Cluster-based MOFs with accelerated chemical conversion of CO2 through C-C bond formation

Article abstract of DOI:10.1039/c7cc01136a

Investigations on metal-organic frameworks (MOFs) as direct catalysts have been well documented, but direct catalysis of the chemical conversion of terminal alkynes and CO₂ as chemical feedstock by MOFs into valuable chemical products has never

Full text of DOI:10.1039/c7cc01136a

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc3N@C2n (2n 68 and 80). Synthesis of the
first methanofullerene derivatives of Sc N@D5h-C80
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Cluster‐based MOFs with Accelerating Chemical Conversion
of CO2 through C‐C Bond Formation
Received 00th January 20xx,
Accepted 00th January 20xx
Gang Xiong‡ ‡
a,c, Bing Yu b, Jie Donga, Ying Shia, Bin Zhao*a, Liang‐Nian He*b
DOI: 10.1039/x0xx00000x
www.rsc.org/
Investigations on metal‐organic frameworks (MOFs) as direct oxidation 12, 17, aza‐Michael reactions18, and Friedländer reaction19.
catalysts have been well documented, but it has never been Besides, the amino, pyridyl and amido Lewis base groups in MOFs
reported that MOFs directly catalyze the chemical conversion of can effectively promote Knoevenagel condensation reaction20, 21
.
terminal alkynes and CO2 as chemical feedstock into valuable Comparably, exploring MOFs‐catalyzed conversion of CO2 is still in
chemical products. We report here two cluster‐based MOFs I and infant, and only cycloaddition reactions of CO2 and epoxide were
II assembled by multinuclear Gd‐cluster and Cu‐cluster, displaying explored5, 7, 22, 23, as well hydrogenation of CO2 to formic acid24.
high thermal and solvent stabilities. I and II as heterogeneous More recently, the carboxylation reactions of terminal alkyne and
catalysts possess active catalytic centers [Cu12I12] and [Cu3I2], CO2 can be well catalyzed by Ag nanoparticles loading into MIL‐
respectively, exhibiting excellent catalytic performance in the 10125, however it has never been reported so far for MOFs
carboxylation reactions of CO2 and 14 kinds of terminal alkynes materials to directly catalyze such type of carboxylation reactions,
under 1 atm and mild conditions. This is the first time for MOFs in which new C‐C bonds were generated.
materials to catalyze the carboxylation reaction of terminal
The carboxylation reaction of CO2 and terminal alkynes exhibits
alkynes and CO2 without any cocatalyst/additive. This work not the some outstanding virtues.26, 27 for example, alkynyl carboxylic
only reduces greenhouse gas emission but also provides high acids or esters as formed products were extensively employed in
valuable materials, opening a wide space in seeking recoverable industry and pharmacy.27In this aspect, development of efficacious
catalysts to accelerate chemical conversion of CO2.
processes using CO2 as chemical feedstock under mild conditions
particularly low CO2 pressure (ideally at 1 bar) could be still highly
desirable. On the other hand, most of catalysts used in the
Metal‐organic frameworks (MOFs) as catalysts have been attracting
a great deal of research interest because of enormous applications
in organic synthesis and catalysis1‐4. MOFs as catalysts possess
unique advantages as following: 1) diversity and tunability of
catalytic active sites, because both metal cations and Lewis basic
carboxylation reaction are homogeneous ones, and examples of
29
using recoverable heterogeneous catalyst are scarce.28,
.
Therefore, it is indispensable and important for such reaction to
design new materials as heterogeneous catalysts, because of their
intrinsic features including easy handling, workup, purification of
products, as well the robustness and reusability of the catalyst
itself.
species in MOFs can serve as catalytic active centers5‐7
Furthermore, post‐synthesized strategies through decorating
organic linkers or metal centers can widely enrich catalytic sites8‐10
2) well‐defined pores as nanoreactors can exhibit size‐ or shape‐
selective effect on substrate molecules11; 3) it is very promising for
MOFs with insolubility and stability in commonly solvents to act as
the heterogeneous catalysts12. Therefore, the investigations on
MOFs as catalysts have been a hotspot field and made significant
progress hitherto. For example, Zn‐ or Cu‐containing MOFs display
excellent catalytic activity in Friedel‐Crafts alkylation13,
cyanosilylation14,, acetalization15, isomerization of a‐pinene oxide16,
.
