View Article Online

View Journal

ChemComm
Chemical Communications
Accepted Manuscript

This article can be cited before page numbers have been issued, to do this please use: N. Wei, R. Zuo, Y.
Zhang, Z. Han and X. Gu, Chem. Commun., 2017, DOI: 10.1039/C7CC00363C.

Volume 52 Number 1 4 January 2016 Pages 1–216 This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
ChemComm
Chemical Communications Accepted Manuscripts are published online shortly after
[Link]/chemcomm

acceptance, before technical editing, formatting and proof reading.

Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.

You can find more information about Accepted Manuscripts in the

author guidelines.

Please note that technical editing may introduce minor changes

to the text and/or graphics, which may alter content. The journal’s
ISSN 1359-7345 standard Terms & Conditions and the ethical guidelines, outlined
COMMUNICATION
in our author and reviewer resource centre, still apply. In no
Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyen et al.
Reactivity differences of Sc3N@C2n (2n = 68 and 80). Synthesis of the
first methanofullerene derivatives of Sc3N@D5h-C80
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.

[Link]/chemcomm
 Please do not adjust margins
Page 1 of 4 ChemComm
View Article Online
DOI: 10.1039/C7CC00363C

Journal Name

COMMUNICATION

Robust high-connected rare-earth MOFs as efficient

Published on 23 February 2017. Downloaded by University of Lethbridge on 23/02/2017 [Link].

heterogeneous catalysts for CO2 conversion

Received 00th January 20xx,
Accepted 00th January 20xx Na Wei,a Rong-Xia Zuo,a Yu-Yang Zhang,a Zheng-Bo Han*a and Xue-Jun Gu*b

ChemComm Accepted Manuscript

DOI: 10.1039/x0xx00000x

[Link]/

Two series of chemical and thermal stable rare-earth MOFs were enhanced stability towards harsh chemical conditions or
7
constructed by trinuclear [M3(μ3-OH)(COO)6] SBUs and linear elevated temperatures. So increasing the connectivity of a
dicarboxylate linkers, which feature three dimensional 12- known SBUs is of great interests. In trinuclear [M3(µ3-O/μ 3-
connected frameworks with hcp topology. These materials contain OH)(COO)6] family, the reported highest connectivity is the 9-
12
a large density of Lewis acidic sites leading to high catalytic connected MCF-19 (ncb network), however, no other higher
activity towards the cycloaddition of CO2 and epoxides under mild connected network have been reported so far.
condition. Herein, two series of 12-connected rare-earth (RE = Y, Tb
and Er) MOFs incorporating [RE3(μ3-OH)(COO)6] SBUs (Fig. 1a)
Over the past two decades, metal-organic frameworks (MOFs) and linear dicarboxylates were synthesized with the formulas
have been studied extensively attribute to their intriguing [(CH3)2NH2][RE3(µ3-OH)(BDC)3(HCOO)3] (RE-BDC) and
architecture and potential applications in multiple areas, such [(CH3)2NH2][RE3(µ3-OH)(NDC)3(HCOO)3 ] (RE-NDC), (H2BDC =
1 2
as gas separation and storage, small-molecule separation, 1,4-benzenedicarboxylic acid, H2NDC = 2,6-
3 4
chemical sensing and catalysis. Because of the highly naphthalenedicarboxylic acid) (Fig. S1†). These materials show
designable nature of MOFs, their multiple structures, very high thermal and chemical stability in common organic
dimensionality and chemical properties can be realized via the solvents and water with pH values ranging from 2−12. Owing
scientific selection and assembly of secondary building units to the high-density of Lewis acidic sites, these complexes all
(SBUs): multifunctional organic linkers and metal ions exhibit high catalytic activity towards the cycloaddition of CO2
5
(clusters) with various shapes and extension nodes. However,
reversible coordination bonding of metal ions and organic
6
ligands generally bring the MOFs material poor stability,
which commonly identified as the major shortcoming for their
practical applications in most research areas. Therefore,
construction of MOFs with improved stability has become a
significant goal to plentiful researchers.
Trinuclear [M3(µ3-O/μ3-OH)(COO)6] cluster, as a classical
shape changeable trigonal-prismatic SBUs, facilitates a
7
plethora of polyhedral nets and highly porous materials. Due
to its flexibility, the MOFs assembled by [M3(µ3-O/µ3-
OH)(COO)6] SBUs and linear dicarboxylate linkers exhibit
various topologies, as exemplified by 6-connected MIL-88 (acs
8 9 10
network), MIL-101 (mtn network), MCF-35 (flu-e network)
and the predicted MIL-hypo-2/constructed nickel-complex
11
(reo-e network), et al. High connected MOFs usually present

