IrIII-based Octahedral Metalloligands Derived Primitive Cubic Frameworks for Enhanced CO2/N2 Separation

Article abstract of DOI:10.1002/asia.201701339

We developed a metalloligand strategy to construct porous frameworks, viz. the combined use of Ir^III-based octahedral metalloligands and the linear unit [Ni(cyclam)] easily afforded two isostructural complexes 1 and 2 with primitive cubic frameworks. Both complexes show good CO₂/N₂ separation property.

Full text of DOI:10.1002/asia.201701339

CHEMISTRY
AN ASIAN JOURNAL
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Accepted Article
Title: IrIII-based Octahedral Metalloligands Derived Primitive Cubic
Frameworks for Enhanced CO2/N2 Separation
Authors: Sheng-Li Huang, Naifang Liu, Yun Ling, and He-Kuan Luo
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COMMUNICATION
III
Ir -based Octahedral Metalloligands Derived Primitive Cubic
Frameworks for Enhanced CO
2
/N
2
Separation
[
a]
[a,b]
[c]
[a]
Sheng-Li Huang, Naifang Liu,
Yun Ling and He-Kuan Luo*
Dedicated to Professor T. S. Andy. Hor on the occasion of his 60th birthday
Abstract: We developed a metalloligand strategy to construct
central metal ions, because their positive charge cannot be
balanced by the coordinating dipyridyl groups. The β-
III
porous frameworks, viz. the combined use of Ir -based octahedral
diketonate,[
11]
dipyrrin
[12]
and pyridine-2-carboxylate
[13]
are
metalloligands and linear unit [Ni(cyclam)] easily afforded two
isostructural complexes 1 and 2 with primitive cubic frameworks.
among the most commonly used anionic primary chelating
groups, but they are not suitable for octahedral metalloligand
formation. In comparison, the 2-phenylpyridine (C^N) derivatives
have not only similar structure with 2,2'-bipyridine (N^N), but
also can provide negative charge through metal induced C-H
activation. The 2-phenylpyridine group can efficiently react with
2 2
Both two complexes show good CO /N separation property.
Metal–organic frameworks (MOFs) are an important class of
functional materials with great scientific interest in both
[
1]
academia and industry alike. The fundamental chemistry on
MOF structure design and synthesis, as well application
development, have progressed rapidly in recent years. The
structural diversity, chemical tunability and functional property of
these architectures have facilitated their application in the
multidisciplinary areas of gas storage/separation,[2] catalysis,[3]
electronic device,[4] and biointerface.[5] The key in MOF research
is to develop effective strategy to construct new frameworks with
unique structures and properties. These hybrid materials are
commonly constructed by the combination of organic linkers and
metal nodes,[6] wherein a large number of organic linkers have
been generated with different shapes including linear, triangular,
square planar and diamond like.[7] However, their types is still
limited in contrast with the metal-containing building blocks
IrIII ions to generate [Ir(C^N) ][14] or [Ir(C^N) [15], and
3 2 2
Cl]
[
[
Ir(C^N)
Ir(C^N)
2
Cl]
2
can further react with dipyridyl derivatives to give
(N^N)][16]. For both two cyclometalated-Ir building
III
2
III
blocks [Ir(C^N)
3
] and [Ir(C^N)
2
(N^N)], the Ir -based octahedral
metalloligands are formed by functionalizing every para-sites of
coordinated atoms with a second linking groups. These two
types of metalloligands have excellent chemical and thermal
stability, owing to the metal centers being coordinatively
saturated and completely surrounded by three bis-chelating
groups, and further being strengthen by the inert C-Ir bonds.