;
In previous work, many d‐f heterometallic MOFs were
systematically explored by us 30,32, and they possess high solvent
and thermal stabilities due to variable and high coordination
number of lanthanide ions, which meets the indispensable
condition of heterogeneous catalysts. Recently we performed the
carboxylation reactions of terminal alkynes with CO2 by using CuI as
a catalyst and ethylene carbonate as media.32Inspired by these
results, we aim to construct novel MOFs consisting of [CuxIy]
clusters and lanthanide ions, and can envisage the MOFs materials
would have high stability and effectively promote such
carboxylation reaction. To come true the target, both isonicotinic
acid (HIN) as connectors in MOFs and solvothermal method were
selected based on the following considerations: 1) given soft‐hard
acid‐base theory, lanthanide and Cu ions have different affinities for
N and O atoms in HIN, indicative of that HIN can bridge Cu and 4f
ions into one heterometallic framework rather than homometallic
one; 2) CuI salt easily forms [CuxIy] clusters under the solvothermal
aDepartment of Chemistry, Key Laboratory of Advanced Energy Material Chemistry of
the Ministry of Education, Tianjin Key Laboratory of Metal and Molecule Based
Material Chemistry, and CollaborativeInnovation Center of Chemical Science and
Engineering (Tianjin),Nankai University, Tianjin 300071, China. E‐mail:
zhaobin@nankai.edu.cn
bState Key Laboratory and Institute of Elemento‐Organic Chemistry, Nankai
University, Tianjin, 300071, China. E‐mail: heln@nankai.edu.cn
cThe Key Laboratory of Inorganic Molecule‐Based Chemistry of Liaoning Province,
Shenyang University of Chemical Technology, Shenyang, 110142,
conditions33
.
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
‡These authors contributed equally to this work.
J. Name., 2013, 00, 1‐3 | 1
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In this contribution, two 3D MOFs [Gd3Cu12I12(IN)9(DMF)4]n∙nDMF centers. In the trinuclear [Cu3I2] cluster, I1 as a μ3‐bridge connects
(I) and [Gd4Cu4I3(CO3)2(IN)9(HIN)0.5(DMF)(H2O)]n∙nDMF∙nH2O (II) three CuI cations to form the Cu3I2 cluster (Fig. S2b), and I2 links Cu1
were successfully prepared and structurally characterized with high and Cu1A with the Cu1‐Cu1A distance of 2.75 Å. Four coordinated
solvent and thermal stabilities. Two robust frameworks were Cu1 locates in a tetrahedron comprised by two iodine anions and
assembled by multinuclear Gd‐cluster and Cu‐cluster as active two nitrogen atoms, while the four coordinated environment of
catalytic centers ([Cu12I12] in I and [Cu3I2] in II). They exhibited Cu2 is finished by one iodine, two nitrogen atoms and one DMF
excellent catalytic performance in the carboxylation reactions of molecule. In [CuI] unit (Fig. S6), the four coordinated Cu3 has a
various terminal alkynes and CO2 under 1 atm and mild conditions. tetrahedral configuration consisting of one iodine ion and three
To the best of our knowledge, this is the first time for MOFs nitrogen atoms. All of the Cu‐N, Cu‐I and Cu‐O bond lengths fall in
materials to directly catalyze the carboxylation reaction of terminal the normal range. All pyridine N atoms in [Gd4(CO3)2(IN)9] cluster
alkynes and CO2 under mild conditions without any coordinate to Cu centers in adjacent [CuI] and [Cu3I2] building
cocatalyst/additive.
