Direct On-Surface Patterning of a Crystalline Laminar Covalent Organic Framework Synthesized at Room Temperature

Article abstract of DOI:10.1002/chem.201501692

We report herein an efficient, fast, and simple synthesis of an imine-based covalent organic framework (COF) at room temperature (hereafter, RT-COF-1). RT-COF-1 shows a layered hexagonal structure exhibiting channels, is robust, and is porous to N₂ and CO₂. The room-temperature synthesis has enabled us to fabricate and position low-cost micro- and submicropatterns of RT-COF-1 on several surfaces, including solid SiO₂ substrates and flexible acetate paper, by using lithographically controlled wetting and conventional ink-jet printing.

Full text of DOI:10.1002/chem.201501692

DOI: 10.1002/chem.201501692
Communication
&
Covalent Organic Frameworks
Direct On-Surface Patterning of a Crystalline Laminar Covalent
Organic Framework Synthesized at Room Temperature
[a, b]
[a, c]
[d]
Alejandro de la PeÇa Ruigómez,
David Rodríguez-San-Miguel, [Kf]yriakos C. Stylianou,
[e]
[e]
[f]
Massimiliano Cavallini, Denis Gentili, Fabiola Liscio, Silvia Milita,
[g, h]
[j]
[d]
Otello Maria Roscioni,
Maria Luisa Ruiz-Gonzµlez, Carlos Carbonell,
[d, i]
[a]
[b]
[a, c]
Daniel Maspoch,* RubØn Mas-BallestØ, JosØ Luis Segura, and FØlix Zamora*
ress in most of these applications is still limited due to the lack
of methodologies that allow processing and integrating these
materials on supports. In this context, advances have been
Abstract: We report herein an efficient, fast, and simple
synthesis of an imine-based covalent organic framework
[
2a,6]
(
COF) at room temperature (hereafter, RT-COF-1). RT-COF-
shows a layered hexagonal structure exhibiting chan-
nels, is robust, and is porous to N and CO . The room-
made in producing thin-films of COFs on several surfaces,
1
but not many in their patterning on surfaces. This is in part be-
cause of the current synthetic methods, which generally
2
2
[
1a]
temperature synthesis has enabled us to fabricate and po-
employ harsh conditions (e.g., high temperatures and pres-
sures) that prevent the use of conventional patterning tech-
niques. To our knowledge, there is only the primary example
reported by Dichtel et al. who used lithographically patterned
single-layer graphene microstructures as chemical affinity tem-
sition low-cost micro- and submicropatterns of RT-COF-
1
on several surfaces, including solid SiO substrates and
2
flexible acetate paper, by using lithographically controlled
wetting and conventional ink-jet printing.
[
7]
plates to selectively grow COF films on them. This indirect
patterning strategy has allowed preparation of microarrays of
COFs on rigid SiO surfaces, but not on flexible substrates.
2
Covalent organic frameworks (COFs) are an emerging class of
materials that integrate organic subunits into periodic 2D or
Lithography-controlled wetting (LCW) and ink-jet printing
technologies are powerful techniques that allow the position-
ing of materials onto surfaces with micron- or sub-micron reso-
3
D porous crystalline structures held together by covalent
[1]
[8]
bonds between elements such as C, B, O, N, and Si. They are
lution. Here, we report the direct on-surface patterning of
[1b,e,2]
low-density porous materials (e.g., boronate ester
and
COFs on rigid and flexible substrates by using both printing
technologies. Our approach relies on the rapid and room-tem-
perature synthesis of a crystalline laminar imine-based COF
(hereafter, RT-COF-1).
We show that the Schiff reaction between two trigonal
building blocks, 1,3,5-tris(4-aminophenyl)benzene (TAPB) and
1,3,5-benzenetricarbaldehyde (BTCA), rapidly occurs at room
[
3]
imine-based COFs) that show great promise for gas storage
[
1b,d,f,g,2d,4]
and separation.
Recent advances in COFs have been
focused on incorporating multifunctional subunits, expanding
their scope to numerous practical applications, including catal-
ysis, clean energy, novel ultrasensitive sensors, optoelectronic
[1c,e,2f,3c,4c,5]
devices, and solar energy collectors.
