A series of robust metal-porphyrinic frameworks based on rare earth clusters and their application in N-H carbene insertion

Article abstract of DOI:10.1039/c6dt03678c

We herein report a series of microporous metal-porphyrinic frameworks (MPFs), denoted as NUPF-2M, based on rare earth (RE) clusters. NUPF-2M represent the first examples of RE cluster-based MPFs, possessing a rarely seen shp-a topology and exhibiting high thermal and thermal stabilities. After a post-metallization process with FeCl₃, NUPF-2M is catalytically active as an efficient heterogeneous catalyst for intermolecular N-H carbene insertion.

Full text of DOI:10.1039/c6dt03678c

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A Series of Robust Metal-Porphyrinic Frameworks Based on Rare
Earth Clusters and Their Application in N-H Carbene Insertion
Lei Xu,a Meng-Ke Zhai,a Fei Wang,a Lin Sun,a Hong-Bin Dua*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
We herein report a series of microporous metal-porphyrinic (RE) metals exhibit unique electronic, optical, and magnetic
frameworks (MPFs), denoted as NUPF-2M, based on rare earth properties and thus make RE-based materials multifunctional.8
(RE) clusters. NUPF-2M represent the first examples of RE cluster- Recently, the incorporation of multinuclear RE clusters of
based MPFs, possessing
a rarely seen shp-a topology and particular geometry into MOFs has attracted much attention,
exhibiting high thermal and thermal stabilities. After post- resulting in unprecedented architectures and excellent
metallized with FeCl3, NUPF-2M is catalytically active as an properties. However, such multidimensional RE cluster based
effiecient heterogeneous catalyst for intermolecular N-H carbene MOFs are scarce because of the difficulty in linking the highly-
insertion.
connected RE cluster into crystalline extended frameworks.9
By using a modulated synthesis strategy, Eddaoudi and co-
workers have successfully synthesized a series of MOFs that
contain multinuclear clusters of RE metal ions.10-15 Because of
the high charge density and connectivity of the RE clusters,
these RE-MOFs exhibit high chemical and thermal stabilities.
Compared with the Zr/Hf clusters, the multinuclear RE clusters
not only exhibit more abundant connectivities,11 but also could
coordinate to both carboxylate and pyrazol based ligands,10
exhibiting more rich coordination chemistry. Moreover, the RE
clusters present advantages over the Zr/Hf clusters as they
offer opportunities to tune the properties of the resulting
MOFs through use of different rare earth metals.14 The
combination of the RE clusters and porphyrinic ligands may
produce RE-MPFs with unprecedented architectures and
fascinating properties. Interestingly, such research has not
been reported before this work.
(Metallo)porphyrins are a class of biologically relevant
tetrapyrrole macrocycles,1 which have attracted ever-growing
research interests due to their unique electronic,
photochemical and catalytic properties.2 Incorporating
(metallo)porphyrins
assemblies linked by metal ions/clusters via coordination bond
gives rise to metal-porphyrinic frameworks (MPFs),3
into
crystalline
multidimensional
a
fascinating subclass of metal-organic frameworks (MOFs).
Since the first report in 1990s,4 MPFs have attracted escalating
research interests due to their intriguing properties in
heterogeneous catalysis, sensing, gas storage/separation,
light-harvesting, etc.5 Nowadays, much effort has been paid on
constructing porous zirconium/hafnium based MPFs (Zr/Hf-
MPFs) and exploring their underlying applications.6 Adopting
Zr/Hf clusters as nodes would not only impart the preeminent
chemical/thermal stabilities to MPFs, but also render them
remarkable catalytic properties,7 diversifying the applications
of MPFs. Nevertheless, compared with the fast developing
MOFs or porphyrin chemistry, the chemistry of MPFs was still
in its infancy. Considering the fascinating properties of
(metallo)porphyrins, the construction of novel MPFs with
diverse structures and the exploitation of their underlying
applications are still highly desirable.