III
Furthermore, some useful properties of the cyclometalated-Ir
cores, such as photoluminescent and photocatalytic applications,
could be retained in their derived frameworks.[17]
(
metalloligands).[8] Importantly, the metalloligand offers structural
versatility with pre-organized auxiliary functional groups that
could link secondary metal ion to give the designed
a
architecture. The utilization of metalloligand not only rationally
immobilizes functionalized metal sites into the frameworks but
also can generate highly ordered architectures and facilitate
placing two or more metals in close proximity in the
heterometallic networks. [9]
The metalloligand approach has been widely used in the
construction of designed architectures, especially, the
octahedral metalloligand is one kind of high symmetric and near
perfect building blocks, even the combination of simplest linear
metal units can generate three-dimensional (3D) porous
networks. Some octahedral metalloligands [M(2,2'-bipyridine-
4
,4'-dicarboxylic acid)
3
, M = Co, Ru, Zn] have been reported,[10]
whereas the coordination ability of attached carboxylate groups
are greatly weakened by the electron-withdrawing effect of
[
a]
Dr. S. -L. Huang, Dr. H. -K. Luo
Institute of Materials Research and Engineering
Agency for Science, Technology and Research
2
Fusionopolis Way. Innovis, #08-03, Singapore 138634
E-mails: luoh@imre.a-star.edu.sg
[
[
b]
c]
N. Liu
Scheme 1. The synthetic method of metalloligands (L
1 6 2 5
-H and L -H ) and
Department of Chemistry, National University of Singapore
3
Science Drive 3, Singapore 117543
primitive cubic frameworks (1 and 2).
Prof. Y. Ling
Department of Chemistry, Fudan University, Shanghai, China
The octahedral metalloligand L
acid groups from six directions of 3D space, its ester precursor
was obtained by microwave irradiation of 2-(3-
1
6
-H , containing six carboxylic
Supporting information for this article is available on the WWW
under http://xxxxxx.
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methoxycarbonylphenyl)pyridine-4-(methoxycarbonyl)
and
1
and each asymmetric unit containing one complete L and three
o
IrCl
3
·3H
2
O at 120 C (Scheme 1). To investigate the cation effect
Ni(cyclam) building blocks. The X-ray crystal structure of 1 (Fig.
1) reveals that each Ir(III) cation lies in the center of a classical
octahedral environment with three nitrogen atoms and three
carbon atoms (The bonds of Ir–N or Ir-C are in the range of
2.05-2.07 Å) from 2-(3-carbonylphenyl)pyridine-4-(carbonyl).
Similarly, Ni(II) also takes the octahedral coordination
of the metalloligand, a structural analogue L
2
5
-H was designed,
which has one coordinated carbon atom being replaced by a
nitrogen atom compared to L
firstly obtained
methoxycarbonylphenyl)pyridine-4-(methoxycarbonyl)]
1
-H
a
6
. For the synthesis of L
2
-H
{Ir[2-(3-
Cl}
which undergoes further reaction with 2,2'-Bipyridine-4,4'-
dicarboxylic acid and subsequent hydrolysis to afford the L -H
5
, we
dinuclear
2
2
,
4 2
environment [NiN O ] formed by four nitrogen atoms from
2
5
.
cyclam (Ni–N 2.03-2.06 Å) and two carboxylate oxygen atoms of
2-(3-carbonylphenyl)pyridine-4-(carbonyl) (Ni–O 2.08-2.13 Å),
respectively. The carboxylate groups at the para-positions of the
coordinated N and C atoms are coordinated to Ni(II), resulting in
a primitive cubic network (Fig. 2a). This is in accordance with
The primitive cubic topological networks are 3D porous
architectures, with typical examples being the series of MOF-5
that were constructed from octahedral Zn-O-C clusters and
organic links.[18] Because the carboxylate groups of octahedral
1 2
metalloligands L and L extend to the six directions of 3D space, our expectations because the metal-macrocyclic Ni(cyclam)
the combination with the simplest linear unit can provide the
simple cubic topological networks. In contrast to free metal ions,
complex act as linear linking unit, offering a simple coordination
mode and easily controlled stable frameworks. Unexpectedly,
two sets of networks interlocked each other, leading to a 2-
interpenetrating compact structure (Fig. 2b). Compared to 1,
complex 2 crystallizes in the Trigonal space group R-3c, but
each Ir(III) cation was coordinated with four nitrogen atoms and
two carbon atoms. Interestingly, the Ni-O bonds of carboxylate-
Ni became shorter than that in framework 1 due to the electron-
[Ni(cyclam)](ClO
)
4 2
(cyclam
=
1,4,8,11-
tetraazacyclotetradecane) has two controlled coordination sites
of the axil site and strong binding ability to carboxylate group,[19]
thus it was applied as the linear unit herein. A solution of
[
Ni(cyclam)](ClO
carefully layered on the top of a solution of L
in (2 mL). Orange needle-shaped crystals
[Ni(cyclam)] (L )·solvents} suitable for X-ray crystallographic
4
)
2
(0.06 mmol) in MeOH–H
2
O (1 : 2, 3 mL) was
1
-Na (0.02 mmol)
6
H
2
O
1
2
withdrawing effect of Ir(III) cation in L .
{
3
1
n
analysis were obtained in high yield after few days. However for
III
L
2
,
due to the non-balanced positive charge of Ir , the
coordination ability of carboxylate groups in L
weakened, hence no precipitate formed upon mixing the solution
of [Ni(cyclam)](ClO with L -Na . A single crystal of 2 suitable
2
is greatly
)
4 2
2
5
for X-ray diffraction was obtained by evaporation of solvents.
Since the neutral dipyridyl group is unable to provide negative
charge upon coordinating to metal centers, metalloligand L can
2
only provide five negative charges. Both the elemental analysis
and XRF analysis of desolvated 2 (Fig. S9) indicated that the
counteranion of 2 should not be ClO –
. The deprotonation of an
amine nitrogen atom of the cyclam provides one counteranion to
balance the framework 2 {[Ni(cyclam–)]
(L )·solvents}
4
3
2
n
.
Figure 2. Crystal structure (a) and 2-interpenetrating primitive cubic
topological structure of complex 1 (or 2) (b).
Figure 1. Ball-stick model showing the connectivity of L
Ni(cyclam)] linear unit from six directions. Gray, C; blue, N; red, O; orange, C
or N; Gold, Ir; Bright green, Ni.
1 2
(or L ) and
Both complexes 1 and 2 are unstable in air arising from the
loss of guest solvates. Thermogravimetric analysis (TGA) of
[
them indicates that all the solvent molecules are lost at about
o
1
50 C (Fig. S12 – S13). Soaking freshly prepared complexes in
o
Complex 1 crystallizes in the Trigonal space group R-3, with
methanol for 2 weeks, and then heating them at 200 C under
the Ir(III) and Ni(II) atoms lying on independent inversion centers, vacuum for 50 h, the guest-free frameworks 1' and 2' were
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obtained and proved by TG analysis (Fig. S12 – S13). For 1' and
(Table S2, Supporting Information) with higher selectivity at
2
', both their phase purity and maintenance of structural
lower pressure. In particular, at 0.3 atm, the CO
for 2' is high at 76.1:1 (v:v, 298 K) and 89.7:1 (v:v, 273 K),
respectively. The high selectivity for capturing CO over N may
be ascribed to the larger quadrupole moment of CO
(13.4 x 10-
) and higher
2 2
/N selectivity
framework integrity were confirmed as evidenced from PXRD
data (Fig. S10 – S11).
Undoubtedly, structural interpenetration is closely associated
with MOF's pore character that could influence the gas
2
2
2
40
Cm2 for CO
polarizability (26.3 x 10 cm for CO
2
N ). The factors that influence adsorptive gas separation include
-40
Cm2 for N
2
vs. 4.7 x 10
2
[
20]
-25
3
-25
3
adsorption and separation. Although complexes 1' and 2' are
-interpenetrating networks, their gas storage and separation
property were investigated. Both open 1' and 2' frameworks
show a type II N gas sorption isotherm that indicates their
permanent microporosity (Fig. S14 – S15). Single-component
CO sorption experiments were carried out up to 1 atm at 273 K
2
vs. 17.6 x 10 cm for
2
the molecular sieving effect, thermodynamic equilibrium effect,
and kinetic effect.[
22]
The Qst value for 1' and 2' indicates
and the frameworks.
2
significant interactions between CO
2
2
2
and 298 K (Fig. 3), and all CO isotherms are of type I (IUPAC
classification).[
21]
Fitting the Langmuir equations to the CO
= 0.05 – 0.25) gave
2
adsorption isotherm (at 273K, P/P
estimated surface areas of 95.2 m g for 1' and 92.3 m g for
0
-1
2
2
-1
2
'. At room temperature, these complexes showed varying
3
-1
2
degrees of CO sorption capacity (13.2 cm g for 1' and 29.6
cm3g-1 for 2', 1 atm). As the temperature was lowered from 298
2
K to 273 K, the CO adsorption capacity increased greatly for all
complexes (20.3 cm g for 1' and 40.5 cm3g-1 for 2', 1 atm).
3 -1
Complexes 1' and 2' are microporous and isostructural, but the
CO
over 2.0 times at both 298 K and 273 K (1 atm). The high CO
adsorption of 2' should be ascribed to the cation effect of
metalloligand L . The enthalpy of CO adsorption for 1' and 2'
2
adsorption amount of 2' is significantly higher than that of 1',
2
2
Figure 4. Isosteric heats of CO adsorption (Qst) values for 1' and 2’.
2
2
were estimated from the sorption isotherms at 273 and 298 K
using the virial equation to understand the strong affinity of two
In conclusion, we designed a novel metalloligand strategy to
construct porous frameworks. The combination of Ir -based
octahedral metalloligands (L and L ) and linear unit [Ni(cyclam)]
1 2
produced two isostructural complexes 1 and 2 with primitive
cubic frameworks. Unexpectedly, they are 2-interpenetrating
networks that significantly reduce the pore sizes and limit their
III
complexes toward CO
2
. At zero coverage, the enthalpy of CO
2
adsorption is 30.4 kJ mol-1 for 1' and 36.0 kJ mol for 2' (Fig. 4),
-1
which indicates the existence of sufficient interactions between
the quadrupolar CO
2
molecules and frameworks. The increase
in the CO adsorption capacity with increasing pressure and
2
available framework space. Hence their N
capacity is limited. However, they show high selectivity of
CO /N . More interestingly, framework 2' bears cationic unit,
thus leading to enhanced CO adsorption and CO /N separation
2
2
and CO adsorption
decreasing temperature is indicative of physisorption in a
microporous solid. It suggests that these materials may be
applied in pressure or temperature swing adsorption processes.
2
2
2
2
2
up to 89.7:1. We are currently investigating new methods to
prohibit the interpenetration, so as to increase the free space of
2
frameworks and further explore their CO adsorption and
separation, as well as other porosity-based applications.
Experimental Section
Synthesis of complexes 1: L
aqueous solution of NaOH (6.0 mmol, 0.24 g). Under stirring, an aqueous
solution of [Ni(cyclam)](ClO (6.0 mmol, 1.38 g) was slowly added. A
1 6
-H (1.0 mmol, 0.92 g) was dissolved in an
4 2
)
red precipitate was formed immediately. The mixture was stirred for a
further 2 h to ensure completion of the reaction. The solid was collected
by filtration, washed with H
powder. Yield 88%.
2
O and THF, and dried in air to afford a red
Synthesis of complexes 2: L
aqueous solution of NaOH (6.0 mmol, 0.24 g). Under stirring, an aqueous
solution of [Ni(cyclam)](ClO (6.0 mmol, 1.38 g) was slowly added. The
mixture was stirred for a further 2 h to ensure completion of the reaction.
The solid was collected by slow evaporation of solvents, and dried in air
to afford a red powder. Yield 81%.
2 5
-H (1.0 mmol, 0.92 g) was dissolved in an
Figure 3. CO
2
and N
2
sorption curves of complexes 1’ and 2' at different
4 2
)
temperatures.
Unlike CO
2
, N
2
gas adsorption was minimal in both two
CCDC 1567031 (1) and 1567032 (2) contain the supplementary
crystallographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
complexes up to 1 atm, indicating that they can preferentially
adsorb CO over N and have possible application in CO /N
separation. The single-component CO /N separation ratios of 1'
and 2' at 0.1, 0.3, and 1.0 atm (273 K or 298 K) were calculated
2
2
2
2
2
2
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COMMUNICATION
Sheng-Li Huang, Naifang Liu, Yun Ling,
He-Kuan Luo*
Page No. – Page No.
III
Ir -based Octahedral Metalloligands
Derived Primitive Cubic Frameworks
2 2
for Enhanced CO /N Separation
III
The combination of Ir -based octahedral metalloligand and linear unit [Ni(cyclam)]
easily afford porous complex with primitive cubic framework. These materials
exhibit promising CO /N separation application.
2 2
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