However, prog-
[
a] A. de la PeÇa Ruigómez, D. Rodríguez-San-Miguel, Dr. R. Mas-BallestØ,
Dr. F. Zamora
Nanostrutturati (CNR-ISMN)
Via Gobetti 101, 40129 Bologna (Italy)
Departamento de Química Inorgµnica
Universidad Autónoma de Madrid
[
f] Dr. F. Liscio, Prof. S. Milita
CNR-IMM, Instituto per la Microelettronica e Microsistemi
via P. Gobetti 101, 40129 Bologna (Italy)
2
8049 Madrid (Spain)
E-mail: felix.zamora@uam.es
[g] Dr. O. M. Roscioni
[
b] A. de la PeÇa Ruigómez, Dr. J. L. Segura
Departamento de Química Orgµnica
Facultad de Ciencias Químicas
Universitàdi Bologna
Dipartimento di Chimica Industriale
“Toso Montanari”, Viale Risorgimento 4, 40136, Bologna (Italy)
Universidad Complutense de Madrid
Avda. Complutense s/n 28040 Madrid (Spain)
[
h] Dr. O. M. Roscioni
School of Chemistry, University of Southampton
Highfield, Southampton SO17 1BJ (United Kingdom)
[
c] D. Rodríguez-San-Miguel, Dr. F. Zamora
Instituto MadrileÇo de Estudios Avanzados en Nanociencia
[i] Prof. D. Maspoch
(
IMDEA Nanociencia)
Institució Catalana de Recerca i Estudis AvanÅats (ICREA)
Cantoblanco, 28049 Madrid (Spain)
0
8100 Barcelona (Spain)
[
d] Dr. K. C. Stylianou, C. Carbonell, Prof. D. Maspoch
ICN2—Institut Catala de Nanociencia i Nanotecnologia
Campus UAB, 08193 Bellaterra, Barcelona (Spain)
[
j] Dr. M. L. Ruiz-Gonzµlez
Departamento de Química Inorgµnica
Universidad Complutense de Madrid
[
e] Dr. M. Cavallini, Dr. D. Gentili
Consiglio Nazionale delle Ricerche
Instituto per lo Studio dei Materiali
2
8040 Madrid (Spain)
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201501692.
Chem. Eur. J. 2015, 21, 10666 – 10670
10666
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Communication
temperature and in air, leading to the formation of RT-COF-
(Figure 1a). To date, formation of imine-based polymers has
ment with the formation of the imine bonds as it shows: i) a
resonance at 157 ppm that corresponds to the carbon atom of
the C=N bond; and ii) a resonance at 148 ppm that corre-
sponds to the quaternary carbon atom of the phenyl group of
the triamine linked with the nitrogen atom. Finally, the ele-
mental analysis of RT-COF-1 confirmed a molecular formula of
C H N O for both RT-COF-1 synthesized in m-cresol and
1
required the use of high temperatures, and syntheses at room
temperature have been only reported for on-surface synthe-
[
3d,9]
tized materials.
RT-COF-1 is crystalline, showing a laminar
hexagonal structure, is stable up to 4508C, and is porous to
both N and CO . Under these specific synthetic conditions, we
2
2
33 26
3
2.5
demonstrate that one can use LCW and ink-jet printing to con-
trol the formation of RT-COF-1 at exact locations of a surface
by directly depositing its precursors. We anticipate that this
direct patterning strategy will allow the creation of micro- and
submicrostructures of RT-COF-1 on both rigid and flexible sub-
strates.
DMSO (Section S2 in the Supporting Information). This data is
in agreement with the weight loss of 6.6% observed in the
thermogravimetric analysis of RT-COF-1 from 30 to 3008C,
which we attributed to the loss of approximately 2.5H O mole-
2
cules (calcd.: 7.2%; Figure S7 in the Supporting Information).
Field-emission scanning electron microscopy (FE-SEM)
images of the powder demonstrated the formation of uniform
aggregates of flakes (Figure 1b). Importantly, we were able to
study the shape and dimensions of isolated flakes by deposit-
ing a methanolic suspension of RT-COF-1 on SiO and using
2
atomic force microscopy (AFM). Figure 1c shows characteristic
AFM images of isolated flakes, confirming that RT-COF-1 is
based on a laminar structure with sharp edge angles of ap-
proximately 608 and 1208, lateral dimensions on the order of
several tens of microns, and apparent heights in the range 4
to 30 nm (see also Figure S8 in the Supporting Information).