a
College of Chemistry, Liaoning University, Shenyang 110036, P. R. China. E-mail:
ceshzb@[Link] Fig. 1 (a) 12-connected trinuclear [RE3(μ3-OH)(COO)6] SBUs. Insert: the
b
Institude of Rare and Scattered Elements, College of Chemistry, Liaoning coordination environment of each RE(III) ion. (b) 2D layer formed by
University, Shenyang 110036, P. R. China. E-mail: sheshen311@[Link] [RE3(μ3-OH)(COO)6] SBUs and HCOO-. View of the structure of RE-NDC along
†Electronic Supplementary Informa,on (ESI) available: Experimental details of the a axis (c) and c axis (d).
synthesis and catalysis, additional characterizations. See DOI: 10.1039/x0xx00000x

This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 1

Please do not adjust margins

 Please do not adjust margins
ChemComm Page 2 of 4
View Article Online
DOI: 10.1039/C7CC00363C
COMMUNICATION Journal Name

and epoxides under mild conditions. respectively.

Reaction of RE(NO3)3 (RE = Y, Tb and Er) with H2BDC/H2NDC Generally, MOFs sustained by high connectivity SBUs tend to
in the mixture of DMF and H2O in the presence of nitric acid perform higher thermal and chemical stability. The trigonal
and 2-fluorobenzoic acid at 105°C affords crystals of RE- prismic [M3(µ3-O)(COO)6] SBUs as multi-connected nodes are
BDC/RE-NDC. Single-crystal X-ray crystallography showed that notable for their historical constructions of many MOFs, and
RE-BDC and RE-NDC crystallize in the hexagonal space group most resulting complexes tend to possess excellent chemical
9,12,14
P63/m. Each RE(III) (Y, Tb and Er) center is seven-coordinated stability. So, it is suspected that the 12-connected
-
by four dicarboxylates, one µ3-OH and two HCOO in a triangle [RE3(µ3-OH)(COO)6] clusters maybe endow these RE-based
capping-square coordination environment (Fig. 1a). Besides MOFs excellent chemical stability. To verify our suspection, the
Published on 23 February 2017. Downloaded by University of Lethbridge on 23/02/2017 [Link].

-
the linear dicarboxylates linkers, the HCOO sites of these chemical stabiliy of Er-BDC and Er-NDC were checked by
clusters also act as µ2-bridging ligands to furnish the [RE3(μ3- powder X-ray diffraction (PXRD) studies. The results show that
OH)(COO)6] SBUs as 12-connected nodes. Due to their higher the experimental PXRD patterns were consistent with the
coordinate numbers, the RE(III) ions provide more extension simulated ones upon soaking in various organic solvents for 48

ChemComm Accepted Manuscript

points than the hexa-coordinated transition metal centers. h (Fig. S4 and S5a†), even in the aqueous solutions with pH = 2
Along the a-axis, the 12-connected [RE3(µ3-OH)(COO)6] SBUs (0.01 M HCl) and 12 (0.01 M NaOH) for 12 h (Fig. 2, S5b and
-
are connected by six coordinated HCOO extending to a 2D S6†), indicating that no framework collapse or phase transition
layer (Fig. 1b), and the ratio between the dicarboxylates and happens during the chemical stability tests. However, when
- 1
coordinated HCOO was determined by H-NMR integral crystal samples are soaked in 0.1 M HCl solution and 0.1 M
results (Fig. S2†). The 2D layers are further connected together NaOH, observable change in color, morphology and
through BDC or NDC linkers along the c-axis direction, resulting transparency will occur in several minutes. Similarly, Y- and Tb-
in a 3D framework (Fig. 1c-d) with an unusual uninodal 12- complexes also show super stability toward aqueous solutions
connected hcp topology (Fig. S3†). The vertex symbol for this with pH = 2 and 12 (Fig. S7†). RE-BDC and RE-NDC also display
24 33 9
net is 3 .4 .5 , as analysized by the TOPOS program. high thermal stability. Thermogravimetric analysis (TGA)
13
PLATON analysis reveals that the frameworks of RE-BDC and curves (Fig. S8†) show that these complexes present no
3 3
RE-NDC are composed of voids of 518.2 Å and 546.6 Å , obvious weight loss below 300 °C (ca. 3.4% weight loss
assigned as the removal of dimethylammonium cation).
Variable-temperature PXRD patterns demonstrated that these
complexes maintain crystalline form with the environmental
temperature ranging from ambient temperature to 300 °C (Fig.
S9†), then the diffraction patterns change obvious until the
o
temperature increased to 350 C. It confirmed that Er-BDC and
Er-NDC keep structural stability until the environmental
temperature exceeded 300 °C, which are superior to 6-
connected MIL-88 MOFs, the latter present similar structure

