention or reduction of such
Metal organic materials (MOMs) emerged in the past two breathing phenomena has been recently reported29 by imple-
decades and are today widely regarded as promising materials menting linker modification. However, 6-c acs nets which are
for a diverse range of applications such as gas storage,1–4 completely rigid should exhibit a higher surface area. We
heterogeneous catalysis,5 drug delivery,6 magnetism7 and con- herein address this matter through an extension of our recently
ductivity.8 In the context of MOM design, high-symmetry uninodal reported 2-step crystal engineering approach (Scheme 1).30
and binodal nets are attractive targets because they can exhibit
topology that is amenable to fine-tuning from a range of readily
available molecular building blocks, MBBs. Uninodal nets are
exemplified by srs, ths (3-connected, 3-c),9,10 dia,11 nbo12 (4-c),
pcu,9,10,13 acs14,15 (6-c), bcu9,10 (8-c) and fcu16 (12-c) topology nets.
Binodal nets are exemplified by combinations of [Cu2(CO2)4] (tbo17
pto18) square paddlewheel MBBs or basic zinc acetate [Zn4(m4-O)-
(CO2)6] octahedral MBBs (6,3-c, qom) with 3-c moieties. However,
despite their promise, MOMs remain underdeveloped largely
because of cost or stability considerations.19
The [M3(m3-O)(RCO2)6] trigonal prismatic cluster (M = Cr, Fe,
In) represents an ideal MBB since it is robust, relatively
inexpensive to prepare and it sustains tetrahedral supercages
in zeolite-like MOMs such as MIL-100 and MIL-101.20,21 The
default net (acs) for 6-c trigonal prismatic nodes is formed by

a
Department of Chemistry, CHE205, University of South Florida,
4202 E. Fowler Avenue, Tampa, FL, 33620, USA. E-mail: xtal@usf.edu
b
Chemistry Department, Faculty of Science, Alexandria University,
P.O. Box 426 Ibrahimia, Alexandria 21321, Egypt
c
Chemical Science, 4700 King Abdullah University of Science and Technology,
Thuwal 23955-6900, Kingdom of Saudi Arabia
† Electronic supplementary information (ESI) available: Synthetic procedures,
additional gas adsorption isotherms and crystallographic tables. CCDC 943023–
943025. For ESI and crystallographic data in CIF or other electronic format see
DOI: 10.1039/c3cc44133d Scheme 1 Schematic representation of the 2-step approach to binodal acs and
‡ These authors equally contributed in this work. stp nets.

8154 Chem. Commun., 2013, 49, 8154--8156 This journal is c The Royal Society of Chemistry 2013
 View Article Online

Communication ChemComm

Two new trigonal prismatic clusters decorated with 3-amino-

phenyl and 4-aminophenyl moieties with the formula
[Cr3(m3-O)(RCO2)6]NO3 (R = 3-aminophenyl or 4-aminophenyl)
were synthesized through a solvothermal reaction of chromium(III)-
nitrate nonahydrate with m-aminobenzoic acid and p-amino-
benzoic acid, respectively, in MeOH (see ESI†). These trigonal
prismatic Primary Molecular Building Blocks (tp-PMMB-5
and -6, respectively) were subsequently reacted with CuCl2 in
a mixture of N,N-dimethylformamide (DMF) and acetonitrile
Published on 22 July 2013. Downloaded by Florida International University on 20/08/2013 18:17:53.