Synchrotron radiation grazing incidence X-ray diffraction
(
GIXRD) performed on samples of RT-COF-1 directly synthe-
sized on SiO confirmed that they are crystalline. Figure 2a and
2
b depicts the 2D GIXRD patterns of RT-COF-1 synthesized in
m-cresol and DMSO, respectively. For both cases, the observa-
tion of the same resolved Bragg peaks (d-spacing: 15.55, 8.94,
7
.71, 5.75, 4.53, and 3.54 Š) in the radially integrated diffracted
intensity profiles provides the signature of the formation of an
identical large-scale structure with crystalline organization (Fig-
ure 2c). Noticeably, the use of DMSO slightly limits the crystal-
linity of RT-COF-1 (supported by the intense halo in the diffrac-
tion pattern typical of the amorphous phase). We used the full
width at half maximum (FWHM) parameter of the better-re-
solved Bragg reflections to estimate the size of the crystal do-
Figure 1. a) Schematic illustration of the room-temperature polyimine con-
densation to form RT-COF-1. b) Representative FE-SEM image of RT-COF-1.
c) Representative AFM topographic image of isolated flakes of RT-COF-1 on
[
10]
mains by using the Scherrer equation; the domains were
found to be 12 and 9 nm for the RT-COF-1 synthesized in m-
cresol and DMSO, respectively. The indexation of Bragg peaks
was performed by taking into account the analogies with the
powder XRD pattern of a known COF synthesized using trigo-
2
SiO (top) and the corresponding height profile (bottom).
RT-COF-1 was synthesized by adding 1 mL of acetic acid to
0 mL of TAPB and BTCA (1:1 molar ratio; 0.028m) in either m-
[
1b]
1
nal units. The above-mentioned Bragg reflections were in-
dexed as the (001), (110), (200), (210), (220), and (001) diffrac-
tion planes, respectively, of a hexagonal unit cell with cell pa-
rameters of a=b=17.9Æ0.3 Š and c=3.54Æ0.03 Š.
cresol or DMSO under gentle stirring at room temperature
Figure 1a). After 1 min, a characteristic yellow gel was formed,
(
which was repeatedly washed with methanol and tetrahydro-
furane, dried under an open atmosphere for 2 days, and dried
further at 1508C under vacuum (50 mbar) overnight to form
RT-COF-1 as a yellow solid (yield: 96%). The formation of RT-
To gain more insights into the crystal structure of RT-COF-1,
we performed plane-wave density functional theory (DFT) cal-
culations using the constrained cell parameters determined
from the GIXRD data. For detailed information on these calcu-
lations, see Section S8 in the Supporting Information. We
found that a structure with a trigonal P3 space group is the
most energetically stable. This structure is likely to be the cor-
rect one owing to the similarity found between the simulated
13
COF-1 at room temperature was confirmed by solid-state
C
cross polarization/magic angle spinning nuclear magnetic reso-
nance (CP-MAS NMR) (Figure S3 in the Supporting Information)
and FTIR spectroscopies (Figure S6 and Table S1 in the Sup-
porting Information), and elemental analysis. The FTIR spec-
trum clearly shows the presence of both imine C=N and C-C= powder XRD derived from the structure and the experimental
À1
À1
N-C stretching bands at 1617 cm and 1280 cm , respectively
one obtained in grazing incidence and specular geometries
(Figure 2c). The structure shows a laminar framework in which
13
(
Figure S6). The C CP-MAS NMR spectrum is also in agree-
Chem. Eur. J. 2015, 21, 10666 – 10670
www.chemeurj.org
10667
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Communication
2
À1
Teller (BET) surface area was found to be 329 m g in the
0
range of p/p =0.05–0.3 (Figure 2 f), which is close to other
[
3c,12]
values recently reported for similar imine-linked COFs.
The
fitting of the N adsorption data to the Dubinin–Radushkevich
2
3
À1
equation provides a pore volume of 0.224 cm g (Figure S15
in the Supporting Information).
RT-COF-1 is also porous to CO at 195, 273, and 298 K, with
2
0
a BET surface area calculated from the CO adsorption (p/p =
2
2
À1
0
.05–0.3) of 369 m g (Figure S16 in the Supporting Informa-
tion). The strength of interactions between RT-COF-1 and CO
2
[
13]
was evaluated by using the Clausius–Clapeyron equation. It
À1
was found that the isosteric heat of adsorption is 16.4 kJmol
À1
at zero coverage, whereas it is between 15.1 and 18.1 kJmol
at high loadings (Figure S17 in the Supporting Information).