One important motivation for pursuing MPFs is their
excellent performance as heterogeneous catalysts. Generally,
homogeneous catalyst (metallo)porphyrins were hard to
synthesize, and catalyst recycling has long been an aspiration
for chemists. Using MPFs as heterogeneous catalysts would
overcome the issues of separation and re-utilization of
porphyrin catalysts encountered in homogeneous catalysis. In
the meanwhile, it could also make the catalytically-active
porphyrinic units highly dispersed and accessible, enhancing
the catalytic performance.16 Transition-metal catalysts such as
Re, Rh, Cu or Ru complexes for carbene insertion into N-H
bonds have attracted significant attention,17 although these
catalysts may suffer from some limitations such as restricted
reaction conditions, catalyst poisoning or low yield.18 Recently,
Fe-porphyrins were found to exhibit great efficiency in
Compared with the d-block transition metals, rare-earth
a.State Key Laboratory of Coordination Chemistry, Collaborative Innovation Center
of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering,
Nanjing University, Nanjing, 210023, China. E-mail: hbdu@nju.edu.cn
†Electronic Supplementary Information (ESI) available: Materials and methods,
synthesis, PXRD, FT-IR, TGA, UV-Vis, GC-MS, 1H-NMR, and other characterization
data, crystallographic data. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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catalyzing N-H insertion.19 However, these reactions were all
performed in homogeneous manner, which would cause issues
In NUPF-2Y, each TCPP ligand links four Y9 clusters through
in catalyst recycling and product purification. Till recently Son its four benzoate arms, while each Y9 cluster is connected by
and co-workers reported a microporous Fe-porphyrin polymer 12 porphyrinic ligands. The combination of Y9 cluster and
as heterogeneous catalyst for N-H carbene insertion.20 Herein, quadrangular porphyrin ligand TCPP gives NUPF-2Y a rare shp-
we report the synthesis of a series of stable RE clusters based
a topology that is similar to its Zr6-based analogue PCN-223
MPFs M9O5(TCPP)3∙(solvents)x (TCPP
=
tetrakis(4- (Fig. 1c).16 NUPF-2Y possesses a highly opened 3D framework
carboxyphenyl)porphyrin, M = Y, Gd, Tb, Dy, Er, Yb), denoted (Fig. 1d). Uniform one-dimensional triangular channels of ~1.2
as NUPF-2M (NUPF: Nanjing University Porphyrinic Framework nm in opening sizes were propagated along the c-axis, while
no. 2), which represent the first examples of MPFs assembled smaller rhombus channels of ~0.9 nm were parallel to a- and
by highly-connected RE clusters. All the NUPF-2M frameworks b-axes. The solvent accessible volume of NUPF-2Y was
exhibit not only large permanent porosity, but also high estimated to be 59.8% by using PLATON.21 Notably, the 12-
chemical and thermal stabilities, which facilitate their potential connected RE9 clusters in NUPF-2M were rarely seen among
applications. As an exemplification, NUPF-2Y was chosen as a the reported poly-nuclear RE clusters, which was only once
platform for post-metalized with FeCl3, the resulting NUPF-2Y- recorded in hybrid clusters of Y-pek-MOF-2 reported in the
FeCl exhibit excellent catalytic property for N-H carbene literature.12
insertion with high yield and good recyclability. To the best of
To assess the permanent porosity of NUPF-2M, N2
our knowledge, no MPFs were reported for such an application. adsorption was performed on the activated samples (S10†). As
Dark purple hexagonal prism-shaped single crystals of shown in Fig. 2a, all the adsorption isotherms of NUPF-2M
NUPF-2M were obtained via solvothermal reactions of exhibit a fully reversible type I behavior with high gas uptakes,
porphyrinic ligand TCPP with rare earth metal nitrates in DMF indicating their microporous nature. The BET surface area of
and H2O at 120 °C for 72 h by using 2-fuorobenzoic acid as a NUPF-2Y derived from the adsorption data was 1948 m2/g,
modulator (S2† and Fig. S1†). The synthesis process could also slight higher than its Zr-analogue PCN-223 (~1600 m2/g).16 As
be achieved by using microwave-assisted reactions in a the molecular weights of NUPF-2M increase from Yttrium to
relatively faster manner (S3† and Fig. S3†). Single-crystal X-ray Ytterbium, the surface areas decrease from 1948 m2/g (NUPF-
diffraction studies disclosed that all the NUPF-2M frameworks 2Y) to 1219 m2/g (NUPF-2(Yb)) (Table S1†). The pore size
are isostructural; thus only NUPF-2Y was described in detail. distributions for NUPF-2M assessed using the N2 sorption
The structure of NUPF-2Y crystallized in a primitive hexagonal curves revealed two types of pores with average sizes
space group, P6/mmm, composed of 4-connected TCPP linker centered around ~0.8 nm and ~0.6 nm (Fig. S8†), which is
and 12-connected Y nonanuclear cluster (Fig. 1). The porphyrin consistent with the crystallographic data. It is noted that RE-
macrocycle of TCPP was core-free and nearly planar without MPFs were rarely explored in areas related to gas sorption
obvious out-of-plane deformation. Each benzoate arm of TCPP because of the difficulty in obtain these materials with
were almost perpendicular to the porphyrin plane with a permanent porosity.22 To the best of our knowledge, NUPF-2M
dihedral angle of 88.7° (Fig. 1a). The 12-connected Y9 cluster may represent the most porous RE-based MPFs to date.
possessed
containing the disordered Y9 atoms, which can be simplified as and framework integrity before and after adsorption
12-connected structural nod with hexagonal-prism experiments as evidenced by PXRD patterns (Fig. S9†).
coordination geometry (Fig. 1b and Fig. S4†).
a truncated hexagonal bipyramid geometry Notably, all the NUPF-2M samples preserved their crystallinity
a
Fig.
1 (a) the 4-connected TCPP linker used in NUPF-2Y. (b) the disordered 12-
connected Y9 cluster observed in NUPF-2Y. (c) the highly opened 3D networks with shp-
a topology found in NUPF-2Y. (d) one dimensional channels propagated along the c-axis.
The connolly surfaces were calculated using a 1.7 Å probe radius.
Fig. 2 (a) N2 adsorption (solid symbols) and desorption (open symbols) isotherms of
NUPF-2M at 77 K. (b) PXRD patterns of NUPF-2M heated at 400 °C under Ar for 30 min.
PXRD patterns of NUPF-2M in pH=2 (c) and pH=12 (d) solutions for 1 day.
2 | J. Name., 2012, 00, 1-3
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prolonged to 30 min in NUPF-2Y-FeCl reaction (entry 4). Such
TG analysis reveals that the decomposition temperature of slow reaction was ascribed to the inherent character of MOF-
NUPF-2M was higher than 500 °C (Fig. S6†), demonstrating an catalyzed heterogeneous reactions, in which the frameworks
excellent thermal stability of NUPF-2M. This high thermal of MOFs served as diffusion barriers for reagents.25
stability was further authenticated by the undamaged PXRD
Table 1 NUPF-2Y-FeCl catalyzed N-H carbene insertion reactions.
patterns of NUPF-2M heated under Ar at 400 °C for 30 min (Fig.
2b). The high chemical and thermal stabilities may be ascribed
to the high charge density (Z/r) of RE metals and highly-
connected RE clusters formed in NUPF-2M, which result in
Entry
Substrate
Catalyst
Product
Yield %a
strong coordination bonds between TCPP linker and metal
23
Besides the thermal stability, NUPF-2M also
clusters.14-16,
blank
1
0
possess high chemical stability. Experimental results show that
NUPF-2M retained their crystallinity in common organic
solvents for 3 days (S11†). Remarkably, NUPF-2M could be
survived in pH= 2~12 aqueous solutions for 1 day, as
demonstrated by their unaltered PXRD patterns (Fig. 2c-d),
exhibiting a high resistance towards acid and base solutions.
The integration of high structural stability, large solvent-
accessible voids and free-based porphyrinic centers in NUPF-
2M make them potential versatile platforms for
heterogeneous catalysis.24 Among the metalloporphyrin
catalyzed reactions, FeIIICl-porphyrin showed an effective
catalytic property towards N-H carbene insertion. However,
such reactions were rarely explored by using MPFs as
heterogeneous catalyst. In order to explore the utilization of
NUPF-2M as heterogeneous catalyst in N-H carbene insertion,
[FeCl] moiety, which served as catalytic active center, must be
planted into the porphyrin core. We chose NUPF-2Y as an
exemplified platform for post-functionalization with FeCl3. The
post-metallization process was easily performed by refluxing
the crystals of NUPF-2Y with FeCl3 followed by filtration
(denoted as NUPF-2Y-FeCl, S12†). ICP-OES measurements
revealed that all the porphyrin cores were metallized (S12†),
demonstrating NUPF-2Y could be facilely functionalized.
FeCl3
2
3
4
5
6
7
0
0
NUPF-2Y
NUPF-2Y-FeCl
Fe(TPP)Cl
96
93b
92 (4th)
90c
NUPF-2Y-FeCl
NUPF-2Y-FeCl
NUPF-2Y-FeCl
8
95
9
93 (4th)
93
NUPF-2Y-FeCl
NUPF-2Y-FeCl
NUPF-2Y-FeCl
10
11
95
NUPF-2Y-FeCl
12
95
NUPF-2Y-FeCl
NUPF-2Y-FeCl
NUPF-2Y-FeCl
13
14
15
96
94
The reaction of aniline with ethyl diazoacetate (EDA) was
employed as a model system to evaluate the catalytic
performance of NUPF-2Y-FeCl. As shown in Table 1, compared
with the trials with the blank, FeCl3 and the pristine NUPF-2Y
(entries 1, 2 and 3), NUPF-2Y-FeCl exhibited unequivocally
catalytic activities with a high yield up to 95% (entry 4), proved
the essential role of [FeCl] unit in porphyrin ligand. The
catalytic activity of NUPF-2Y-FeCl was comparable to the
homogeneous catalyst Fe(TPP)Cl (entry 5). However, NUPF-2Y-
FeCl could be easily separated and reused for further catalytic
runs. For example, the catalytic yield of NUPF-2Y-FeCl was up
to 92% in the 4th run in the case of aniline (entry 6, Fig. S13†
and Fig. S13†), demonstrating a huge advantage over the
homogeneous catalyst. Furthermore, the catalytic activity of
NUPF-2Y-FeCl could be primarily reserved in large-scale runs,
as demonstrated in entry 7 which performed in 10 mmol scale
with 90% yield. The high catalytic activity and good reusability
of NUPF-2Y-FeCl were further verified by using more
substrates bearing different groups (entries 8-15, Fig. S13† and
Fig. S14†). Notably, NUPF-2Y-FeCl exhibit a slow reaction rate
compared with the homogeneous reactions. For example, the
reaction catalyzed by homogeneous Fe(TPP)Cl could be
accomplished in 10 min (entry 5), while the same reaction was
93d
Reactions were run under high-purity Ar atmosphere in dry CH2Cl2 with 0.3
mmol of substrate, 0.36 mmol of EDA and 1 mmol% catalyst (3.7 mg for
NUPF-2Y-FeCl and 2.1 mg for Fe(TPP)Cl, based on Fe-porphyrin unit) at
room temperature for 30 min unless stated otherwise. Isolated yield.
c
Reaction complete in 10 min. Yield was determined by GC-MS and
reaction time was 5 h. d Reaction was performed in dry acetone.
a
b
In summary,
a series of porous rare-earth metal-
porphyrinic frameworks M9O5(TCPP)3∙(solvents)x (M = Y, Gd, Tb,
Dy, Er, Yb) have been successfully synthesized, which
represents the first examples of highly-connected RE cluster-
based MPFs. These MPFs exhibit not only high permanent
porosity, but also desirable chemical and thermal stabilities,
which enable their utilization as versatile platforms for various
applications. As an exemplification, the post-metalated NUPF-
2Y-FeCl demonstrated the superior catalytic property toward
the N-H carbene insertion. Considering the versatile
coordination modes of multinuclear RE clusters documented
by literatures and the fascinating properties of
(metallo)porphyrins, it could be envisioned that more stable
RE-MPFs with intriguing properties could be constructed in the
near future.
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Sarjeant, J. T. Miller, K. W. Chapman, J. F. Stoddart, C. J.
Cramer, J. T. Hupp, O. K. Farha, J. Am. Chem. Soc., 2015, 137
13624; K. Manna, P. Ji, Z. Lin, F. X. Greene, A. Urban, N. C.
Thacker and W. Lin, Nat. Commun., 2016, , 12610.
The authors are grateful for financial support from the
National Natural Science Foundation of China (grant number
21471075).
,
7
8. J. Rocha, L. D. Carlos, F. A. A. Paz and D. Ananias, Chem. Soc.
Rev., 2011, 40, 926; Y. Cui, Y. Yue, G. Qian and B. Chen, Chem.
Rev., 2012, 112, 1126; S. Roy, A. Chakraborty, T. K. Maji,
Coord. Chem. Rev., 2014, 273, 139; B. Li, H.-M. Wen, Y. Cui, G.
Qian and B. Chen, Prog. Polym. Sci., 2015, 48, 40.
9. L. Chen, F. Jiang, K. Zhou, M. Wu and M. Hong, Lanthanide
Metal-Organic Frameworks, Springer Berlin Heidelberg,
Berlin, Heidelberg, 2015; F.-L. Hu, F.-L. Jiang, J. Zheng, M.-Y.
Wu, J.-D. Pang and M.-C. Hong, Inorg. Chem., 2015, 54, 6081.
10. D.-X. Xue, A. J. Cairns, Y. Belmabkhout, L. Wojtas, Y. Liu, M. H.
Alkordi and M. Eddaoudi, J. Am. Chem. Soc., 2013, 135, 7660.
11. V. Guillerm, J. WeselińskiŁukasz, Y. Belmabkhout, A. J. Cairns,
V. D'Elia, WojtasŁukasz, K. Adil and M. Eddaoudi, Nat. Chem.,
Notes and references
1. E. B. Fleischer, Acc. Chem. Res., 1970, 3, 105; K. M. S. a. R. G. K.
M. Kadish, The Porphyrin Handbook, Academic Press, San
Diego, 2000.
2. C.-M. Che, V. K.-Y. Lo, C.-Y. Zhou and J.-S. Huang, Chem. Soc.
Rev., 2011, 40, 1950; C. M. B. Carvalho, T. J. Brocksom and K. T.
de Oliveira, Chem. Soc. Rev., 2013, 42, 3302; S. Singh, A.
Aggarwal, N. V. S. D. K. Bhupathiraju, G. Arianna, K. Tiwari and
C. M. Drain, Chem. Rev., 2015, 115, 10261.
3. W.-Y. Gao, M. Chrzanowski and S. Ma, Chem. Soc. Rev., 2014,
43, 5841; Z. Guo and B. Chen, Dalton Trans., 2015, 44, 14574;
S. Huh, S.-J. Kim and Y. Kim, CrystEngComm, 2016, 18, 345.
4. B. F. Abrahams, B. F. Hoskins and R. Robson, J. Am. Chem. Soc.,
1991, 113, 3606; O. M. Yaghi, G. Li and H. Li, Nature, 1995,
378, 703.
2014, 6, 673.
12. D. Alezi, A. M. P. Peedikakkal, Ł. J. Weseliński, V. Guillerm, Y.
Belmabkhout, A. J. Cairns, Z. Chen, Ł. Wojtas and M.
Eddaoudi, J. Am. Chem. Soc., 2015, 137, 5421.
13. A. H. Assen, Y. Belmabkhout, K. Adil, P. M. Bhatt, D.-X. Xue,
H. Jiang and M. Eddaoudi, Angew. Chem. Int. Ed., 2015, 54,
5. For examples, see: A. M. Shultz, O. K. Farha, J. T. Hupp and S. T.
Nguyen, J. Am. Chem. Soc., 2009, 131, 4204; M.-H. Xie, X.-L.
Yang, C. Zou and C.-D. Wu, Inorg. Chem., 2011, 50, 5318; M.-
14353.
14. R. Luebke, Y. Belmabkhout, L. J. Weselinski, A. J. Cairns, M.
H. Xie, X.-L. Yang and C.-D. Wu, Chem. Commun., 2011, 47
,
Alkordi, G. Norton, L. Wojtas, K. Adil and M. Eddaoudi, Chem.
Sci., 2015, 6, 4095.
15. D.-X. Xue, Y. Belmabkhout, O. Shekhah, H. Jiang, K. Adil, A. J.
Cairns and M. Eddaoudi, J. Am. Chem. Soc., 2015, 137, 5034.
16. D. Feng, Z.-Y. Gu, Y.-P. Chen, J. Park, Z. Wei, Y. Sun, M. Bosch,
S. Yuan and H.-C. Zhou, J. Am. Chem. Soc., 2014, 136, 17714.
5521; C. Zou, C.-D. Wu, Dalton Trans., 2012, 41, 3879; X. L.
Yang, M. H. Xie, C. Zou, Y. B. He, B. L. Chen, M. O'Keeffe, C. D.
Wu, J. Am. Chem. Soc., 2012, 134, 10638; C. Zou, Z. Zhang, X.
Xu, Q. Gong, J. Li, C.-D. Wu, J. Am. Chem. Soc., 2012, 134, 87;
D. Feng, Z.-Y. Gu, J.-R. Li, H.-L. Jiang, Z. Wei and H.-C. Zhou,
Angew. Chem. Int. Ed., 2012, 51, 10307; L. Meng, Q. Cheng, C.
Kim, W.-Y. Gao, L. Wojtas, Y.-S. Chen, M. J. Zaworotko, X. P.
Zhang and S. Ma, Angew. Chem. Int. Ed., 2012, 51, 10082; A.
Fateeva, P. A. Chater, C. P. Ireland, A. A. Tahir, Y. Z. Khimyak, P.
V. Wiper, J. R. Darwent and M. J. Rosseinsky, Angew. Chem.
Int. Ed., 2012, 51, 7440; H.-L. Jiang, D. Feng, K. Wang, Z.-Y. Gu,
Z. Wei, Y.-P. Chen and H.-C. Zhou, J. Am. Chem. Soc., 2013,
135, 13934; M.-H. Xie, X.-L. Yang, Y. He, J. Zhang, B. Chen and
C.-D. Wu, Chem. Eur. J., 2013, 19, 14316; X.-L. Yang, C.-D. Wu,
Inorg. Chem., 2014, 53, 4797; X.-L. Yang, C. Zou, Y. He, M.
Zhao, B. Chen, S. Xiang, M. O'Keeffe and C.-D. Wu, Chem. Eur.
J., 2014, 20, 1447; M. Zhao, S. Ou and C.-D. Wu, Acc. Chem.
Res., 2014, 47, 1199; B. J. Deibert and J. Li, Chem. Commun.,
2014, 50, 9636; K. Lu, C. He and W. Lin, J. Am. Chem. Soc.,
2014, 136, 16712; J. Zheng, M. Wu, F. Jiang, W. Su and M.
17. Z. Zhu and J. H. Espenson, J. Am. Chem. Soc., 1996, 118
9901; E. C. Lee and G. C. Fu, J. Am. Chem. Soc., 2007, 129
,
,
12066; B. Shi, A. J. Blake, W. Lewis, I. B. Campbell, B. D.
Judkins and C. J. Moody, J. Org. Chem., 2010, 75, 152; C.-M.
Ho, J.-L. Zhang, C.-Y. Zhou, O.-Y. Chan, J. J. Yan, F.-Y. Zhang,
J.-S. Huang and C.-M. Che,J. Am. Chem. Soc., 2010, 132, 1886;
S.-F. Zhu, B. Xu, G.-P. Wang and Q.-L. Zhou, J. Am. Chem. Soc.,
2012, 134, 436.
18.M. A. M. M. P. Doyle, T. Ye, Modern Catalytic Methods for
Organic Synthesis with Diazo Compounds, Wiley, New York,
1998; E. Galardon, P. Le Maux and G. Simonneaux,
Tetrahedron, 2000, 56, 615; S. Bachmann, D. Fielenbach and
K. A. Jorgensen, Org. Biomol. Chem., 2004,
Rodríguez, A. Caballero, M. M. Díaz-Requejo, M. C. Nicasio
and P. J. Pérez, Org. Lett., 2006, , 557.
19. I. Aviv and Z. Gross, Synlett, 2006, , 951; I. Aviv and Z. Gross,
2, 3044; P.
8
Hong, Chem. Sci., 2015, 6, 3466; H.-Q. Xu, J. Hu, D. Wang, Z. Li,
6
Q. Zhang, Y. Luo, S.-H. Yu and H.-L. Jiang, J. Am. Chem. Soc.,
2015, 137, 13440; Z. Guo, D. Yan, H. Wang, D. Tesfagaber, X. Li,
Y. Chen, W. Huang and B. Chen, Inorg. Chem., 2015, 54, 200; J.
A. Johnson, B. M. Petersen, A. Kormos, E. Echeverría, Y.-S.
Chen and J. Zhang, J. Am. Chem. Soc., 2016, 138, 10293; W.-Y.
Gao, C.-Y. Tsai, L. Wojtas, T. Thiounn, C.-C. Lin and S. Ma, Inorg.
Chem., 2016, 55, 7291; S.-L. Zhu, X. Xu, S. Ou, M. Zhao, W.-L.
He and C.-D. Wu, Inorg. Chem., 2016, 55, 7295.
6. Y. Bai, Y. Dou, L.-H. Xie, W. Rutledge, J.-R. Li and H.-C. Zhou,
Chem. Soc. Rev., 2016, 45, 2327; M. Bosch, S. Yuan and H.-C.
Zhou, The Chemistry of Metal–Organic Frameworks, Wiley-
VCH Verlag GmbH & Co. KGaA, 2016.
Chem. Eur. J., 2008, 14, 3995; C. Ma, D. Xing, C. Zhai, J. Che, S.
Liu, J. Wang and W. Hu, Org. Lett., 2013, 15, 6140; R. L.
Khade and Y. Zhang, J. Am. Chem. Soc., 2015, 137, 7560.
20. J. Yoo, N. Park, J. H. Park, J. H. Park, S. Kang, S. M. Lee, H. J.
Kim, H. Jo, J.-G. Park and S. U. Son, ACS Catal., 2015,
21. A. Spek, J. Appl. Crystallog., 2003, 36, 7.
5, 350.
22. B. K. Tripuramallu, H. M. Titi, S. Roy, R. Verma and I.
Goldberg, CrystEngComm, 2016, 18, 515.
23. A. H. Assen, Y. Belmabkhout, K. Adil, P. M. Bhatt, D. X. Xue,
H. Jiang and M. Eddaoudi, Angew. Chem. Int. Ed., 2015, 54
14353.
,
24. L. Xu, Y.-P. Luo, L. Sun, Y. Xu, Z.-S. Cai, M. Fang, R.-X. Yuan
and H.-B. Du, Chem. Eur. J., 2016, 22, 6268.
25. J. S. Seo, D. Whang, H. Lee, S. I. Jun, J. Oh, Y. J. Jeon and K.
Kim, Nature, 2000, 404, 982; A. Corma, H. García and F. X.
7. For examples, see: J. E. Mondloch, M. J. Katz, W. C. Isley Iii, P.
Ghosh, P. Liao, W. Bury, G. W. Wagner, M. G. Hall, J. B.
DeCoste, G. W. Peterson, R. Q. Snurr, C. J. Cramer, J. T. Hupp
and O. K. Farha, Nat. Mater., 2015, 14, 512; S.-Y. Moon, Y. Liu,
Llabrés i Xamena, Chem. Rev., 2010, 110, 4606; A.
Dhakshinamoorthy and H. Garcia, Chem. Soc. Rev., 2014, 43,
5750.
J. T. Hupp and O. K. Farha, Angew. Chem. Int. Ed., 2015, 54
,
6795; P. Li, R. C. Klet, S.-Y. Moon, T. C. Wang, P. Deria, A. W.
Peters, B. M. Klahr, H.-J. Park, S. S. Al-Juaid, J. T. Hupp and O. K.
Farha, Chem. Commun., 2015, 51, 10925; M. H. Beyzavi, N. A.
Vermeulen, A. J. Howarth, S. Tussupbayev, A. B. League, N. M.
Schweitzer, J. R. Gallagher, A. E. Platero-Prats, N. Hafezi, A. A.
4 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C6DT03678C
Journal Name
COMMUNICATION
TOC
The unprecedented highly porous and stable rare earth cluster
based metal-porphyrinic frameworks can be used as efficient
catalysts for N-H carbene insertion.
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