blocks, giving rise to an unprecedented 3D framework with 1D
The structure determination revealed that the three channels with the size of 0.8×0.5 nm along [100] direction. The total
dimensional framework of I is assembled by two types of building potential solvent accessible void is 1822.9 Å3 (18.6% of cell volume)
blocks: dodeca‐nuclear Cu‐cluster [Cu12I12] (Fig.1b) and tri‐nuclear calculated by PLATON program34 upon moving the free DMF
Gd‐cluster [Gd3(IN)9(DMF)4] (Fig.1c). The [Cu12I12] cluster comprises molecules.
three crystallographically independent [Cu4I4] cubic units. Cu3, Cu7
and Cu10 are four‐coordinate with [I4] sets, while the remaining
nine Cu atoms are also four‐coordinate but with [I3N] sets, in which
N atoms come from the pyridine rings. Each of three I atoms (I4, I5
and I10) connects four Cu atoms from two [Cu4I4] clusters, and each
of the other nine I atoms coordinates to three Cu atoms from one
[Cu4I4] cluster. Interestingly, I4 atoms further bridge adjacent
[Cu12I12] clusters into a complicated cluster‐based 1D chain along b
axis (Fig. S1), which is rather rare although [Cu4I4] clusters and Cu‐I
chains were well documented33. In the [Gd3(IN)9(DMF)4] cluster,
three crystallography independent Gd3+cations locate in the eight‐
coordinated distorted square antiprisms (Fig. S2). The coordination
environments of Gd1 and Gd3 are similar and complete by seven
carboxyl oxygen atoms from IN anions and one DMF molecule. Gd2
is coordinated with six monodentate carboxyl oxygen atoms and
two DMF molecules. Both O5 and O8 as μ2‐bridges connect Gd1 and
Fig. 1 (a) The three dimensional structure of I. (b) [Cu12I12] cluster
Gd2, while four carboxyl groups with the typical paddle‐wheel
drawn at 50% probability level. (c) tri‐nuclear [Gd3(IN)9(DMF)4] units
mode bridge Gd2 and Gd3. The adjacent [Gd3(IN)9(DMF)4] clusters
drawn at 30% probability level.
are further connected into a 1D chain (Fig. S3) by two carboxyl
groups in a μ1,3‐bridge mode. Each pyridine N atom in the
[Gd3(IN)9(DMF)4] cluster coordinates to one Cu atom from the
adjacent [Cu12I12] cluster, constructing a mixed high‐nuclear cluster‐
based 3D framework with 1D channels with the size of 1.2×0.5 nm
along [010] direction (Fig.1a). The coordinated DMF molecules
point to the channels, and the isolated ones locate in the channels.
The total potential solvent accessible void is 1105 Å3 (10.4% of cell
volume) calculated by PLATON program34 after moving the isolated
DMF molecules, To our knowledge, many impressive MOFs based
on d‐f heterometallic, or high‐nuclear f or d clusters, have been
widely investigated35,however, systematic investigation on that
such MOFs containing both high‐nuclear f and d clusters has been
less explored so far.33
The structure of II significantly differs from that of I, and the 3D
framework of II is constructed by three types of building blocks:
[Gd4(CO3)2(IN)9] cluster (Fig. 2c), [Cu3I2] cluster (Fig. 2b) and [CuI]
units ((Fig. S6)). In [Gd4(CO3)2(IN)9] cluster, four Gd3+ are generated
by centrosymmetric operation on two crystallographically
Fig. 2 (a) The three dimensional structure of II. (b) [Cu3I2] cluster
drawn at 40% probability level. (c) Gd4(CO3)2 chains in II drawn at
30% probability level.
2‐
independent Gd3+ (Gd1 and Gd2), and further stitched by two CO3
The thermogravimetric analyses of I and II (Fig. S7 and S8)
revealed 3D framework in I begins to collapse at about 430 , while
that in II starts to decomposition at about 300 , implying high
thermal stabilities of the two compounds. Furthermore, the PXRD
patterns of I and II dipped in the ethanol, acetonitrile, DMF (100 ),
hexane and ethylene carbonate (EC) (100 ) were investigated (Fig.
S10 and 11), well consistent with the simulated one from individual
single crystal data, and the results exhibit that 3D frameworks still
keep intact and crystalline in solvents. X‐ray photoelectron
anions. Both Gd1 and Gd2 coordinate to eight oxygen atoms from
2‐
IN ligands, CO3 or H2O, and the corresponding coordination
2‐
configurations are slightly distorted square antiprisms. The CO3
ions adopt the coordination mode of μ4: η2, η2, η2 (Fig. S4) to bridge
four Gd3+ into a square with the side length of about 4.40 Å. The
adjacent squares are further connected into a unique belt‐like chain
2‐
by sharing CO3 anions along a axis (Fig. S5) , in which many IN
anions cover the periphery of the chain by coordinated to Gd
2 | J. Name., 2012, 00, 1‐3
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spectroscopy (XPS) of I and II (Fig. S13 and S14) give the typical heterocycle‐containing substrates 2‐ethynylthiophene (1j), 2‐
peaks of Cu(I) at 931.83 or 931.98 eV, indicative of that the pyridylacetylene (1k) and 3‐pyridylacetylene (1l) were also
oxidation state of Cu in I and II is +1.
examined, and the products 2j‐lwere obtained with good yields.
Furthermore, the aliphatic alkyne 1m underwent the reaction
without any difficulties affording the desired product 2m (entries
13). Importantly, 1,4‐diethynylbenzene 1n was also smoothly
converted to the bis‐carboxylative product 2n in moderate yield,
thus offering a convenient alternative route to useful poly(alkyl
alkynoates) materials, accordingly.
Table 1. Optimization of the carboxylation of phenylacetylenea
I or II
O
O
Cs2CO3 (1.2 equiv.)
CO2
H +
(Balloon)
Ph
Ph
nBuI (1.2 equiv.)
Solvent
nBu
1a
2a
a
Table 2. Carboxylation of terminal alkynes with CO2
Entr
y
Catalyst
(mol% of Cu)
solven
t
Yield[b]
(%)
T (oC)
t (h)
1
2
3
4
5
6
7
8
9
‐‐
DMF
DMF
DMF
EC
80
80
100
80
80
80
100
80
80
12
12
24
12
4
12
24
12
4
9c, 4d
47
17
61
74
34
28
70
80
Yield (%)[b]
Cat‐I (7)
Cat‐I (7)
Cat‐I (6)
Cat‐I (6)
Cat‐II (3)
Cat‐II (3)
Cat‐II (3)
Cat‐II (4)
Entry R1C≡CH
1
Product
A
B
1a
80
86
2a
EC
2
3
4
70
73
81
77
85
82
1b
1c
1d
1e
2b
2c
DMF
DMF
EC
2d
2e
EC
5
6
65
72
74
73
a
Reaction conditions: Phenylacetylene (51 mg, 0.5 mmol),
Cs2CO3 (196mg, 0.6 mmol), n‐BuI (110 mg, 0.6 mmol), DMF
or ethylene carbonate (EC, 3 mL), CO2 (99.999%, balloon),
indicated amount of catalyst, 12 h.b The yields were
determined by GC with biphenyl as internal standard.c
Without catalyst. d Without CO2.
1f
1g
2f
2g
7
67
60
56
76
66
70
74
69
80
77
8
1h
1i
2h
2i
9
Furthermore, phenylacetylene (1a) was chosen as the model
substrate for the carboxylation with CO2 and extensive
investigations were carried out to define the optimal reaction
conditions. As shown in Table 1, the carboxylative reaction was
conducted under atmospheric CO2 in DMF with the copper clusters
as catalysts in the presence of Cs2CO3and n‐BuI. The product n‐butyl
2‐alkynoate (2a) was obtained in 47% and 34% yield, respectively,
with the catalysis of Cat‐I (7 mol%)and Cat‐II(3 mol%) at 80 oC for 12
h (Table 1, entries3 and 7). Control experiments established that, in
the absence of catalyst or CO2, essentially no carboxylation product
was observed (entries1 and 2). The yields of 2a were decreased
by increasing the reaction temperature to 100 oC and prolonging
reaction time to 24 h (entries 3 and 7). We reasoned that the
decarboxylation process might happen in the reaction mixture
under relatively high temperature.On the basis of our previous
report32, ethylene carbonate is thought to facilitate the
carboxylation of terminal alkynes without utilizing any additional
ligands or additives. To our delight, improved yields were thus
attained in EC (entries 5 and 9). After further optimization, only 4
hours were required for Cat‐I (6 mol%) and Cat‐II (4 mol%) to afford
2a in yield of 74% and 80%, respectively(entries 6 and 10).
After establishing optimal reaction conditions, 14 kinds of typical
alkynes with various substituents were applied to this carboxylation
reaction (Table 2). The carboxylation reactions of terminal alkynes
(1a‐n) and CO2 were conducted with I (method A) or II (method B)
as catalysts, providing alkyl 2‐alkynoates (2a‐n) as products. As a
result, the alkynes with electron‐donating substituents showed high
reactivity to afford alkynoates2a‐e in good yields. Interestingly, the
alkynes with electron‐withdrawing substituents, including F‐, Cl‐, Br‐
, at the meta‐ or para‐position of the benzene ring, also gave 2f‐i
with considerable yields from 56% to 74%. Additionally, the
10
11
1j
1k
1l
1m
2j
2k
2l
2m
12
13
58
71
52
65
75
60
14c
a
1n
2n
Reaction conditions: Terminal alkyne (1.0 mmol), catalyst I (6
mol%, method A) or catalyst II (4 mol%, method B), Cs2CO3 (0.391
g, 1.2 mmol), n‐BuI (0.221 g, 1.2 mmol) and ethylene carbonate (3
mL), CO2 (99.999%, balloon), 80 oC, 4 h.
bIsolated yield.
cI(12 mol%) or II (8 mol%), Cs2CO3 (2.4 mmol), n‐BuI (2.4 mmol),
EC (5 mL) were used.
When performing the carboxylation reaction of CO2 and terminal
alkynes catalyzedby I and II, the robust 3D frameworks with [CuxIy]
clusters play a crucial role with the following functions: 1) directly
providing active catalytic centers to avoid uploading cocatalysts.
Similar to the reported those33, all Cu(I) atoms in I and II are four‐
coordinated, and the remaining coordinated positions allow the
alkyne to interact with Cu(I) in MOFs, generating the intermediate
copper acetylide. Subsequently, the insertion of CO2 into the Cu‐C
bond occurs to provide the copper propynoate intermediate.
Further on, the ester product can be generated through the
esterification with iodoalkane, acompanying with the regeneration
of the copper cluster catalyst; 2) possessing the high thermal and
solvent stabilities. The case can make these MOFs materials as
heterogeneous catalysts to be reused; 3) due to the intrinsic
porosity feature of MOFs materials, I and II can capture CO2 of 11.8
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and 17.3 cm3/g at 273 K and 1 atm (Fig. S17), respectively. Such
adsorption possibly enhances the concentration of CO2 around
[CuxIy] clusters, which maybe accounts for the divergence of
catalytic active between I and II due to the higher CO2 adsorption
capacity of II than I.
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In summary, two unique cluster‐based d‐f heterometallic 3D
frameworks (I and II) were synthesized and structurally
characterized. They display high solvent and thermal stabilities.
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carboxylation reaction of terminal alkynes and CO2 could open a
wide space in the chemical conversion field of CO2 to valuable
chemicals and materials. To the best of our knowledge, it is the first
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[30] B. Zhao , X.‐Y.Chen , P. Cheng, D. ‐Z. Liao , S.‐P.Yanand Z.‐H.Jiang.J. Am.
Chem. Soc.2004,126, 15394.
Gd(NO3)3∙6H2O, 0.5 mmol isonicotinic acid and 10 mL DMF was
sealed in a Teflon lined stainless steel container and heated at 125
for 24 h, and then cooled slowly controlled procedures to room
temperature during 24 h. Finally, light green block crystals were
collected with a yield of about 60% (based on CuI).Anal. Calcd. for
C65H56.5Cu4Gd4I3N11.5O29 (%): C: 34.02, H: 2.48, N: 7.02. Found:
C:33.98, H: 2.46, N: 6.99.
Syntheses of II.A mixture of 0.5 mmol CuI, 0.5 mmol Gd2O3, 1
mmol isonicotinic acid, 10 mL DMF (N, N‐Dimethylformamide) and
160 μL HNO3was sealed in a Teflon lined stainless steel container
and heated at 155 for 96 h, and then cooled slowly controlled
procedures to room temperature during 96 h. Finally, light yellow
block crystals were collected with a yield of 71% (based on CuI).
Anal. Calcd. for C69H71Cu12Gd3I12N14O23 (%): C:19.59, H: 1.65, N: 4.60
；Found：C: 19.63, H: 1.70, N: 4.64.
General procedure for the carboxylation of terminal alkynes
with CO2.In a 20 mL Schlenk flask, terminal alkyne (1.0 mmol),
Cs2CO3 (0.391 g, 1.2 mmol), indicated amount of catalyst, n‐BuI
(0.221 g, 1.2 mmol) and ethylene carbonate (3 mL) were added. The
flask was capped with a stopper and sealed. Then the freeze‐pump‐
thaw method was employed for gas exchanging process. The
reaction mixture was stirred at 80 oC for desired time under the
atmosphere of CO2 (99.999%, balloon). After the reaction, the
mixture was cooled to room temperature, extracted with n‐hexane.
The combined organic layers were washed with saturated NaCl
solution then dried with anhydrous Na2SO4. The residue was
purified by column chromatography (silica gel, petroleum
ether/EtOAc) to afford the desired product alkyl 2‐alkynoates.The
products were further identified by NMR and MS (see the
Supporting Information), which are consistent with those reported in
the literature and in good agreement with the assigned structures.
[31]B. Zhao, P. Cheng, Y. Dai, C. Cheng, D.‐Z.Liao, S. ‐P. Yan, Z. ‐H. Jiangand G.
‐L. Wang.Angew.Chem. Int. Ed. 2003, 42,934.
[32] B. Yu,Z. ‐F. Diao, C. ‐X.Guo,C.‐L.Zhong, L. ‐N.He,Y. ‐NZhao,Q. ‐W. Song,
A.‐H.Liuand J. ‐Q. Wang.Green Chem. 2013, 15, 2401.
[33] J.‐W. Cheng, J. Zhang, S.‐T.Zhengand G.‐Y.Yang.Chem. Eur. J.2008, 14,
88.
[34] S. P. Vanderand Spek A. L.ActaCrystallogr., Sect. A64: Found.
Crystallogr., 1990, 194.
[35] Y.‐L. Hou, G. Xiong,P. ‐F. Shi,R. ‐R. Cheng,J.‐Z. Cuiand B. Zhao.Chem.
Commun.2013, 49, 6066
Notes and references
[1] D. Farrusseng, S. Aguado and C. Pinel. Angew.Chem. Int. Ed.2009, 48,
7502.
4 | J. Name., 2012, 00, 1‐3
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DOI: 10.1039/C7CC01136A
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We report here two cluster-based MOFs I and II assembled by multinuclear Gd-cluster and Cu(I)-
cluster, displaying high thermal and solvent stabilities. I and II as heterogeneous catalysts possess
active catalytic centers [Cu12I12] and [Cu3I2], respectively, exhibiting excellent catalytic performance
in the carboxylation reactions of CO2 and 14 kinds of terminal alkynes under 1 atm and mild
conditions. This is the first time for MOFs materials to catalyze the carboxylation reaction of terminal
alkynes and CO2 without any cocatalyst/additive. This work not only reduces greenhouse gas
emission but also provides high valuable materials, opening a wide space in seeking recoverable
catalysts to accelerate chemical conversion of CO2.