This constant value suggests that the interactions between
CO and RT-COF-1 are strong either at zero coverage or high
2
loadings owing to the presence of the Lewis basic imine
groups.
It is worth mentioning that besides insoluble COFs, soluble
porous cage compounds have been demonstrated to be proc-
[
14]
essable on surfaces for several purposes. Here, the gentle re-
action conditions required for the preparation of RT-COF-1 al-
lowed us to overcome the typical limitations preventing COF-
based materials from being deposited on surfaces in a con-
trolled manner. Our approach relied on confining the room-
temperature synthesis of RT-COF-1 into small volumes contain-
ing the RT-COF-1 precursors, volumes that were pre-patterned
on the surfaces.
We first fabricated RT-COF-1 stripes on SiO substrates by
2
Figure 2. a,b) 2D-GIXRD images collected for RT-COF-1 prepared using m-
cresol and DMSO as solvents, respectively. c) Radial integration of all the 2D-
GIXRD images (red=in m-cresol; blue=in DMSO) and the calculated PXRD
for the structure represented in (d). d,e) Schematic views of the crystalline
structure of RT-COF-1 with the unit cell parameters indicated. Carbon, nitro-
gen and hydrogen are represented as grey, blue and white spheres, respec-
using lithographically controlled wetting (LCW). LCW is
a simple, fast, and sustainable wet patterning process that ex-
ploits the self-organization of soluble materials under the pro-
trusion of a soft stamp (Section S11 in the Supporting Informa-
[
8a–c]
tion).
RT-COF-1 stripes were fabricated by patterning an m-
2
tively. f) N isotherms at 77 K collected on RT-COF-1; filled dots: adsorption,
empty dots: desorption.
cresol solution of TAPB and BTCA into 1 mm wide microchan-
nels of a poly(dimethylsiloxane) (PDM) stamp (Scheme S2 in
the Supporting Information). Then, acetic acid was poured into
the open ends of the microchannels, confining the RT-COF-
1 synthesis into these channels. Figure 3a and b shows the re-
sulting 1 mm wide RT-COF-1 stripes that remain after removing
the stamp. We could also reduce the size of the stripes by
using a PDM stamp with thinner channels (width=500 nm), re-
sulting in correspondingly thinner RT-COF-1 stripes of 500 nm
(Figure 3c).
the imine-based sheets are stacked in an AA fashion (separa-
tion between sheets: 3.5 Š; Figure 2e), resulting in the forma-
tion of 1D hexagonal-shaped pores with dimensions of
11.9 Š”11.9 Š (including van der Waals radii) along the c-axis
(
Figure 2d). The solvent-accessible volume of RT-COF-1 deter-
[11]
mined by using PLATON is 50% per unit cell.
Transmission electron microscopy analysis of RT-COF-1 con-
firms the presence of nanodomains exhibiting periodicities of
GIXRD, polarized optical microscopy (POM), and AFM were
used to characterize the patterned stripes (Figure 3a–d). Im-
portantly, GIXRD performed on the 1 mm wide RT-COF-1 stripes
showed a powder XRD spectrum that coincides with those de-
rived from the structure and from the bulk synthesis (Fig-
ure 3d). This evidence confirms that RT-COF-1 maintained its
crystal structure once synthesized and structured on surfaces.
The crystallinity of the stripes was also corroborated by POM,
images from which show a slight birefringence (Figure 3b).
Here, the stripes appeared homogeneously colored in blue, in-
dicating that their mean thickness is almost constant over the
entire stripe and, therefore, that the confined synthesis by
LCW has induced a coherent order along the direction of the
1
.2 nm (Figure S13 in the Supporting Information). This dis-
tance fits well to the pore dimensions of RT-COF-1. A careful
analysis allows us to infer the hexagonal distribution of the
pores (Section S9 in the Supporting Information). The absence
of a long-range ordered hexagonal distribution is in agreement
with the GIXRD data, apart from the degradation induced
under the electron beam.