(MeCN) at room temperature to afford the novel MOMs,
tp-PMBB-5-acs-1 and tp-PMBB-6-stp-1.
tp-PMBB-5-acs-1 and tp-PMBB-6-stp-1 are sustained by
[Cr3(m3-O)(RCO2)6] and [Cu3(m3-Cl)(RNH2)6Cl6] MBBs, and to
our knowledge these MOMs represent the first use of the latter
cluster in a MOM. This is perhaps surprising since Cu3(m3-X)
clusters (X = F, Cl, Br or I) are long and well-known to exist as
discrete complexes according to a Cambridge Structural Data-
base31 survey (CSD version 5.34, updates to Nov. 2012). Indeed,
there are 279 entries for Cu3(m3-Cl), 201 for Cu3(m3-Br) and 463
for Cu3(m3-I). However, only 5 of these Cu3(m3-Cl) clusters are
decorated with NH2 groups, only one of which is similar to the
cluster reported herein.
tp-PMBB-5-acs-1 represents the first example of an under-
lying32 acs net formed from two different 6-c MBBs, [Cr3(m3-O)-
(maba)6], which uses its peripheral NH2 moieties to link
[Cu3(m3-Cl)(RNH2)6Cl6] MBBs. The single crystal structure
reveals that tp-PMBB-5-acs-1 crystallizes in the hexagonal space
group P6% c2 (a = b = 13.469(12) Å, c = 27.51(2) Å, V = 4322.1 Å3).
The Cu2+ cations of the [Cl6Cu3(m3-Cl)(NH2)6] clusters are
5-coordinate with 2NH2 ligands, 2 terminal Cl ligands and a
m3-Cl ligand. The cluster geometry is controlled by intra-
molecular H-bonding between the RNH2 moieties and terminal
Cl ligands (N  Cl = 3.190(16) Å, see Fig. 1a and b). tp-PMBB-5-
acs-1 exhibits triangular channels parallel to [0,0,1] with a pore
limiting diameter (PLD) of 14.50 Å, and 41.5% void space PLD
is determined by measuring the diagonal of the channel and
subtracting 3.5 Å for van der Waals distances. Reaction of
tp-PMBB-6 with CuCl2 in a 3 : 2 molar ratio afforded tp-PMBB-
6-stp-1, which crystallizes in the hexagonal space group P63/
mcm (a = b = 29.72(2) Å, c = 26.388(18) Å, V = 20185.3 Å3). The
single crystal structure reveals that only 4NH2 moieties of
tp-PMBB-6 are coordinated to the [Cu3(m3-Cl)(RNH2)6Cl6] MBB
so they serve as 4-c and 6-c nodes, respectively, resulting in a
square trigonal prismatic (stp) net (Fig. 2). The two free amine
Fig. 1 (a) Hydrogen bonding in [Cu3(m3-Cl)(RNH2)6Cl6] MBBs; (b) hydrogen
bonds in tp-PMBB-5-acs-1; (c) hydrogen bonds in tp-PMBB-stp-1 (CH hydrogen
atoms have been omitted for clarity).
Fig. 2 Illustrations of (a) the acs net of tp-PMBB-5-acs-1, (b) the stp net of
tp-PMBB-6-stp-1.
Fig. 3 Variable temperature PXRD patterns of tp PMBB-6-acs-1 under vacuum.
groups are oriented toward the interior of the 21.34 Å diameter
hexagonal channels that run parallel to [001] (Scheme 1).
We addressed whether or not tp-PMBB-5-acs-1 exhibits
breathing by variable temperature powder X-ray diffraction
(Fig. 3) and immersion in a variety of solvents (see ESI†). In
contrast to the MIL-88 series, tp-PMBB-5-acs-1 showed no shifts
in peak positions upon heating under vacuum or immersing
the crystals for 24 hours in solvents such as acetone, toluene
and DMF. The crystals are water stable, retaining crystallinity
following immersion of the crystals in water for 24 hours (see
ESI†). The rigidity of tp-PMBB-5-acs-1 might be attributable to
the NH  Cl hydrogen bonds in the [Cu3(m3-Cl)(RNH2)6Cl6]
MBBs (Fig. 1). We subsequently tested tp-PMBB-5-acs-1 for
porosity. Crystals of tp-PMBB-5-acs-1 were activated by
exchange with MeCN for 2 days (3 times per day) and then
with CH2Cl2 for 3 days (3 times per day) followed by degassing
under dynamic vacuum at 60 1C for 12 h. CO2 adsorption at
195 K revealed a Brunauer–Emmett–Teller surface area (BET) of
710 m2 g1 and a Langmuir surface area of 909 m2 g1. In
addition, tp-PMBB-5-acs-1 was found to exhibit CO2 uptake of
80 cm3 g1 (90 cm3 cm3 ) and 60 cm3 g1 (68 cm3 cm3 ) at
273 K and 298 K, respectively (see ESI†).
tp-PMBB-6-stp-1 is comprised of the same MBBs as tp-PMBB-5-
acs-1 but because the [Cr3(m3-O)(RCO2)6] MBB is only 4-c it has free
amine groups, a feature that would be expected to result in high
affinity towards CO2. Crystals of tp-PMBB-6-stp-1 were activated by
soaking in EtOH and supercritical CO2 drying. The N2 adsorption
isotherm at 77 K revealed Brunauer–Emmett–Teller (BET) and
Langmuir surface areas of 323 and 403 m2 g1, respectively.

This journal is c The Royal Society of Chemistry 2013 Chem. Commun., 2013, 49, 8154--8156 8155
 View Article Online

ChemComm Communication

Table 1 Summary of acs nets with respect to the observed swelling amplitude 5 J. Lee, O. K. Farha, J. Roberts, K. A. Scheidt, S. T. Nguyen and
and BET surface area J. T. Hupp, Chem. Soc. Rev., 2009, 38, 1450.
6 P. Horcajada, R. Gref, T. Baati, P. K. Allan, G. Maurin, P. Couvreur,
%Swelling BET SA G. Férey, R. E. Morris and C. Serre, Chem. Rev., 2012, 112,
Net amplitude (m2 g1) Ref. 1232–1268.
7 P. D. Dietzel, R. E. Johnsen, R. Blom and H. Fjellvag, Chem.–Eur. J.,
Sc-bdc N/A 634 35 2008, 14, 2389–2397.
Sc-dobdc N/A 0 36 8 G. Givaja, P. Amo-Ochoa, C. J. Gómez-Garcı́a and F. Zamora, Chem. Soc.
MOF-235 0 0 14 Rev., 2012, 41, 115.
MOF-236 0 0 14 9 O. Delgado-Friedrichs, M. O’Keeffe and O. M. Yaghi, Phys. Chem.
PCN-19 N/A 723 37 Chem. Phys., 2007, 9, 1035–1043.
MIL-88-B(4H) 136 8 29
Published on 22 July 2013. Downloaded by Florida International University on 20/08/2013 18:17:53.

10 M. O’Keeffe, M. A. Peskov, S. J. Ramsden and O. M. Yaghi, Acc. Chem.

MIL-88-B(Cl) 117 19 29 Res., 2008, 41, 1782–1789.
MIL-88-B(Br) 94 o1 29 11 M. J. Zaworotko, Chem. Soc. Rev., 1994, 23, 283–288.
MIL-88-B(NH2) 132 14 29 12 M. Eddaoudi, J. Kim, M. O’Keeffe and O. M. Yaghi, J. Am. Chem. Soc.,
MIL-88-B(NO2) 63 15 29 2001, 124, 376–377.
MIL-88-B(CH3) 97 80 29 13 H. Li, M. Eddaoudi, M. O’Keeffe and O. M. Yaghi, Nature, 1999, 402,
MIL-88-B(2CH3) 97 60 29 276–279.
MIL-88-B(2OH) 92 3 29 14 A. C. Sudik, A. P. Côté and O. M. Yaghi, Inorg. Chem., 2005, 44,
MIL-88-B(4F) 54 35 29 2998–3000.
MIL-88-B(2CF3) 49 330 29 15 L. Carlucci, G. Ciani, S. Maggini, D. M. Proserpio and M. Visconti,
MIL-88-B(4CH3) 25 1220 29 Chem.–Eur. J., 2010, 16, 12328–12341.
MIL-88-D(4CH3) 105 210 29 16 J. H. Cavka, S. Jakobsen, U. Olsbye, N. Guillou, C. Lamberti,
MIL-88-D(2CH3) 228 29 29 S. Bordiga and K. P. Lillerud, J. Am. Chem. Soc., 2008, 130,
MIL-88-D(4H) 237 N/A 29 13850–13851.
MCF-18(L,M) 75–125 224a 26 17 S. S. Y. Chui, S. M. F. Lo, J. P. H. Charmant, A. G. Orpen and
tp-PMBB-5-acs-1 0 710 This work I. D. Williams, Science, 1999, 283, 1148–1150.
a 18 B. Chen, M. Eddaoudi, S. T. Hyde, M. O’Keeffe and O. M. Yaghi,
Langmuir S.A.
Science, 2001, 291, 1021–1023.
19 K. A. Cychosz and A. J. Matzger, Langmuir, 2010, 26, 17198–17202.
20 G. Férey, C. Serre, C. Mellot-Draznieks, F. Millange, S. Surblé,
CO2 uptakes for tp-PMBB-6-stp-1 at 1 atm were measured to be J. Dutour and I. Margiolaki, Angew. Chem., Int. Ed., 2004, 43,
54 cm3 g1 (39 cm3 cm3 ) and 37 cm3 g1 (27 cm3 cm3 ) at 6296–6301.
273 K and 298 K, respectively (see ESI†). The heat of adsorption 21 G. Férey, C. Mellot-Draznieks, C. Serre, F. Millange, J. Dutour,
S. Surblé and I. Margiolaki, Science, 2005, 309, 2040–2042.
(Qst) for both tp-PMBB-5-acs-1 and tp-PMBB-6-stp-1 was calcu- 22 C. Serre, F. Millange, S. Surblé and G. Férey, Angew. Chem., Int. Ed.,
lated from their 273 K and 298 K isotherms and are compared in 2004, 43, 6285–6289.
Fig. S18 (see ESI†). tp-PMBB-5-acs-1 exhibits a Qst of 22 kJ mol1 23 S. Surblé, C. Serre, C. Mellot-Draznieks, F. Millange and G. Férey,
Chem. Commun., 2006, 284.
at zero coverage decreasing only slightly at full coverage. The 24 C. Mellot-Draznieks, C. Serre, S. Surblé, N. Audebrand and G. Férey,
corresponding values for tp-PMBB-6-stp-1 were found to J. Am. Chem. Soc., 2005, 127, 16273–16278.
be 36 kJ mol1 and 23 kJ mol1, respectively. The higher initial 25 C. Serre, C. Mellot-Draznieks, S. Surblé, N. Audebrand, Y. Filinchuk
and G. Férey, Science, 2007, 315, 1828–1831.
Qst in the case of tp-PMBB-6-stp-1 is presumably due to the 26 H. Chun, D. N. Dybtsev, H. Kim and K. Kim, Chem.–Eur. J., 2005, 11,
presence of free amino groups.3,33,34 3521–3529.
Table 1 compares the porosity of acs topology nets and 27 A. C. McKinlay, J. F. Eubank, S. Wuttke, B. Xiao, P. S. Wheatley,
P. Bazin, J. C. Lavalley, M. Daturi, A. Vimont, G. De Weireld,
reveals that most of them exhibit small or no surface area P. Horcajada, C. Serre and R. E. Morris, Chem. Mater., 2013, 25,
because of the aforementioned breathing effect (Table 1), 1592–1599.
although bulky substituents that reduce the swelling amplitude 28 N. A. Ramsahye, T. K. Trung, L. Scott, F. Nouar, T. Devic,
P. Horcajada, E. Magnier, O. David, C. Serre and P. Trens, Chem.
of MIL-88 nets29 can afford increased surface area. Mater., 2013, 25, 479–488.
In summary, we herein demonstrate that non-breathing acs 29 P. Horcajada, F. Salles, S. Wuttke, T. Devic, D. Heurtaux, G. Maurin,
and stp nets can be prepared using two robust MBBs linked by A. Vimont, M. Daturi, O. David, E. Magnier, N. Stock, Y. Filinchuk,
D. Popov, C. Riekel, G. Férey and C. Serre, J. Am. Chem. Soc., 2011,
aminobenzoate ligands. The [Cu3(m3-Cl)(RNH2)6Cl6] MBBs 133, 17839–17847.
reported herein for the first time are simple, cheap and facile 30 A. Schoedel, L. Wojtas, S. P. Kelley, R. D. Rogers, M. Eddaoudi and
to prepare and likely to become broadly applicable for crystal M. J. Zaworotko, Angew. Chem., Int. Ed., 2011, 50, 11421–11424.
31 F. Allen, Acta Crystallogr., Sect. B, 2002, 58, 380–388.
engineering of new MOMs. 32 E. V. Alexandrov, V. A. Blatov, A. V. Kochetkova and D. M. Proserpio,
CrystEngComm, 2011, 13, 3947–3958.
Notes and references 33 A. Demessence, D. M. D’Alessandro, M. L. Foo and J. R. Long, J. Am.
Chem. Soc., 2009, 131, 8784–8786.
1 J.-R. Li, R. J. Kuppler and H.-C. Zhou, Chem. Soc. Rev., 2009, 38, 1477. 34 T. M. McDonald, W. R. Lee, J. A. Mason, B. M. Wiers, C. S. Hong and
2 M. P. Suh, H. J. Park, T. K. Prasad and D. W. Lim, Chem. Rev., 2012, J. R. Long, J. Am. Chem. Soc., 2012, 134, 7056–7065.
112, 782–835. 35 I. A. Ibarra, X. Lin, S. Yang, A. J. Blake, G. S. Walker, S. A. Barnett,
3 K. Sumida, D. L. Rogow, J. A. Mason, T. M. McDonald, E. D. Bloch, D. R. Allan, N. R. Champness, P. Hubberstey and M. Schröder,
Z. R. Herm, T.-H. Bae and J. R. Long, Chem. Rev., 2012, 112, 724–781. Chem.–Eur. J., 2010, 16, 13671–13679.
4 M. H. Mohamed, S. K. Elsaidi, L. Wojtas, T. Pham, K. A. Forrest, 36 P. D. C. Dietzel, R. Blom and H. Fjellvåg, Dalton Trans., 2006, 2055.
B. Tudor, B. Space and M. J. Zaworotko, J. Am. Chem. Soc., 2012, 134, 37 S. Ma, J. M. Simmons, D. Yuan, J.-R. Li, W. Weng, D.-J. Liu and
19556–19559. H.-C. Zhou, Chem. Commun., 2009, 4049–4051.

8156 Chem. Commun., 2013, 49, 8154--8156 This journal is c The Royal Society of Chemistry 2013