Table 1. Cycloaddition of CO2 and propylene oxide

catalyzed by variety of catalysts.

Entry Catalyst Conversion (%)a TONb

1 Y-BDC, TBAB 95 543

2 Er-BDC, TBAB 91 521
3 Tb-BDC, TBAB 89 509
4 Y-NDC, TBAB 94 538
5 Er-NDC, TBAB 90 515
6 Tb-NDC, TBAB 87 498
7 TBAB 30 29
8c Y(NO3)3, TBAB 90 --
9d Y2O3, TBAB 12 --
Reaction conditions: propylene oxide (28.6 mmol), catalyst (0.05 mmol,
corresponding to RE3 cluster), TBAB (0.3 mmol) under CO2 (1.0 MPa), 60 oC
Fig. 2 (a) Pictures of Er-BDC under optical microscope. As-synthesized (A), and 12 hours. The conversions were determined by GC. bTON is the
after soaking in n-hexane (B), 0.01 M HCl (C) and 0.01 M NaOH (D). (b) PXRD turnover number (product (mmol)/catalyst (mmol)). cY(NO3)3 (0.15 mmol),
patterns of Er-BDC and the samples treated with n-hexane, H2O, 0.01M HCl TBAB (0.3 mmol), CO2 (1.0 MPa), 60oC, 10 h. dY2O3 (0.075 mmol), TBAB (0.3
and 0.01 M NaOH. mmol), CO2 (1.0 MPa), 60oC, 12 h.

2 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

Please do not adjust margins

 Please do not adjust margins
Page 3 of 4 ChemComm
View Article Online
DOI: 10.1039/C7CC00363C
Journal Name COMMUNICATION
8
but with lower connectivity. For instance, when heated to
15 Table 2. Cycloaddition of CO2 and various epoxides
200°C, the PXRD patterns of MIL-88B(V) exhibited a large
catalyzed by Y-BDC and Y-NDC.
variation in the position of the peaks, indicating the crystalline
phase have changed.
RE-BDC and RE-NDC are potential Lewis acidic catalysts
owing to their high concentration of the Lewis acidic seven-
coordinated RE(III) ions in their structures. To determine this
point, pyridine adsorption experiments were carried out on Y-
Y-BDC Y-NDC
BDC and Y-NDC at room temperature. The pyridine adsorption
Entry Epoxides Conversion Conversion
Published on 23 February 2017. Downloaded by University of Lethbridge on 23/02/2017 [Link].

fourier-transform infrared (Py-IR) spectra show the peaks at TON b

TON
-1 -1 (%)a (%)
1448 cm and 1605 cm typical for pyridine adsorbed on
Lewis acid sites, confirming the Lewis acidity of Y-BDC and Y- 1 88 503 86 492
16
NDC (Fig. S10†). Combination of Lewis acidity and excellent

ChemComm Accepted Manuscript

stability of these complexes inspired us to investigate their 85 486 83 475
2
heterogeneous Lewis acidic catalytic activities towards the
cycloaddition of CO2 and epoxides. 3 80 458 82 469
Recently, the cycloaddition of CO2 and epoxides as one of
the most powerful and attractive strategies for the CO2
chemical fixation have attracted more concern of 4 72 412 70 400
researchers.17 In this reaction, the valuable chemical products
cyclic carbonates can be converted from CO2 as a cheap C-1 Reaction conditions: epoxides (28.6 mmol), catalyst (0.05 mmol,
source.18 So, the cycloaddition of CO2 and propylene oxide (PO) corresponding to Y3 cluster), TBAB (0.3 mmol) under CO2 (1.0 MPa), 60 oC
and 12 hours. aThe yields were determined by GC. bTON is the turnover
acts as a typical reaction to study the catalytic activity of RE- number (product (mmol)/catalyst (mmol)).
BDC and RE-NDC. The reactions were processed in an
autoclave reactor using the epoxides (28.6 mmol) and CO2
under 1 MPa pressure at 60 °C in the presence of 0.05 mmol which outperform some MOF-based catalysts. For instance,
RE-BDC as catalyst and 0.3 mmol TBAB (tetrabutylammonium {Cu(Hip)2(Bpy)}n reported by Park et al. gave allyl glycidyl ether
bromide) as co-catalyst. The conversions of the PO were conversion of 89.2% using approximate tenfold amount of
confirmed by gas chromatography (GC) analyses and the catalyst (1.6 mol%) at 80oC under 1.2 MPa CO2 pressure.20
results were summarized in the Table 1. After 12 hours, the Another Y-based catalyst, gea-MOF-1,21 demonstrates catalytic
conversion of PO catalyzed by Y-BDC reaches 95%, activity for the cycloaddition of propylene oxide/epoxybutane
demonstrating the highest catalysis activity of Y-BDC with a and CO2 with yields of 88% and 94% under a relatively harsh
TON value of 543 followed by Er-BDC and Tb-BDC with values conditions (120 oC and 2 MPa CO2 pressure). The
of 521 and 509, respectively. The different atomic radius of comparatively lower conversions of styrene oxide (72% and
central RE atoms (Y < Er < Tb) may contribute to the diversity 70%) are attributable to the low reactivity at its β-carbon
of their catalytic capacities.19 Under the same conditions, RE- center (Table 2, entry 4).20
NDC series exhibit high activities toward the cycloaddition of A tentative mechanism for the cycloaddition of CO2 and
CO2 and PO (Table 1, entries 4-6), in which Y-NDC also gives epoxide into cyclic carbonate is proposed to be the Lewis acid
the highest conversion (94%) of PO. Compared with other catalysis.22 As illustrated in Fig. 3, epoxides first bind to the
benchmark MOFs catalysts (Table S3†), Y-BDC and Y-NDC also Lewis acidic RE sites through the O atoms to activate the epoxy
exhibit well catalytic activity towards the cycloaddition of CO2 ring. Then, TBAB attacks the less-hindered C atoms of the
with PO. We also tested simple Y(NO3)3 (0.15 mmol) as a epoxide using its Br- as nucleophile to open the epoxy ring.
homogeneous catalyst for the cycloaddition of CO2 with PO. Subsequently, the opened epoxy ring interacts with CO2
The result shows that Y(NO3)3/TBAB system displays a forming an alkylcarbonate anion, which is converted into
powerful catalytic activity under the same conditions (Table 1, corresponding cyclic carbonate through the final ring-closing
entry 8). Y2O3, because of its insolubility in the reaction system, step, and TBAB is recycled simultaneously. In view of the small
was also studied as a heterogeneous catalyst for this reaction window size of the 12-connected framework (ca. 1.7 Å2), the
under similar conditions (Table 1, entry 9). The low catalytic substrates can’t enter the pore, and the reactions almost occur
activity of Y2O3 indicated that the high accessibility of the on the external surface of the catalysts.
Lewis acidic Y(III) sites is indispensable for epoxide activation Leaching tests have been performed to testify the
as a first reaction step. heterogeneous nature of the catalysts Y-BDC and Y-NDC. The
results show that the transformation of the PO dramatically
In consideration of the higher activities of Y-based
decreases after removal of catalysts at 6 h (Fig. S11†). In
complexes, we choose Y-BDC and Y-NDC to investigate the
addition, inductively coupled plasma (ICP) analyses also
cycloaddition of CO2 and other epoxides. After 12 hours, Y-BDC
excluded the leaching of Y, confirming the stability and
and Y-NDC (0.05mmol, 0.17 mol%) both afforded highly
insolubility of the catalysts in this reaction system. The
conversion of epoxybutane (88% and 86%), allyl glycidyl ether
recyclability and reusability of the catalysts for the
(85% and 83%) and butyl glycidyl ether (80% and 82%, Table 2),

This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 3

Please do not adjust margins

 Please do not adjust margins
ChemComm Page 4 of 4
View Article Online
DOI: 10.1039/C7CC00363C
COMMUNICATION Journal Name

X. Bu, T. Wu, S.-T. Zheng, L. Wang and P. Feng, Nat. Commun.,

2013, 4, 2344; (c) J.-R. Li, J. Sculley and H.-C. Zhou, Chem.
Rev., 2011, 112, 869-932.
3 (a) Y. Cui, Y. Yue, G. Qian and B. Chen, Chem. Rev., 2011, 112,
1126-1162; (b) Z. Hu, B. J. Deibert and J. Li, Chem. Soc. Rev.,
2014, 43, 5815-5840.
4 (a) J. Liu, L. Chen, H. Cui, J. Zhang, Li Zhang and C.-Y. Su,
Chem. Soc. Rev., 2014, 43, 6011-6061; (b) L. Ma, C. Abney
and W. Lin, Chem. Soc. Rev., 2009, 38, 1248-1256; (c) J. Lee,
O. K. Farha, J. Roberts, K. A. Scheidt, S. T. Nguyen and J. T.
Hupp, Chem. Soc. Rev., 2009, 38, 1450-1459.
Published on 23 February 2017. Downloaded by University of Lethbridge on 23/02/2017 [Link].

5 (a) W. Lu, Z. Wei, Z.-Y. Gu, T.-F. Liu, J. Park, J. Park, J. Tian, M.
Zhang, Q. Zhang, T. Gentle III, M. Bosch and H.-C. Zhou,
Chem. Soc. Rev., 2014, 43, 5561-5593; (b) D. J.
Tranchemontagne, J. L. Mendoza-Cortés, M. O’Keeffe and O.
M. Yaghi, Chem. Soc. Rev., 2009, 38, 1257-1283; (c) O. M.

ChemComm Accepted Manuscript

Yaghi, M. O’Keeffe, N. W. Ockwig, H. K. Chae, M. Eddaoudi
and J. Kim, Nature, 2003, 423, 705-714; (d) S. Qiu and G. Zhu,
Coord. Chem. Rev., 2009, 253, 2891-2911.
6 (a) J. Canivet, A. Fateeva, Y. Guo, B. Coasne and D.
Farrusseng, Chem. Soc. Rev., 2014, 43, 5594-5617; (b) J.
Fig. 3 Proposed catalytic mechanism for the cycloaddition of CO2 and Gascon and F. Kapteijn, Angew. Chem., Int. Ed., 2010, 49,
epoxide into cyclic carbonate over RE-BDC and RE-NDC. 1530-1532; (c) S. Keskin, T. M. van Heest and D. S. Sholl,
ChemSusChem, 2010, 3, 879-891.
7 A. Schoedel and M. J. Zaworotko, Chem. Sci., 2014, 5, 1269-
cycloaddition of CO2 and PO were further investigated. After 5
1282.
runs of reactions, the complexes still keep equivalent catalytic 8 C. Serre, C. Mellot-Draznieks, S. Surblé, N. Audebrand, Y.
activity to the original ones (Fig. S12†), which can be isolated Filinchuk and G. Férey, Science, 2007, 315, 1828-1831.
from the reaction suspensions by a simple filtration. The PXRD 9 G. Férey, C. Mellot-Draznieks, C. Serre, F. Millange, J. Dutour,
patterns of recycled Y-BDC and Y-NDC after 5 cycles are S. Surblé and I. Margiolaki, Science, 2005, 309, 2040-2042.
10 Y.-S. Wei, J.-Q. Shen, P.-Q. Liao, W. Xue, J.-P. Zhang and X.-M.
complete to the fresh ones (Fig. S13†), indicating the stability
Chen, Dalton Trans., 2016, 45, 4269-4273.
of the catalysts. Thus, the remarkably high efficient catalytic 11 (a) C. Mellot-Draznieks, J. Dutour and G. Férey, Z. Anorg. Allg.
activities towards cycloaddition of CO2 and epoxieds confirm Chem., 2004, 630, 2599-2604. (b) G. Ren, S. Liu, F. Wei, F. Ma,
that both Y-BDC and Y-NDC present significant advantages for Q. Tang and S. Li, Dalton Trans., 2012, 41, 11562-11564.
chemical fixation of CO2 and preparation of cyclic carbonates. 12 Y.-B. Zhang, W.-X. Zhang, F.-Y. Feng, J.-P. Zhang and X.-M.
Chen, Angew. Chem., Int. Ed., 2009, 48, 5287-5290.
In conclusion, we have successfully synthesized two series of
13 A. L. Spek, PLATON, A. M. C. T. Utrecht University: Utrecht.
trinuclear RE cluster-based MOFs, RE-BDC and RE-NDC (RE = Y, The Netherlands, 1998.
Tb, Er) with 12-connected hcp topology. These constructed 14 D. Feng, T.-F. Liu, J. Su, M. Bosch, Z. Wei, W. Wan, D. Yuan,
MOFs exhibit remarkable thermal stability in a wide Y.-P. Chen, X. Wang, K. Wang, X. Lian, Z.-Y. Gu, J. Park, X. Zou
temperature range and chemical stability in water and and H.-C. Zhou, Nat. Commun., 2015, 6, 5979.
15 F. Carson, J. Su, A. E. Platero-Prats, W. Wan, Y. Yun, L. Samain
common organic solvents. In particular, RE-BDC and RE-NDC
and X. Zou, Cryst. Growth Des., 2013, 13, 5036-5044.
contain high density of accessible Lewis acidic RE(III) sites, 16 S. A. Bagshaw and R. P. Cooney, Chem. Mater., 1993, 5,
which demonstrated to be highly efficient heterogeneous 1101-1109.
catalysts for the CO2 chemical fixation. This work was hoped to 17 M. H. Beyzavi, C. J. Stephenson, Y. Liu, O. Karagiaridi, J. T.
open a new way in constructing novel and stable MOFs. Hupp and O. K. Farha, Front. Energy Res., 2015, 2, 63.
18 (a) M. Cokoja, C. Bruckmeier, B. Rieger, W. A. Herrmann and
F. E. Kühn, Angew. Chem., Int. Ed., 2011, 50, 8510-8537; (b) I.
Omae, Coord. Chem. Rev., 2012, 256, 1384-1405.
ACKNOWLEDGMENT 19 (a) R. F. D’Vries, M. Iglesias, N. Snejko, S. Alvarez-García, E.
Gutierrez-Puebla and M. A. Monge, J. Mater. Chem., 2012,
22, 1191-1198; (b) N. C. Jeong, J. S. Lee, E. L. Tae, Y. J. Lee
This work was granted financial support from National Natural and K. B. Yoon, Angew. Chem., Int. Ed., 2008, 47, 10128-
Science Foundation of China (Grant 21671090, 21271096). 10132.
20 A. C. Kathalikkattil, D.-W. Kim, J. Tharun, H.-G. Soek, R.
Roshan and D.-W. Park, Green Chem., 2014, 16, 1607-1616.
Notes and references 21 V. Guillerm, Ł. J. Weseliński, Y. Belmabkhout, A. J. Cairns, V.
D’Elia, Ł. Wojtas, K. Adil and M. Eddaoudi, Nat. Chem., 2014,
1 (a) K. Sumida, D. L. Rogow, J. A. Mason, T. M. McDonald, E. D. 6, 673-680.
Bloch, Z. R. Herm, T.-H. Bae and J. R. Long, Chem. Rev., 2012, 22 (a) L. Liu, S.-M. Wang, Z.-B. Han, M. Ding, D.-Q. Yuan and H.-
112, 724-781; (b) L. J. Murray, M. Dincă and J. R. Long, Chem. L. Jiang, Inorg. Chem., 2016, 55, 3558-3565; (b) Z.-R. Jiang, H.
Soc. Rev., 2009, 38, 1294-1314; (c) S. T. Meek, J. A. Wang, Y. Hu, J. Lu and H.-L. Jiang, ChemSusChem, 2015, 8,
Greathouse and M. D. Allendorf, Adv. Mater., 2011, 23, 249- 878-885.
267.
2 (a) Q. Zhang, J. Yu, J. Cai, R. Song, Y. Cui, Y. Yang, B. Chen and
G. Qian, Chem. Commun., 2014, 50, 14455-14458; (b) X. Zhao,

4 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

Please do not adjust margins