À3
Thermal treatment of RT-COF-1 at 1508C and 10 bar over-
night produced the activation of the material (Figure S14 in
the Supporting Information). Nitrogen isotherms were record-
ed to confirm the permanent porosity of the activated RT-
COF-1 at 77 K. From the N isotherm, the Brunauer–Emmett–
2
Chem. Eur. J. 2015, 21, 10666 – 10670
www.chemeurj.org
10668
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Communication
Figure 3. a) Bright-field optical image of 1 mm wide RT-COF-1 stripes fabricated by LCW. The inset shows a representative AFM image showing the formation
of the characteristic RT-COF-1 flakes. Z scale is 0–50 nm. b) Corresponding POM image. c) Representative FE-SEM image of 500 nm wide RT-COF-1 stripes fab-
ricated by LCW. d) Radial integration of the 2D-GIXRD image collected for the 1 mm wide RT-COF-1 stripes (middle) compared to the one obtained in the syn-
thesis of bulk RT-COF-1 (top) and to the one derived from the theoretical structure (bottom). e) Representative optical image a 70 mm-in-diameter dot array
of RT-COF-1 on SiO
2
generated by an ink-jet printer. f) Representative FE-SEM image of a 40 mm-in-diameter dot array of RT-COF-1 on flexible acetate paper
generated by an ink-jet printer. g,h) Zoomed FE-SEM images of one of these dots, showing again the formation of the characteristic RT-COF-1 flakes.
stripes. Finally, a detailed investigation of the stripes by AFM
showed that they are formed by the characteristic flakes of RT-
COF-1, the size of which ranges from 25 to 100 nm (inset of
Figure 3a). It is important to note here that the fabricated
stripes were shown to remain stable for a few months after
preparation as well as after their treatment with water and al-
cohol solutions.
1 on solid and flexible supports that enable future applica-
tions. The preliminary results using ink-jet printing are very
promising for automation and enables patterning with high
resolution covering large areas in minutes, therefore being at-
tractive for manufacturing. Our ongoing studies are focusing
on the expansion of the family of RT-COFs and studying their
tailored properties when are already integrated on surfaces.
To expand the diversity of surfaces as well as to prove the
scalability of the patterning, we also explored ink-jet printing.
Ink-jet printing is a scale-up and inexpensive patterning tech-
nology that enables the organization of materials on a variety
Acknowledgements
We thank the MINECO (Spain) for financial support through
[8d]
of surfaces, including rigid and flexible substrates. Accord-
projects
MAT2013-46753-C2-1-P,
MAT2012-30994,
and
ingly, we fabricated large dot arrays of RT-COF-1 on both rigid
MAT2014-52305-P). A.P. acknowledges UCM for a predoctoral
fellowship. The authors acknowledge the use of the IRIDIS
High Performance Computing Facility, and associated support
services at the University of Southampton, for the theoretical
work presented in this article.
SiO surfaces (Figure 3e) and flexible acetate paper (Figure 3 f–
2
h) by simply depositing an ink consisting of a stoichiometric
DMSO solution of TAPB and BTCA using a commercial Dimatrix
Fuji ink-jet printer. On both type of surfaces, all printed pat-
terns showed significant uniformity and resolution (dot size
controlled from 50 to 70 mm), confirming the reliability and ef-
2
Keywords: covalent organic frameworks · ink-jet printing ·
porous crystalline materials · processability · soft-lithography
ficiency of the printing over extensions of 1 cm . The printed
structures on SiO and acetate paper were characterized by op-
2
tical microscopy, FE-SEM, and AFM (Figure 3e–h and Figur-
es S19–20 in the Supporting Information), showing in all cases
the characteristic formation of flakes of RT-COF-1.
[
1] a) S. Y. Ding, W. Wang, Chem. Soc. Rev. 2013, 42, 548–568; b) A. P. Cote,
A. I. Benin, N. W. Ockwig, M. O’Keeffe, A. J. Matzger, O. M. Yaghi, Science
2
005, 310, 1166–1170; c) S. Wan, J. Guo, J. Kim, H. Ihee, D. L. Jiang,
Angew. Chem. Int. Ed. 2008, 47, 8826–8830; Angew. Chem. 2008, 120,
958–8962; d) R. W. Tilford, W. R. Gemmill, H. C. zur Loye, J. J. Lavigne,
In conclusion, we have reported the synthesis of an extend-
ed imine-based COF using a simple and one-pot reaction at
room temperature. Under these conditions, RT-COF-1 is crystal-
line with hexagonal structure, possesses pronounced thermal
stability, and is permanently porous to N and CO . We have
8
Chem. Mater. 2006, 18, 5296–5301; e) E. L. Spitler, W. R. Dichtel, Nat.
Chem. 2010, 2, 672–677; f) R. W. Tilford, S. J. Mugavero, P. J. Pellechia,
J. J. Lavigne, Adv. Mater. 2008, 20, 2741–2744; g) H. M. El-Kaderi, J. R.
Hunt, J. L. Mendoza-Cortes, A. P. Cote, R. E. Taylor, M. O’Keeffe, O. M.
Yaghi, Science 2007, 316, 268–272; h) J. X. Jiang, A. I. Cooper, Top. Curr.
Chem. 2010, 293, 1–33.
2
2
demonstrated that the room-temperature synthesis of RT-COF-
can be miniaturized on surfaces by using a soft-lithography
1
[
2] a) J. W. Colson, A. R. Woll, A. Mukherjee, M. P. Levendorf, E. L. Spitler,
V. B. Shields, M. G. Spencer, J. Park, W. R. Dichtel, Science 2011, 332,
228–231; b) J. F. Dienstmaier, A. M. Gigler, A. J. Goetz, P. Knochel, T.
technique and ink-jet printing. Both techniques have allowed
the fabrication of micro/submicrometer patterns of RT-COF-
Chem. Eur. J. 2015, 21, 10666 – 10670
www.chemeurj.org
10669
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Communication
Bein, A. Lyapin, S. Reichlmaier, W. M. Heckl, M. Lackinger, ACS Nano
011, 5, 9737–9745; c) Z. Kahveci, T. Islamoglu, G. A. Shar, R. Ding, H. M.
El-Kaderi, CrystEngComm 2013, 15, 1524–1527; d) A. P. Côte, H. M. El-
Kaderi, H. Furukawa, J. R. Hunt, O. M. Yaghi, J. Am. Chem. Soc. 2007,
A. R. Woll, M. R. Giovino, A. Saldivar, W. R. Dichtel, Angew. Chem. Int. Ed.
2012, 51, 2623–2627; Angew. Chem. 2012, 124, 2677–2681.
[7] J. W. Colson, J. A. Mann, C. R. DeBlase, W. R. Dichtel, J. Polym. Sci. Part A
2015, 53, 378–384.
2
1
29, 12914–12915; e) A. Nagai, Z. Q. Guo, X. Feng, S. B. Jin, X. Chen,
[8] a) M. Cavallini, D. Gentili, P. Greco, F. Valle, F. Biscarini, Nat. Protoc. 2012,
7, 1668–1676; b) M. Cavallini, C. Albonetti, F. Biscarini, Adv. Mater. 2009,
21, 1043–1053; c) M. Cavallini, F. Biscarini, Nano Lett. 2003, 3, 1269–
1271; d) V. Subramanian in Inkjet-Based Micromanufacturing (Eds.: J. P.
Korvink, P. J. Smith, D.-Y. Shin), Wiley-VCH, Weinheim, Germany, 2012,
pp. 313–329.
[9] a) M. G. Schwab, B. Fassbender, H. W. Spiess, A. Thomas, X. L. Feng, K.
Mullen, J. Am. Chem. Soc. 2009, 131, 7216–7218; b) X. D. Zhuang, F.
Zhang, D. Q. Wu, X. L. Feng, Adv. Mater. 2014, 26, 3081–3086; c) L. R.
Xu, X. Zhou, Y. X. Yu, W. Q. Tian, J. Ma, S. B. Lei, ACS Nano 2013, 7,
8066–8073.
[10] B. E. Warren, X-Ray Diffraction, Addison-Wesley, Massachusetts, 1969.
[11] A. L. Spek, Acta Crystallogr. Sect. D 2009, 65, 148–155.
[12] a) S. Kandambeth, A. Mallick, B. Lukose, M. V. Mane, T. Heine, R. Bane-
rjee, J. Am. Chem. Soc. 2012, 134, 19524–19527; b) P. Pachfule, M. K.
Panda, S. Kandambeth, S. M. Shivaprasad, D. D. Diaz, R. Banerjee, J.
Mater. Chem. A 2014, 2, 7944–7952; c) Y. H. Jin, Y. L. Zhu, W. Zhang,
CrystEngComm 2013, 15, 1484–1499; d) P. Pandey, A. P. Katsoulidis, I. Er-
yazici, Y. Y. Wu, M. G. Kanatzidis, S. T. Nguyen, Chem. Mater. 2010, 22,
4974–4979.
[13] K. Sumida, D. L. Rogow, J. A. Mason, T. M. McDonald, E. D. Bloch, Z. R.
Herm, T. H. Bae, J. R. Long, Chem. Rev. 2012, 112, 724–781.
[14] a) M. J. Bojdys, T. Hasell, N. Severin, K. E. Jelfs, J. P. Rabe, A. I. Cooper,
Chem. Commun. 2012, 48, 11948–11950; b) M. Brutschy, M. W. Schneid-
er, M. Mastalerz, S. R. Waldvogel, Adv. Mater. 2012, 24, 6049–6051; c) M.
Brutschy, M. W. Schneider, M. Mastalerz, S. R. Waldvogel, Chem.
Commun. 2013, 49, 8398–8400.
X. S. Ding, D. L. Jiang, Nat. Commun. 2011, 2, 536; f) X. A. Feng, L. Chen,
Y. P. Dong, D. L. Jiang, Chem. Commun. 2011, 47, 1979–1981.
3] a) S. L. Cai, Y. B. Zhang, A. B. Pun, B. He, J. H. Yang, F. M. Toma, I. D.
Sharp, O. M. Yaghi, J. Fan, S. R. Zheng, W. G. Zhang, Y. Liu, Chem. Sci.
[
2
014, 5, 4693–4700; b) S. B. Jin, T. Sakurai, T. Kowalczyk, S. Dalapati, F.
Xu, H. Wei, X. Chen, J. Gao, S. Seki, S. Irle, D. L. Jiang, Chem. Eur. J. 2014,
0, 14608–14613; c) S. Y. Ding, J. Gao, Q. Wang, Y. Zhang, W. G. Song,
2
C. Y. Su, W. Wang, J. Am. Chem. Soc. 2011, 133, 19816–19822; d) X. H.
Liu, C. Z. Guan, S. Y. Ding, W. Wang, H. J. Yan, D. Wang, L. J. Wan, J. Am.
Chem. Soc. 2013, 135, 10470–10474; e) M. G. Rabbani, A. K. Sekizkardes,
Z. Kahveci, T. E. Reich, R. S. Ding, H. M. El-Kaderi, Chem. Eur. J. 2013, 19,
3
324–3328.
[
4] a) J. X. Jiang, F. Su, A. Trewin, C. D. Wood, H. Niu, J. T. A. Jones, Y. Z. Khi-
myak, A. I. Cooper, J. Am. Chem. Soc. 2008, 130, 7710–7720; b) F. J.
Uribe-Romo, J. R. Hunt, H. Furukawa, C. Klock, M. O’Keeffe, O. M. Yaghi,
J. Am. Chem. Soc. 2009, 131, 4570–4572; c) H. Furukawa, O. M. Yaghi, J.
Am. Chem. Soc. 2009, 131, 8875–8883; d) C. J. Doonan, D. J. Tranche-
montagne, T. G. Glover, J. R. Hunt, O. M. Yaghi, Nat. Chem. 2010, 2, 235–
2
38.
5] a) P. Kuhn, M. Antonietti, A. Thomas, Angew. Chem. Int. Ed. 2008, 47,
450–3453; Angew. Chem. 2008, 120, 3499–3502; b) E. L. Spitler, M. R.
[
[
3
Giovino, S. L. White, W. R. Dichtel, Chem. Sci. 2011, 2, 1588–1593;
c) X. S. Ding, J. Guo, X. A. Feng, Y. Honsho, J. D. Guo, S. Seki, P. Maitarad,
A. Saeki, S. Nagase, D. L. Jiang, Angew. Chem. Int. Ed. 2011, 50, 1289–
1
293; Angew. Chem. 2011, 123, 1325–1329.
6] a) D. D. Medina, V. Werner, F. Auras, R. Tautz, M. Dogru, J. Schuster, S.
Linke, M. Doblinger, J. Feldmann, P. Knochel, T. Bein, ACS Nano 2014, 8,
4
042–4052; b) E. L. Spitler, B. T. Koo, J. L. Novotney, J. W. Colson, F. J.
Uribe-Romo, G. D. Gutierrez, P. Clancy, W. R. Dichtel, J. Am. Chem. Soc.
011, 133, 19416–19421; c) E. L. Spitler, J. W. Colson, F. J. Uribe-Romo,
Received: April 30, 2015
Published online on June 19, 2015
2
Chem. Eur. J. 2015, 21, 10666 – 10670
www.chemeurj.org
10670
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim