Coordination networks of a ditopic macrocycle exhibiting anion-controlled dimensional changes and crystal-to-crystal anion exchange

Article abstract of DOI:10.1021/acs.inorgchem.5b00422

A rationally designed NO₂S₂-donor macrocycle L was synthesized, and anion variation (PF₆^-, CF₃CO₂^-, NO₃^-, and CF₃SO₃^-) of i

Full text of DOI:10.1021/acs.inorgchem.5b00422

Article
pubs.acs.org/IC
Coordination Networks of a Ditopic Macrocycle Exhibiting Anion-
Controlled Dimensional Changes and Crystal-to-Crystal Anion
Exchange
Eunji Lee, Ki-Min Park, Mari Ikeda, Shunsuke Kuwahara, Yoichi Habata,* and Shim Sung Lee*,†
†
†
‡,§
§,∥
,§,∥
†
Department of Chemistry and Research Institute of Natural Science, Gyeongsang National University, Jinju 660-701, South Korea
‡
Education Center, Faculty of Engineering, Chiba Institute of Technology, 2-1-1 Shibazono, Narashino, Chiba 275-0023, Japan
§
∥
Research Center for Materials with Integrated Properties and Department of Chemistry, Faculty of Science, Toho University,
-2-1Miyama, Funabashi, Chiba 274-8510, Japan
2
*
S Supporting Information
ABSTRACT: A rationally designed NO S -donor macrocycle L was synthesized, and
2
2
−
−
−
−
anion variation (PF , CF CO , NO , and CF SO ) of its silver(I) complexes was
6
3
2
3
3
3
employed as a strategy for controlling their coordination modes and network
dimensions. The assembly reactions of L with four silver(I) salts afforded the
complexes [Ag L ](PF ) (1), [Ag L (CF CO ) ] (2), [Ag L (NO ) ] (3), and
2
2
6 2
4
2
3
2 4 n
4
2
3 4 n
{
[Ag L (CF SO ) ]CF SO } (4) that adopt cyclic dimer, 1D, 2D, and pseudo 3D
3 2 3 3 2 3 3 n
network structures, respectively, with the structure adopted depending on the
coordination ability and coordination modes of the anion used. Interestingly,
quantitative anion exchange accompanying an irreversible structural conversion from
2
, 3, or 4 to 1 was observed in the crystalline state by powder X-ray diffraction (PXRD)
−
and IR spectroscopy. A stepwise mechanistic process from 2 (CF CO , 1D) to 3
3
2
−
(
NO , 2D) by anion exchange was also proposed.
3
INTRODUCTION
We have been involved in a series of investigations aimed at
preparing new types of exo- and endo/exocoordinated
macrocyclic complexes. In this regard, several examples of
silver(I) complexes showing anion-controlled endo- or
■
The rational design of host ligand systems for the programmed
self-assembly of metallosupramolecules via coordinative
networking has attracted intense interest not only because of
the fascinating structures generated but also because of their
8
exocoordination, heterometallic endo/exocoordinated net-
9
1
works, solvent-induced single-crystal-to-single-crystal trans-
potential applications. This is also true for macrocyclic host
10
formation of endo/exocyclic silver(I) coordination polymers,
cation-selective/anion-controlled chromogenic mercury(II)
systems, which bind the metal ion inside the cavity
2
(
endocoordination). However, the networking of macrocycles
1
1
12
sensors in solution, and solid states have all been
demonstrated.
upon complexation brought by the endocoordination mode has
severe limits due to tying up the metal center in the cavity by
the bound macrocycle. Thus, very often the use of bridging
organic coligands or coordinating anions leads to the
networking of individual macrocyclic complex units to give
larger oligomer or polymer structures. In the case of bound
anions, these can also act as potential (anion) exchange sites for
the construction of new supramolecular entities.
8
−12
10
Indeed, the silver(I) ion with its d electron
configuration (being free of crystal field effects) readily binds to
macrocyclic ligands with S, S/O, and N/O donors to form
products with a variety of coordination arrangements that
commonly include endo- and/or exocyclic coordination
3
7a,13
modes.
4
In the course of our ongoing studies to prepare new types of
macrocyclic network complexes containing simultaneous endo-
and exocoordination, we have been interested in merging
individual controlling factors elucidated previously for the
Exocyclic coordination (or exocoordination), in which the
metal binds outside the macrocyclic cavity, has been employed
as an alternate means for inducing the networking of
5
5
design of new macrocyclic ligand systems. For example, a
macrocyclic species. In particular, sulfur-containing thiamacro-
primary task here was to investigate the dual coordination
cycles often exhibit metal exocoordination due to inherent
mode of the proposed NO S -macrocycle L that was
electronic and steric influences associated with the presence of
2 2
6
anticipated to bind metal ion(s) in defined position(s) inside
and/or outside of the cavity (Schemes 1 and 2). In particular,
the introduction of one pyridine unit into the macrocyclic
the sulfur donors. However, exocoordination-based network-
ing of metal-bound macrocycles as a means of directing the
formation of assembled products displaying zero to higher
dimensional topologies had remained largely unexplored, even
though a range of exocyclic macrocyclic complex products have
Received: February 20, 2015
7
been reported.
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.5b00422
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Article
Scheme 1. Influence of the Ligand and Anion on the
Coordination Mode and Networking
The bimolecular ditosylate−diol macrocyclization reaction
enables the preparation of macrocycles via C−O bond
formation, with macrocycle L being synthesized by coupling
reactions between diol 5 and ditosylate 6 in the presence of
sodium hydride under high dilution conditions (yield, 30%;
Scheme 2). Compounds 5 and 6 were prepared using known
literature procedures. The NMR spectra of L exhibit some
signal complexity due to its unsymmetrical nature (Figures S1
and S2, Supporting Information) but is in accord with the
target structure.
15
Crystal Structure of L. The structure of L is shown in
Figure 1. Single crystals of L were grown by slow evaporation
Scheme 2. Synthesis of L
Figure 1. Crystal structure of L. Torsion angles between selected
adjacent donors are S1−C−C−O1 (72.1°), O1−C−C−N1 (42.3°),
N1−C−C−O2 (150.0°), and O2−C−C−S2 (173.6°).
donor set coupled with the expected exocoordination of the
sulfur donors could induce the formation of desired endo/
exocoordinated network species. In addition to generating
discrete or polymeric structures based on endo/exocoordina-
tion, control of the dimensionality of the polymeric systems was
another goal of interest. Thus, in the present work, the use of
several anions with different coordinating abilities and bridging
modes was employed. This strategy was expected to prepare
distinct endo- and/or exocoordinated complexes of L with
discrete or polymeric structures with the coordination modes
being as depicted in Scheme 1, with the overall crystal
topologies having different dimensionalities that are anion
dependent.
from its dichloromethane solution. In the structure, the
pyridine nitrogen and one oxygen (O2) are directed toward
the cavity center while both sulfur atoms and oxygen (O1) are
oriented in an exo fashion. Accordingly, the S1···S2 distance
(
7.60 Å) in L is larger than that for O1···O2 (6.10 Å). From the
torsion angles in the ligand backbone associated with the
orientation of the donors, the conformation of the S1−O1−
N1−O2−S2 linkage in the macrocycle unit can be described as
g-g-t-t (t = trans, g = gauche).
Synthesis and Structural Description of the Silver
Complexes Incorporating Different Anions. The influence
of changing the anion on the coordination modes and network
dimensions of the silver(I) complexes of L was investigated. As
mentioned already, the use of four silver(I) salts resulted in the
formation of discrete to pseudo 3D polymeric products when
the syntheses were performed under related conditions
(Scheme 3).
In this study, we prepared four silver(I) complexes of L,
displaying different coordination modes (endo/endo and
endo/exo) and topologies (dimer and network) that clearly
−
−
−
depend on the nature of the anions (PF , CF CO , NO ,
6
3
2
3
−
−
−
−
and CF SO ) used. Changing CF CO to NO3 or CF SO3
3
3
3
2
3
resulted in dimensional changes of the resulting solid-state
network structures from 1D to 2D or pseudo 3D. These anion-
controlled structural differences in the crystalline state have
been systemically investigated, and a stepwise mechanistic
process for the unique structural transformations accompanying
the dimensional changes has been proposed.
Reaction of L with AgPF in dichloromethane/methanol
6
yielded colorless crystals suitable for X-ray analysis. The crystal
structure showed the product to be an unusual dinuclear
bis(macrocycle) species of type {[Ag L ](PF ) (1) in which
2
2
6 2
no anion or solvent molecules are present in its coordination
sphere (Figure 2 and Table 1). Selected structural parameters
are listed in Table 2. Due to the inversion symmetry, the
RESULTS AND DISCUSSION
■
asymmetric unit contains one L molecule, one Ag atom, and
−
Ligand Design and Synthesis. The macrocycle L has
lower symmetry arising from the introduction of both endo-
and exocoordination domains (Scheme 1). In an attempt to
induce endocyclic coordination, one pyridine and two ether
oxygen donors were introduced. The relatively large separation
of the two sulfur donors in the 1,3-benzylic positions is
expected to result in each sulfur donor coordinating to
individual metal ions, with the presence of both endo- and
exocoordination sites expected to result in endo/exocoordi-
one PF . In 1, the endocyclic Ag1 atom which lies inside the
6
cavity is five coordinate, being bound to the NO S donors from
2
one L. Notably, the remaining one site is occupied by one S
donor (S2A) from an adjacent L to form a dimeric
arrangement.
The silver(I) center in 1 can be considered as being in a
16
distorted square pyramidal environment (τ value = 0.125).
The bridging Ag1−S2A [2.452(1) Å] bond is shorter than
Ag1−S1 [2.568(1) Å] in the same plane, but both are within
the normal range for this bond type. The Ag1−O1 bond
5
a,14
nated complexes.
B
DOI: 10.1021/acs.inorgchem.5b00422
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Scheme 3. Silver(I) Complexes Prepared in This Work
dimer. With respect to this, cyclic oligomeric complexes of
macrocycles (including cyclic dimers) have been recently
5b
reviewed by us.
As outlined in Scheme 1, we examined the ditopic behavior
of L by employing different silver(I) salts. When silver(I)
trifluoroacetate was used under the same reaction conditions to
those employed for silver(I) hexafluorophosphate, a colorless
crystalline product 2 suitable for X-ray analysis was isolated.
Unlike the discrete structure of 1, the crystal structure showed
that 2 is a 1D polymeric complex of type [Ag L (CF CO ) ] ,
4
2
3
2 4 n
in which two crystallographically independent silver atoms
(
Ag1 and Ag2) are positioned inside (Ag1) and outside (Ag2)
the cavity (Figure 3). Selected structural parameters are given
in Table 3. In this case, two endocyclic silver(I) complex units
are bridged by two exocyclic silver(I) centers to generate a
tetranuclear bis(macrocycle) unit which is further linked by two
bidentate trifluoroacetate ions to give a 1D polymer structure.
The asymmetric unit contains one L, two Ag atoms, and two
trifluoroacetate ions. In 2, the endocyclic Ag1 atom is five
coordinate, being bound to NO S donors from one L, with the
2
fifth site occupied by one monodentate trifluoroacetate ion.
The exocyclic Ag2 atom is four coordinate, being bound to two
sulfur donors (S1 and S2A) from two adjacent L ligands, with
the remaining two sites occupied by two monodentate bridging
trifluoroacetate ions. In connecting the tetranuclear bis-
Figure 2. (a) Discrete cyclic dimer structure of the silver(I)
hexafluorophosphate complex 1, [Ag L ](PF ) . (b) Side view
showing its dinuclear sandwich-type structure. Noncoordinating
anions are omitted.
2
2
6 2
(
macrocycle) units, the two bridging trifluoroacetate ions and
two silver atoms form an octagonal cycle, and this metal-
distance [2.638(2) Å] is typical, but that of the Ag1−O2 bond
lacyclization limits the topology of the resulting product to be
19
[
[
3.038(3) Å] lies at the longer end of the database range
one dimensional. The separation of the two aromatic rings
(centroid-to-centroid distance 5.54 Å) in the adjacent macro-
cycles is well outside the range expected for a π−π stacking
1
7
2.40−3.06 Å].
In terms of the conformational changes of the ligand upon
20
complexation, O2 and S1 donors in 1 are oriented toward the
inside of the macrocyclic cavity. Accordingly, the S1···S2
distance (5.86 Å) in 1 is shorter than in free L (7.60 Å) but still
large enough to induce the two sulfur donors to bind to two
interaction. The S1···S2 distance (6.27 Å) in 2 is shorter than
that in free L (7.60 Å) but longer than that (5.86 Å) in 1, which
allows the two sulfur donors to bind two different endocyclic
silver atoms. Compared with the noncoordinating nature of
14a
−
−
different metal ions. Hence, the metal center in 1 is shielded
PF6 in 1, the influence of the coordinating ability of CF CO
3 2
by the bound macrocycles from the anion and solvent
in 2 to induce the endo/exocoordination as well as the linking
the bis(macrocycle) complex units to form a 1D polymer chain
is noteworthy.
The preparation of the anion-dependent silver(I) complexes
1 and 2 displaying different dimensions encouraged us to probe
the possible formation of corresponding coordination networks
with higher dimensions. We assumed that the use of smaller
molecules. The formation of this structure is also likely
−
influenced by the weaker coordinating ability of the PF
6
1
8
anion. Consequently, the preferred anion/solvent non-
coordinated cyclic dimer structure obtained presumably reflects
that when the coordination ability of the anion is weak two
adjacent complex units interact directly to form a discrete
C
DOI: 10.1021/acs.inorgchem.5b00422
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Table 1. Crystal and Experimental Data
L
1
2
3
4
formula
fw
C H N O S
C H Ag P F N O S
C H Ag F N O S
C H Ag N O S
C20.5H Ag1.5F4.5N O6.5S3.5
23 1
1
9
23
1
2
2
19 23
2
1
6
1
2
2
23 23
2
6
1
6
2
19 23
2
3
8
2
361.50
173(2)
triclinic
P-1
614.34
803.28
701.26
746.91
temp (K)
cryst syst
space group
Z
173(2)
173(2)
triclinic
P-1
173(2)
173(2)
orthorhombic
Pccn
monoclinic
monoclinic
P2 /n
1
P2 /c
1
2
4
2
4
8
a (Å)
9.3283(2)
10.2295(2)
10.6795(2)
11.2267(2)
17.0130(3)
12.2564(2)
90
9.51350(10)
11.5738(2)
13.9234(2)
107.5140(10)
101.7770(10)
97.0910(10)
1402.88(3)
1.902
15.0491(8)
18.8422(10)
8.0315(4)
90
10.1091(3)
19.8081(6)
25.7293(7)
90
b (Å)
c (Å)
α (deg)
β (deg)
γ (deg)
V (Å3)
Dcalcd (g/cm3)
87.9530(10)
71.8170(10)
67.7530(10)
892.17(3)
1.346
108.1490(10)
90
91.875(2)
90
90
90
2224.51(7)
1.834
2276.2(2
2.046
5152.1(3)
1.926
2θmax (deg)
52.00
56.00
56.00
56.00
56.00
R , wR [I > 2σ(I)]
0.0300, 0.0777
0.0341, 0.0814
1.032
0.0383, 0.0929
0.0453, 0.0980
1.005
0.0218, 0.0470
0.0285, 0.0499
1.017
0.0656, 0.1855
0.0708, 0.1884
1.050
0.0248, 0.0558
0.0318, 0.0598
1.011
1
2
R , wR [all data]
1
2
goodness-of-fit on F2
no. of reflns used [>2σ(I)]
refinement
3477 [Rint = 0.0226]
full matrix
5365 [Rint = 0.0306]
6750 [Rint = 0.0238]
5497 [Rint = 0.0337]
6225 [Rint = 0.0463]
full matrix
full matrix
full matrix
full matrix
Table 2. Selected Bond Lengths (Angstroms) and Bond
with the centroid-to-centroid distance between the two
aromatic rings involved being 4.56 Å; this falls at the long
end of the literature range (3.7−4.6 Å) for such an
a
Angles (degrees) for 1, [Ag L ](PF )
2
2
6 2
Ag1−N1
Ag1−O2
Ag1−S2A
2.299(2)
3.038(3)
2.452(1)
Ag1−O1
Ag1−S1
2.638(2)
2.568(1)
20
interaction.
As an extension of the above, when silver(I) trifluorometha-
nesulfonate was employed a pseudo 3D polymeric product of
N1−Ag1−S1
N1−Ag1−O2
O1−Ag1−O2
S1−Ag1−O2
O2−Ag1−S2A
102.8(1)
N1−Ag1−O1
N1−Ag1−S2A
S1−Ag1−O1
O1−Ag1−S2A
S1−Ag1−S2A
69.2(1)
133.0(1)
74.6(1)
type {[Ag L (CF SO ) ]CF SO } (4) was isolated (Figure 5).
64.2(1)
119.4(1)
80.2(1)
3
2
3
3 2
3
3 n
The asymmetric unit of 4 contains 1 L molecule, 1.5 Ag atoms,
−
−
1
coordinated CF SO , and 0.5 uncoordinated CF SO .
114.3(1)
123.7(1)
3 3 3 3
Again, there are two kinds of Ag atoms (Ag1 and Ag2)
occupying different positions and showing different coordina-
tion environments. Thus, the Ag1 atom inside the cavity is five-
125.5(1)
a
Symmetry operations: (A) −x + 1, y, −z + 1.
coordinate, being bound to NO S donors from one L, with the
2
multidentate anions with trigonal or tetrahedral shapes might
lead to the formation of not only endo/exocoordination but
remaining site occupied by one S donor (S2A) from an
adjacent L to form a 1D polymeric chain via Ag1−S2A bond
[2.476(1) Å] formation, Table 5. The adjacent 1D chains are
cross-linked by Ag2 atoms outside the cavity via an Ag2−S1
bond [2.552(1) Å], resulting in the formation of a brick-wall-
type 2D polymer structure. One brick unit consists of eight Ag
atoms and six macrocycles (Figure 5c). The exocyclic Ag2 atom
7a,21
also higher dimensional networks.
In fact, the role of the
anions on the dimensionality of silver(I) adducts for the linear
22
ligand system has been largely investigated.
When silver(I) nitrate was used in the reaction with L,
crystalline product 3 was isolated. Compound 3 features a 2D
polymeric structure of type [Ag L (NO ) ] in which two
4
2
3 4 n
is four coordinate, and its coordination sphere is completed by
crystallographically different silver(I) ions are positioned inside
Ag1) and outside (Ag2) the cavity (Figure 4). Again, bridging
−
two CF SO3 ions as terminal monodentate ligands, with a
3
(
Ag2−O3 bond distance of 2.415(2) Å. As a result, the anion in
of two endocyclic silver(I) complex units by two exocyclic
silver(I) atoms affords a tetranuclear bis(macrocycle) unit
which is further linked by one nitrate ion to give a 1D
polymeric wavy chain. The parallel 1D wavy chains are cross-
linked by another bridging nitrate ion to generate a 2D network
structure (Figure 4a−c). The asymmetric unit in 3 contains one
L molecule, two Ag atoms, and two nitrate ions.
4
does not participate in the networking of the resulting
structure. This contrasts with the situation in 2 and 3 in which
the anions link the metal centers as linker ligands and lead to
the formation of the observed higher dimensional topologies.
The preferred infinite endo/exocyclic 2D structure of 4 is also
associated with the role of one sulfur donor (S1) which
coordinates to the endocyclic Ag1 and exocyclic Ag2 atoms
simultaneously.
In the packing structure of 4, the face-to-face π−π stacking
interaction (centroid-to-centroid distance 3.61 Å) between two
layers allows the formation of the pseudo 3D polymeric
The Ag1 atom in the macrocyclic cavity is five coordinate,
being bound to NO S donors (N1, O1, O2, and S1) from one
2
L, with the fifth site occupied by one monodentate terminal
nitrate ion (Figure 4d and Table 4). The Ag2 atom outside the
cavity is four coordinate, being bound to two sulfur donors (S1
and S2A) from two adjacent L ligands with the two sites
occupied by two monodentate bridging nitrate ions. Addition-
ally, face-to-face π−π stacking interactions between two
adjacent macrocycles is observed (dashed line in Figure 4d),
structure (dashed lines in Figure 5a). The surrounding empty
−
space is occupied by disordered CF
SO
3
ions stabilized by
3
CH···F H bonding (Figure S4, Supporting Information). This is
a rare case in which a high-dimensional structure of a
D
DOI: 10.1021/acs.inorgchem.5b00422
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Figure 3. (a) 1D polymeric structure of the silver(I) trifluoroacetate complex 2, [Ag L (CF CO ) ] . (b) View of the coordination environments.
4
2
3
2 4 n
(
c) Side view.
Table 3. Selected Bond Lengths (Angstroms) and Bond
perhaps reflecting the presence of the interlayer π−π stacking
interactions between aromatic units in the solid state as seen in
its X-ray structure (Figure 5a).
a
Angles (degrees) for 2, [Ag L (CF CO ) ]
4
2
3
2 4 n
Ag1−N1
Ag1−O2
Ag1−S1
Ag2−O6B
2.315(2)
Ag1−O1
Ag1−O3
Ag2−O5
Ag2−S1
2.615(1)
2.337(2)
2.549(1)
2.478(1)
Thermal Stability. TGA analyses were performed in order
to investigate the thermal stabilities of 1−4 (Figure 7). The
2.594(1)
2.491(1)
2.370(1)
2.468(1)
65.5(1)
TGA curves revealed that the thermal stabilities of 1−4 are not
−
very different. For example, the PF -containing dimer 1 is
6
Ag2−S2A
stable up to 222 °C, while the TGA curves for the polymeric
products 2, 3, and 4 indicate no loss of solvent molecules
occurs until 210, 200, and 240 °C, respectively, in accord with
the presence of tightly packed solid-state structures. This result
is also consistent with the high calculated densities of 2, 3, and
N1−Ag1−O1
N1−Ag1−O3
O1−Ag1−O2
O1−Ag1−S1
O2−Ag1−S1
O5−Ag2−O6B
O5−Ag2−S2A
O6B−Ag2−S2A
N1−Ag1−O2
N1−Ag1−S1
O1−Ag1−O3
O2−Ag1−O3
O3−Ag1−S1
O5−Ag2−S1
O6B−Ag2−S1
S1−Ag2−S2A
68.8(1)
130.2(1)
123.8(1)
78.1(1)
107.0(1)
133.4(1)
73.4(1)
136.2(1)
99.8(1)
119.0(1)
90.4(1)
4
(Dcalcd = 1.834−2.046) found for these structures (Table 1).
Further heating of each complex up to ∼450 °C resulted in
complex decomposition.
100.3(1)
110.3(1)
100.5(1)
144.8(2)
a
Structural Transformation via Anion Exchange in the
Crystalline State. Since the anion-dependent products 1−4
with different dimensionalities are insoluble in water and
common organic solvents, structural conversion of these
products by anion exchange in the crystalline state was
investigated. Each crystalline sample was immersed in a 3 M
aqueous solution of the sodium salt of the required anion, and
the solid was periodically collected by filtration. The structural
conversions associated with anion exchange in the respective
solids were systemically monitored by their PXRD patterns and
IR spectra.
Symmetry operations: (A) −-x + 2, −y + 1, −z + 1. (B) −x + 2, −y +
, −z + 1.
2
macrocyclic ligand system is formed without direct anion
involvement.
Photophysical Properties. The photoluminescence prop-
erties of L and its silver(I) complexes 1−4 were investigated in
the solid state (Figure 6). While free L shows no significant
emission, its complexes display blue photoluminescence
resulting from the π−π* transition in the respective aromatic
moieties. For each complex the emission intensity of the
complexes may likely be enhanced through the presence of the
endo/exocyclic metal coordination by the macrocyclic ligand
which increases the structural rigidity of the ligand and thereby
Interestingly, in particular cases the anion-exchange
procedure induced a dimensional increase in the crystalline
sample. For example, when 2 was immersed in 3 M NaNO
3
23
reduces the loss of energy by nonradiative decay. The
aqueous solution and left undisturbed at ambient temperature
to allow anion exchange, the PXRD patterns for the samples
collected after 0.5 and 1 h show a decreased intensity for 2 (red
square in Figure 8a) and an increased intensity for 3 (green
emission spectra of 1, 2, 3, and 4 show maxima at 428, 409,
410, and 419 nm, respectively. Among the polymeric species, 4
shows a red-shifted peak (419 nm) with the highest intensity,
E
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Figure 4. (a) 2D polymeric network structure of silver(I) nitrate complex 3, [Ag L (NO ) ] , showing two types of anion linking. (b) Schematic
4
2
3 4 n
presentation of the 2D network. (c) One block unit with four tetranuclear bis(macrocycle) subunits. (d) View of the coordination environments.
the NO − ion but also the solid-state topology fully changes
from 2D to 3D within 3 h.
Table 4. Selected Bond Lengths (Angstroms) and Bond
3
a
Angles (degrees) for 3, [Ag L (NO ) ]
4
2
3 4 n
To investigate the reversibility of the anion exchange
between 2 and 3, the insoluble crystals of 3 were immersed
in 3 M NaCF CO aqueous solution. As shown in Figure 9, the
Ag1−N1
Ag1−O2
Ag1−S1
Ag2−O8B
2.324(7)
Ag1−O1
Ag1−O3
Ag2−O6
Ag2−S1
2.597(6)
2.412(2)
2.541(7)
2.553(2)
2.630(6)
2.551(2)
2.445(7)
2.510(2)
66.7(2)
3
2
PXRD patterns and IR spectra for the samples collected after 2
days show decreased peak intensities for 3 (green circle) and
the appearance of new peaks for 2 (red square), indicating the
presence of a partially anion-exchanged sample. After 1 week
under the same conditions, the peaks for 3 showed weaker
intensities but were still present along with increased peak
intensity for 2, indicating that the anion exchange is not
Ag2−S2A
N1−Ag1−O1
N1−Ag1−O3
O1−Ag1−O2
O1−Ag1−S1
O2−Ag1−O3
O6−Ag2−S1
O6−Ag2−S2A
O8B−Ag2−S2A
N1−Ag1−O2
N1−Ag1−S1
O1−Ag1−O3
O2−Ag1−S1
O3−Ag1−S1
O6−Ag2−O8B
O8B−Ag2−S1
S1−Ag2−S2A
68.8(2)
133.0(2)
127.7(8)
136.8(1)
126.6(4)
121.0(2)
95.0(2)
97.7(6)
134.3(2)
73.4(2)
68.2(5)
−
completely reversible, as only about 50% of NO3 could be
86.4(2)
−
exchanged with CF CO .
3
2
111.8(2)
99.6(2)
The above anion-exchange procedure can be extended to
other anions. When 2, 3, and 4 were each immersed in a 3 M
NaPF6 aqueous solution and left undisturbed at ambient
temperature, the PXRD pattern and IR spectrum for each
sample collected after 12 h was completely coincident with that
for 1, indicating that 2, 3, and 4 (with polymeric structures)
were each converted to the discrete dimer 1 quantitatively by
145.4(1)
a
Symmetry operations: (A) −x + 1, −y + 1, −z + 1. (B) x, −y + 1.5, z
0.5.
−
circle in Figure 8a), indicating that partial anion exchange had
occurred. Moreover, the PXRD pattern for the sample collected
after 3 h was completely coincident with that of 3, indicating
that the 1D structure of 2 had been quantitatively converted to
−
−
−
−
the exchange of CF
CO
, NO
, and CF
SO
3
with PF ,
3
2
3
3
6
respectively (Figures S6−S8, Supporting Information). How-
−
−
−
−
−
the 2D structure 3 by the exchange of CF CO with NO .
ever, the PF
6
in 1 did not exchange with CF
SO even when 1 was immersed in the 3 M sodium salt
3 3
3 2 3
CO , NO , and
3
2
3
−
The IR spectra are in accord with the above PXRD results.
As shown in Figure 8b, the IR spectra for the samples collected
after 0.5 and 1 h show the gradual disappearance of an intense
CF
solution with the chosen anion for 1 week. Similarly, CF
in 4 underwent complete exchange with CF CO and NO
−
SO
3
3
−
−
3 2
3
−
−1
CF CO2 peak at 1685 cm (red square) and the growth of a
to give 2 and 3, respectively, when the crystals of 4 were
3
−
−1
−
new NO3 band at 1383 cm (green circle). The CF CO2
immersed in an aqueous solution of NaCF CO and NaNO
3
3
2
3
peak disappears completely after 3 h, and the resulting IR
for 12 h (Figures S9 and S10, Supporting Information).
However, the CF CO in 2 and NO3− in 3 did not exchange
−
spectrum does not differ significantly from that of 3, suggesting
3
2
−
−
that not only is the CF CO ion quantitatively displaced by
with CF SO3 under similar conditions.
3
3
2
F
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Figure 5. (a) Pseudo 3D polymeric structure of the silver(I) trifluoromethanesulfonate complex 4, {[Ag L (CF SO ) ]CF SO } , formed via
3
2
3
3
2
3
3 n
−
interlayer π−π stacking (centroid-to-centroid distance 3.61 Å). (b) Brick-wall-type 2D layer structure. (c) One-brick unit (two terminal CF SO
3
3
ions coordinated to Ag2 atoms are omitted). (d) View of the coordination environments.
Table 5. Selected Bond Lengths (Angstroms) and Bond
a
Angles (degrees) for 4, {[Ag L (CF SO ) ]CF SO }
3
2
3
3 2
3
3
n
Ag1−N1
Ag1−O2
Ag1−S2A
Ag2−S1
N1−Ag1−O1
N1−Ag1−S1
O1−Ag1−O2
O1−Ag1−S2A
O2−Ag1−S2A
O3−Ag2−O3B
O3−Ag2−S1
2.293(2)
2.586(2)
2.476(1)
2.552(1)
69.3(1)
Ag1−O1
Ag1−S1
Ag2−O3
2.603(2)
2.655(1)
2.415(2)
N1−Ag1−O2
N1−Ag1−S2A
O1−Ag1−S1
O2−Ag1−S1
S2A−Ag1−S1
O3−Ag2−S1B
S1−Ag2−S1B
69.2(1)
140.0(1)
74.5(1)
110.9(1)
138.3(1)
109.6(1)
104.3(1)
90.8(1)
117.9(1)
106.8(2)
123.2(1)
131.5(1)
91.7(1)
a
Symmetry operations: (A) x + 1/2, −y + 1, −z + 1/2. (B) −x + 1/2,
−
y + 3/2, z.
Figure 6. Solid-state photoluminescence spectra of 1−4 at room
The observed anion-exchange results are summarized in
temperature (excitation at 360 nm).
Scheme 4. All products displayed anion-exchange abilities, with
−
−
−
−
PF6 being preferred over CF CO , NO , and CF SO . On
3
2
3
3
3
−
24
the basis of the pairwise results, the anion exchanges show the
for CF SO follow the Hofmeister series, which shows the
3 3
−
−
−
order PF6 ≫ ClO4− > BF4− > CF CO > NO3− > Cl >
−
−
−
−
following order: PF (1) > NO3 (3) > CF CO2 (2) >
6
3
3
2
−
−
− −
CF SO3 (4). The preference for PF6 and the lowest affinity
CF SO3 > HCO2 > H PO . However, the observed
3 2 4
3
G
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Inorganic Chemistry
Article
Figure 7. TGA curves for 1−4.
Figure 9. (a) PXRD patterns for 3 after anion exchange with 3 M
NaCF CO aqueous solution for 2 days and 1 week. (b) IR spectra for
3
2
3
after anion exchange with 3 M NaCF CO aqueous solution for 2
3 2
days and 1 week. Data shown in the top and bottom represent the
PXRD patterns and the IR spectra for 3 and 2 prepared by direct
synthesis, respectively.
Scheme 4. Structural Transformation of 1−4 by Anion
Exchange in the Crystalline State
Figure 8. (a) PXRD patterns for 2 after anion exchange employing 3
M NaNO aqueous solution for 0.5, 1, and 3 h. (b) IR spectra of 2
knowledge, the present anion-exchange systems are the first
examples of bifunctional macrocycle-based coordination
polymers to show dimensional changes resulting from anion
exchange in the crystalline state.
3
after anion- exchange employing 3 M NaNO aqueous solution for 0.5,
3
1
, and 3 h. Data shown in the top and bottom represent the PXRD
patterns and the IR spectra for 2 and 3 prepared by direct synthesis,
respectively.
In order to investigate the mechanistic process of the anion
exchange, single crystals of 2 before and after immersing to 3 M
NaNO3 aqueous solution were used for atomic force
microscope (AFM). Apparently, the sample does not change
size or shape but loses transparency and single crystallinity
during anion exchange. The AFM images and profiles in Figure
10 reveal that the crystal surface undergoes significant
transformation, suggesting a restructuring of the crystal surface.
Within 10 min, for example, the relatively homogeneous and
flat crystal surface of the sample (Figure 10a) becomes rough,
showing holes and clefts (Figure 10b). Soon a new crystal
phase appears and continues to grow across the crystal surface.
The entire process is compete about after 12 h, resulting in the
final surface of the anion-exchanged sample more regularly
preference of NO3− (3) over CF CO (2) represents a
−
3
2
deviation from the Hofmeister series. As already discussed, the
anion exchange of CF CO in 2 with NO3 to yield 3 is
−
−
3
2
noteworthy because it occurs quantitatively in the crystalline
state, accompanied by a dimensional increase from 1D to 2D.
There have been a few reports so far of structural
transformations accompanying dimensional changes in the
crystalline state when insoluble MOFs were treated with
solvents. These systems differ from the present ones in that
the latter involve crystalline complexes and coordination
polymers incorporating the ditopic macrocycle L, instead of
2
5
4
,25
the usual linear-ligand-based MOFs.
To the best of our
H
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Article
Figure 10. AFM images and profiles (bottom) of the surface of a crystal of 2 after immersing in 3 M NaNO aqueous solution: (a) before anion-
3
exchange, (b) 10 min, (c) 30 min, (d) 1 h, (e) 2 h, and (f) 12 h. Image size is 2 × 2 μm in all cases.
Scheme 5. Postulated Structural Conversion Process Accompanying the Dimensional Change from 1D (2) to 2D (3) by Anion
Exchange in the Crystalline State
ordered and consists of microcrystallites. These observations
are typical for solvent-mediated transformation, which forms
a new crystalline phase on the surface.
solvent-mediated dissolution (bond-breaking) and recrystalliza-
tion (bond-making) process.
26
26
Although the detailed mechanism of the above structural
CONCLUSION
■
−
−
transformations from 2 (CF CO , 1D) to 3 (NO , 2D) is not
3
2
3
In this work, a rationally designed NO S -macrocycle L that
2
2
clear cut, we postulate the operation of a stepwise mechanistic
process on the basis of the AFM images, PXRD patterns, IR
spectra, and crystal packing structures as depicted in Scheme 5.
Considering the packing structure of 2 and the network pattern
was expected to induce the formation of endo/exocoordinated
network products was synthesized and this goal was realized.
Indeed, the use of silver(I) allowed the formation of products
with different metal coordination modes that included endo-
and/or exocyclic binding. Furthermore, depending on the silver
salt employed for complexation, a discrete cyclic dimer (1) and
three polymeric products with 1D (2), 2D (3), and pseudo 3D
(4) structures were isolated. The formation of the dinuclear
sandwich-type cyclic dimer 1 appears to be mainly influenced
of 3 shown in the top of Scheme 5, on immersing in an aqueous
−
solution of NO , the crystalline sample of 2 with a parallel
3
packing of 1D chains could be rearranged to give a waved
intermediate with a herringbone packing pattern followed by
initiation of anion exchange. Then the intermediate is
considered to be converted to the final nitrate-containing 2D
by the presence of the large S···S distance in L and the
noncoordinating behavior of the PF .
−
−
−
structure by replacing CF CO with NO3 through the
3
2
6
I
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Inorganic Chemistry
Article
In both 2 (1D with trifluoroacetate anion) and 3 (2D with
nitrate anion), the tetranuclear bis(macrocycle) complex units
performed in a transmission mode with a Bruker GADDS
diffractometer equipped with graphite-monochromated Cu Kα
radiation (λ = 1.54073 Å). Atomic force microscope (AFM) imaging
was performed in a noncontact mode under the following conditions:
scan rate of 0.6 Hz; PPP-NCHR 10 M cantilever (Park systems).
are linked by anion coordination in a bridging bidentate
−
manner to give infinite structures. However, CF CO2 in 2
3
−
induces the formation of a 1D polymeric chain, while NO3 in
15a
Synthesis and Characterization of L. The precursor diol 5
2.00 g, 7.74 mmol) was dissolved in anhydrous THF (30 mL) and
3
results in the formation of a 2D network product. In 2, two
(
−
bridging CF CO2 ions form an octagonal metallacycle with
3
added dropwise to a stirred suspension of NaH (0.47 g, 19.6 mmol) in
anhydrous THF (50 mL) under nitrogen. After addition of the diol at
room temperature, the mixture was refluxed for 1 h and then cooled to
two exocyclic Ag atoms. Thus, it is the networking via two
−
CF CO2 ions that results in the propagation of the single
3
1
5b
metallacyclic units in one direction to generate the 1D
polymeric chain. This behavior appears mainly due to the
steric hindrance of the large trifluoromethyl group and the
preferred tendency to form a cyclic structure via H bonding or
metal coordination. Unlike 2, two nitrate ions in 3 propagate in
two directions resulting in the formation of the 2D network.
The smaller size and variable coordination modes of the nitrate
ion are apparently advantageous in aiding the generation of this
higher dimensional product.
The same reaction with silver(I) trifluoromethanesulfonate
induced the formation of the pseudo 3D product 4 in which the
endocyclic Ag atoms link macrocycles to generate 1D chains
which are further cross-linked by the exocyclic Ag atoms to
form a brick-wall-type 2D polymeric structure. The interligand
π−π stacking between the layers yields a pseudo 3D polymeric
structure. In this case, the anion acts as a terminal monodentate
ligand.
0 °C. 2,6-Bis(tosyloxymethyl)pyridine 6 (3.47 g, 7.75 mmol) was
dissolved in anhydrous THF (40 mL) and added slowly dropwise to
the reaction mixture. The reaction mixture was rapidly stirred for 48 h
at room temperature and then evaporated. The residue was partitioned
between water and dichloromethane. The aqueous phase was
separated and extracted with two further portions of dichloromethane.
The combined organic phases were dried with anhydrous sodium
sulfate and then evaporated to dryness. The flash column
chromatography (SiO ; dichloromethane−ethyl acetate 8:2) afforded
2
1
the product as a white solid in 30% yield. Mp: 102−104 °C. H NMR
(300 MHz, CDCl ): δ 7.70 (s, 1H, Ar), 7.30−7.19 (m, 5 H, Ar), 7.11
3
(s, 1 H, Ar), 4.61 (s, 4 H, ArCH O), 3.74 (s, 4 H, ArCH OS), 3.71 (t,
2
2
13
4
H, SCH CH O), 2.56 (t, 4 H, SCH CH O). C NMR (75 MHz,
2 2 2 2
CDCl ): 157.59, 138.45, 137.23, 130.26, 129.16, 127.41, 121.73, 73.74,
3
7
1
8
0.97, 36.06, 29.66. IR (KBr pellet): 3040, 2957, 2919, 2899, 2846,
591, 1577, 1454, 1418, 1360, 1343, 1152, 1110, 1086, 1040, 1022,
−1
01, 765, 727, 708 cm . Anal. Calcd for [C H N O S ]: C, 63.13;
19
23
1
2 2
H, 6.41; N, 3.87; S, 17.74. Found: C, 62.86; H, 6.51; N, 3.88; S, 17.49.
+
Mass spectrum: m/z = 362.16 [C H N S ] .
19
24
1 4
It is interesting that the respective products obtained share
some common structural features. First, one silver(I) occupies
the center of the macrocyclic cavity undoubtedly reflecting the
presence of the pyridine subunit. Second, except for 1 where L
Preparation of [Ag L ](PF ) (1). In a glass tube, silver(I)
2 2 6 2
hexafluorophosphate (11.1 mg, 0.044 mmol) in methanol (2 mL) was
layered onto a solution of L (10.5 mg, 0.029 mmol) in dichloro-
methane (2 mL). The X-ray quality colorless crystalline product 1 was
obtained. Yield: 60%. Mp: 234−236 °C (decomp.). IR (KBr pellet):
binds to one silver(I) via NO S donors and another silver(I)
2
3
1
[
023, 2907, 2869, 1603, 1579, 1449, 1417, 1368, 1292, 1167, 1111,
through a Ag−S bond, the exocyclic silver(I) links the
endocyclic complex units. Third, depending on the anion
coordination mode, different topological products were
prepared.
−
1
086, 1046, 841, 761, 706 cm
. Anal. Calcd for
C H Ag P F N O S ]: C, 37.15; H, 3.77; N, 2.28; S, 10.44.
38 46 2 2 12 2 4 4
Found: C, 37.05; H, 3.94; N, 2.28; S, 10.58.
Preparation of [Ag L (CF CO ) ] (2). Silver(I) trifluoroacetate
4
2
3
2 4 n
For the anion-exchange experiments in the crystalline state,
all products displayed anion-exchange abilities that followed the
(
9.5 mg, 0.043 mmol) in methanol (2 mL) was added to a solution of
L (10.2 mg, 0.028 mmol) in dichloromethane (2 mL). Slow
evaporation of the solution afforded a colorless crystalline product 2
suitable for X-ray analysis. Yield: 70%. Mp: 220−222 °C (decomp.).
IR (KBr pellet): 3039, 2957, 2921, 2849, 1685, 1639, 1593, 1578,
1459, 1424, 1362, 1208, 1129, 1087, 1042, 1023, 838, 802, 723, 710
−
−
following order: PF (1) > NO3 (3) > CF CO (2) >
6
3
2
−
−
CF SO3 (4). The preference for PF and the lowest affinity
for CF SO3 indicate Hofmeister behavior. On the basis of the
structural transformation from 2 (CF CO , 1D) to 3 (NO ,
3
6
−
3
−
−
3
2
3
−1
cm . Anal. Calcd for [C H Ag F N O S ]: C, 34.39; H, 2.89; N,
46
46
4
12
2
12 4
2
D), the stepwise solvent-mediated mechanistic process shown
1
.74; S, 7.98. Found: C, 34.52; H, 2.83; N, 1.74; S, 8.08.
previously was proposed.
Preparation of [Ag L (NO ) ] (3). Silver(I) nitrate (6.5 mg,
4
2
3 4 n
From these results, it is concluded that the use of the ditopic
macrocycle L enabled us to prepare new types of endo/
exocyclic network complexes with their coordination modes
and dimensions also under anion control both in the synthetic
stage and also via anion exchange in the crystalline state.
Further investigations of these and related novel supra-
molecular complexes displaying different coordination modes
along with their applications are in progress.
0
.042 mmol) in methanol (2 mL) was added to a solution of L (10.2
mg, 0.028 mmol) in dichloromethane (2 mL). Slow evaporation of the
solution afforded a colorless crystalline product 3 suitable for X-ray
analysis. Yield: 75%. Mp: 206−208 °C. IR (KBr pellet): 3022, 2922,
2860, 1599, 1578, 1480, 1440, 1383, 1301, 1133, 1106, 1088, 1033,
−1
1
004, 933, 813, 791, 710 cm . Anal. Calcd for [C H Ag N O S ]:
38 46 4 6 16 4
C, 32.54; H, 3.31; N, 5.99; S, 9.14. Found: C, 32.37; H, 3.31; N, 5.90;
S, 8.82.
Preparation of {[Ag L (CF SO ) ]CF SO } (4). Silver(I) trifluor-
3
2
3
3 2
3
3 n
omethanesulfonate (8.5 mg, 0.033 mmol) in methanol (2 mL) was
added to a solution of L (10.2 mg, 0.028 mmol) in dichloromethane
(2 mL). Slow evaporation of the solution afforded a colorless
crystalline product 4 suitable for X-ray analysis. Yield: 65%. Mp: 202−
204 °C. IR (KBr pellet): 3073, 2999, 2920, 2872, 1604, 1578, 1471,
1445, 1366, 1279, 1260, 1225, 1165, 1110, 1085, 1050, 1026, 997, 901,
EXPERIMENTAL SECTION
■
General. All chemicals and solvents used in the syntheses were of
reagent grade and used without further purification. NMR spectra
were recorded on a Bruker 300 spectrometer (300 MHz). The FT-IR
spectra were measured with a Nicolet iS10 spectrometer. The ESI-
mass spectra were obtained on a Thermo Scientific LCQ Fleet
spectrometer. The elemental analysis was carried out on a Thermo
Scientific Flash 2000 Series elemental analyzer. Thermogravimetric
analyses were recorded in a TA Instruments TGA-Q50 thermogravi-
−1
809, 797, 781, 757, 707 cm . Anal. Calcd for [C H Ag F N O S ]:
41
46
3
9
2
13 7
C, 32.97; H, 3.10; N, 1.88. Found: C, 33.26; H, 3.11; N, 1.93.
Anion Exchange. The anion-exchange experiments were
performed with complexes 1−4 (5 mg) by immersing in a 3 M
aqueous solution (2 mL) of each corresponding sodium salt and
leaving undisturbed at ambient temperature. Each solid sample was
periodically collected by filtration, washed several times with distilled
−1
metric analyzer. Samples were heated at a constant rate of 5 °C min
from room temperature to 900 °C in a continuous-flow nitrogen
atmosphere. The powder X-ray diffraction (PXRD) experiments were
J
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Inorganic Chemistry
Article
water, and then dried in air. The crystalline samples collected from the
anion-exchange experiments were unacceptable for single-crystal X-ray
diffraction analysis. Thus, the structural conversion associated with
anion exchange was monitored by the PXRD patterns and their IR
spectra.
(3) (a) Choi, H.-S.; Suh, M. P. Angew. Chem., Int. Ed. 2009, 48, 6865.
(b) Janzen, D. E.; Botros, M. E.; VanDerveer, D. G.; Grant, G. J.
Dalton Trans. 2007, 5316. (c) Lee, S. J.; Hupp, J. T. Coord. Chem. Rev.
2006, 250, 1710.
(4) (a) Muthu, S.; Yip, J. H. K.; Vittal, J. J. J. Chem. Soc., Dalton Trans.
2002, 4561. (b) Custelcean, R.; Moyer, B. A. Eur. J. Inorg. Chem. 2007,
1321. (c) Zhao, W.; Fan, J.; Okamura, T.; Sun, W.-Y.; Ueyama, N. New
J. Chem. 2004, 28, 1142. (d) Du, M.; Guo, Y.-M.; Chen, S.-T.; Bu, X.-
H. Inorg. Chem. 2004, 43, 1287. (e) Sarkar, M.; Biradha, K. Cryst.
Growth Des. 2007, 7, 1318. (f) Tzeng, B.-C.; Chiu, T.-H.; Chen, B.-S.;
Lee, G.-H. Chem.Eur. J. 2008, 14, 5237. (g) Liu, J.-Y.; Wang, Q.;
Zhang, L.-J.; Yuan, B.; Xu, Y.-Y.; Zhang, X.; Zhao, C.-Y.; Wang, D.;
Yuan, Y.; Wang, Y.; Ding, B.; Zhao, X.-J.; Yue, M. M. Inorg. Chem.
X-ray Crystallographic Analysis. All data were collected on a
Bruker SMART APEX II ULTRA diffractometer equipped with
graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) generated
by a rotating anode. The cell parameters for the compounds were
obtained from a least-squares refinement of the spot (from 36
collected frames). Data collection, data reduction, and semiempirical
absorption correction were carried out using the software package of
27
APEX2. All of the calculations for the structure determination were
2
8
carried out using the SHELXTL package. In all cases, all
nonhydrogen atoms were refined anisotropically and all hydrogen
atoms were placed in idealized positions and refined isotropically in a
riding manner along with the their respective parent atoms. Relevant
crystal data collection and refinement data for the crystal structures of
2
014, 53, 5972. (h) Hashemi, L.; Morsali, A.; Bϋyϋkgϋngor, O. New J.
Chem. 2014, 38, 3187. (i) Halper, S. R.; Do, L.; Stork, J. R.; Cohen, S.
M. J. Am. Chem. Soc. 2006, 128, 15255.
(
5) (a) Park, S.; Lee, S. Y.; Park, K.-M.; Lee, S. S. Acc. Chem. Res.
012, 45, 391. (b) Lee, E.; Lee, S. Y.; Lindoy, L. F.; Lee, S. S. Coord.
Chem. Rev. 2013, 257, 3125.
6) (a) Wolf, R. E., Jr.; Hartman, J. R.; Storey, J. M. E.; Foxman, B.
M.; Cooper, S. R. J. Am. Chem. Soc. 1987, 109, 4328. (b) Blake, A. G.;
Schroder, M. Adv. Inorg. Chem. 1990, 35, 1. (c) Hill, S. E.; Feller, D. J.
Phys. Chem. A 2000, 104, 652.
7) (a) Lee, S. Y.; Lee, S. S. Inorg. Chem. 2010, 12, 3471. (b) Kim, H.
2
1
−4 are summarized in Table 1. In 3, O3 and O5 atoms are disordered
into two positions (64:36 and 50:50, respectively). In 4, the
noncoordinated CF SO3 is disordered about the special position,
(
−
3
and its F5 atom is disordered over two positions (50:50). The “ISOR”
command has been used in the refinement of 4 (O6).
̈
(
ASSOCIATED CONTENT
Supporting Information
NMR spectra, additional crystal structures, PXRD patterns, IR
■
J.; Lindoy, L. F.; Lee, S. S. Cryst. Growth Des. 2010, 10, 3850. (c) Kim,
H. J.; Park, I.-H.; Lee, J.-E.; Park, K.-M.; Lee, S. S. Cryst. Growth Des.
*
S
2
(
014, 14, 6269.
8) (a) Kim, H. J.; Lee, S. S. Inorg. Chem. 2008, 47, 10807. (b) Kim,
H. J.; Sultana, K. F.; Lee, J. Y.; Lee, S. S. CrystEngComm 2010, 12,
spectra, and X-ray crystallographic files (CIFs). CCDC-
1047895 (L), -1047896 (1), -1047897 (2), -1047898 (3),
1
494. (c) Lee, H.-H.; Park, I.-H.; Lee, S. S. Inorg. Chem. 2014, 53,
and -1047899 (4) contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Center via www.
ccdc.cam.ac.uk/data_request/cif. The Supporting Information
is available free of charge on the ACS Publications website at
DOI: 10.1021/acs.inorgchem.5b00422.
4
763.
(9) (a) Yoon, I.; Seo, J.; Lee, J.-E.; Park, K.-M.; Kim, J. S.; Lah, M. S.;
Lee, S. S. Inorg. Chem. 2006, 45, 3487. (b) Jin, Y.; Kim, H. J.; Lee, J. Y.;
Lee, S. Y.; Shim, W. J.; Hong, S. H.; Lee, S. S. Inorg. Chem. 2010, 49,
10241. (c) Lee, E.; Lee, S. S. Inorg. Chem. 2011, 50, 5803. (d) Kim, J.-
Y.; Park, I.-H.; Lee, J. Y.; Lee, J.-H.; Park, K.-M.; Lee, S. S. Inorg. Chem.
2
013, 52, 10176. (e) Ryu, H.; Park, K.-M.; Ikeda, M.; Habata, Y.; Lee,
S. S. Inorg. Chem. 2014, 53, 4029.
AUTHOR INFORMATION
Corresponding Authors
E-mail: habata@chem.sci.toho-u.ac.jp.
E-mail: sslee@gnu.ac.kr.
■
(
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10) Lee, E.; Lee, S. S. CrystEngComm 2013, 15, 1814.
11) (a) Lee, S. J.; Jung, J. H.; Seo, J.; Yoon, I.; Park, K.-M.; Lindoy,
*
L. F.; Lee, S. S. Org. Lett. 2006, 8, 1641. (b) Lee, H.; Lee, S. S. Org.
Lett. 2009, 11, 1393.
*
(
12) Lee, S. J.; Lee, J.-E.; Seo, J.; Lee, S. S.; Jung, J. H. Adv. Funct.
Mater. 2007, 17, 3441.
13) (a) Kang, E.-J.; Lee, S. Y.; Lee, H.; Lee, S. S. Inorg. Chem. 2010,
9, 7510. (b) Seo, J.; Song, M. R.; Lee, J.-E.; Lee, S. Y.; Yoon, I.; Park,
K.-M.; Kim, J.; Jung, J. H.; Park, S. B.; Lee, S. S. Inorg. Chem. 2006, 45,
952. (c) Kumar, S.; Hundal, M. S.; Hundal, G.; Singh, P.; Bhalla, V.;
Singh, H. J. Chem. Soc., Perkin Trans. 2 1998, 925.
Notes
The authors declare no competing financial interest.
(
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ACKNOWLEDGMENTS
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This work was supported from NRF (2012R1A4A1027750 and
013R1A2A2A01067771), S. Korea, and the Supported
(14) (a) Lee, S. Y.; Park, S.; Kim, H. J.; Jung, J. H.; Lee, S. S. Inorg.
Program for Strategic Research Foundation at Private
Universities (2012−2016) from the Ministry of Education,
Culture, Sports, Science and Technology of Japan. E.L.
acknowledges the support by NRF-2013-Fostering Core
Leaders of the Future Basic Science Program.
Chem. 2008, 47, 1913. (b) Lee, S. Y.; Seo, J.; Yoon, I.; Kim, C.-S.;
Choi, K. S.; Kim, J. S.; Lee, S. S. Eur. J. Inorg. Chem. 2006, 3525.
(
15) (a) de Groot, B.; Loeb, S. J.; Shimizu, G. K. H. Inorg. Chem.
994, 33, 2663. (b) Constable, E. C.; King, A. C.; Raithby, P. R.
Polyhedron 1998, 17, 4275.
16) Addison, A. W.; Rao, T. N.; Reedijk, J.; Van Rijin, J.; Verschoor,
1
(
REFERENCES
■
G. C. J. Chem. Soc., Dalton Trans. 1984, 1349.
(
1
1) (a) Batten, S. R.; Robson, R. Angew. Chem., Int. Ed. 1998, 37,
460. (b) Eddaoudi, M.; Moler, D. B.; Li, H.; Chen, B.; Reineke, T.
(17) (a) MOGUL; Cambridge Crystallographic Database: Cam-
bridge, U.K., 2006. (b) Lee, S. Y.; Park, S.; Seo, J.; Lee, S. S. Inorg.
Chem. Commun. 2007, 10, 1102.
(18) Jung, O.-S.; Kim, Y. J.; Lee, Y.-A.; Park, K.-M.; Lee, S. S. Inorg.
Chem. 2003, 42, 844.
M.; O’Keeffe, M.; Yaghi, O. M. Acc. Chem. Res. 2001, 34, 319.
(c) Kitagawa, S.; Matsuda, R. Coord. Chem. Rev. 2007, 251, 2490.
(d) Kawano, M.; Fujita, M. Coord. Chem. Rev. 2007, 251, 2592.
(e) Northrop, B. H.; Zheng, Y.-R.; Chi, K.-W.; Stang, P. J. Acc. Chem.
(19) (a) Brammer, L.; Burgard, M. D.; Rodger, C. S.; Swearingen, J.
K.; Rath, N. R. Chem. Commun. 2001, 2468. (b) Lu, X. L.; Leong, W.
K.; Goh, L. Y.; Hor, A. T. S. Eur. J. Inorg. Chem. 2004, 2504.
(20) Dance, I.; Scudder, M. J. Chem. Soc., Chem. Commun. 1995,
1039−1040.
̆
Res. 2009, 42, 1554. (f) Murray, L. J.; Dinca, M.; Long, J. R. Chem. Soc.
Rev. 2009, 38, 1294. (g) Lindoy, L. F.; Park, K.-M.; Lee, S. S. Chem.
Soc. Rev. 2013, 42, 1713.
(
2) (a) Izatt, R. M.; Pawlak, K.; Bradshaw, J. S. Chem. Rev. 1991, 91,
721. (b) Lindoy, L. F. Coord. Chem. Rev. 1998, 174, 327. (c) Izatt, R.
M.; Pawlak, K.; Bradshaw, J. S. Chem. Rev. 1995, 95, 2529.
1
(21) (a) Kim, H. J.; Song, M. R.; Lee, S. Y.; Lee, J. Y.; Lee, S. S. Eur. J.
Inorg. Chem. 2008, 3532. (b) Park, S.; Lee, S.-G.; Jung, J. H.; Ikeda, M.;
K
DOI: 10.1021/acs.inorgchem.5b00422
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
Habata, Y.; Lee, S. S. CrystEngComm 2012, 14, 6515. (c) Liang, G.;
Liu, Y.; Zhang, X.; Yi, Z. CrystEngComm 2014, 16, 9896. (d) Feng, Y.;
Wang, D.-B.; Wan, B.; Li, X.-H.; Shi, Q. Inorg. Chim. Acta 2014, 413,
1
(
2
87.
̈
22) (a) Haj, M. A.; Aakeroy, C. B.; Desper, J. New J. Chem. 2013, 37,
04. (b) Pogozhev, D.; Baudron, S. A.; Hosseini, M. W. Dalton Trans.
2
011, 40, 437. (c) Pocic, D.; Planeix, J.-M.; Kyritsakas, N.; Jouaiti, A.;
Hosseini, M. W. CrystEngComm 2005, 7, 624. (d) Khlobystov, A. N.;
Blake, A. J.; Champness, N. R.; Lemenovskii, D. A.; Majouga, A. G.;
Zyk, N. V.; Schro
̈
der, M. Coord. Chem. Rev. 2001, 222, 155.
(
23) (a) Archer, R. D.; Dardiman, C. J.; Lee, A. Y. In Photochemistry
and Photophysics of Coordination Compounds; Yersin, H., Vogler, A.,
Eds.; Spriger-Verlag: Berlin, 1987; p 285. (b) Valeur, B. Molecular
Fluorescence: Principles and Applications; Wiley-VCH: Weinheim,
Germany, 2002.
(
24) Hofmeister, F. Arch. Exp. Pathol. Pharmakol. 1888, 24, 247.
(
25) (a) Min, K. S.; Suh, M. P. J. Am. Chem. Soc. 2000, 122, 6834.
(
b) Jung, O.-S.; Kim, Y. J.; Lee, Y.-A.; Chae, H. K.; Jang, H. G.; Hong,
J. Inorg. Chem. 2001, 40, 2105. (c) Noro, S.-i.; Kitaura, R.; Kondo, M.;
Kitagawa, S.; Ishii, T.; Matsuzaka, H.; Yamashita, M. J. Am. Chem. Soc.
2
2
002, 124, 2568. (d) Wu, J.-Y.; Liu, Y.-C.; Chao, T.-C. Inorg. Chem.
014, 53, 5581.
(
26) (a) Wei, W.; Yu, H.; Jiang, F.; Liu, B.; Ma, J.; Hong, M.
CrystEngComm 2012, 14, 1693. (b) Yang, H.; Li, L.; Wu, J.; Hou, H.;
Xiao, B.; Fan, Y. Chem.Eur. J. 2009, 15, 4049. (c) Khlobystov, A. N.;
Champness, N. R.; Roberts, C. J.; Tendler, S. J.B.; Thompson, C.;
Schro
Champness, N. R.; Khlobystov, A. N.; Roberts, C. J.; Schro
Tendler, S. J. B.; Wilkinson, M. J. J. Microsc. 2004, 214, 261.
̈
der, M. CrystEngComm 2002, 4, 426. (d) Thompson, C.;
̈
der, M.;
(
(
e) Rodriguez-hornedo, N.; Murphy, D. J. Pharm. Sci. 1999, 88, 651.
f) Booth, J.; Compton, R. G.; Atherton, J. H. J. Phys. Chem. B 1998,
1
02, 3980. (g) Booth, J.; Hong, Q.; Compton, R. G.; Prout, K.; Payne,
R. M. J. Colloid Interface Sci. 1997, 192, 207. (h) Pina, C. M.;
Fernandez-Diaz, L.; Prieto, M.; Putnis, A. Geochim. Cosmochim. Acta
2
000, 64, 215. (i) Malkin, A. J.; Kuznetsov, Yu. G.; McPherson, A. J.
Cryst. Growth 1999, 196, 471.
27) APEX 2 Bruker, SAINT (ver. 6.22): Area Detector Control and
Integration Software; Bruker AXS Inc.: Madison, WI, 2000.
28) SHELXTL (ver. 6.10): Program for Solution and Refinement of
Crystal Structures; Bruker AXS Inc.: Madison, WI, 2000.
(
(
L
DOI: 10.1021/acs.inorgchem.5b00422
Inorg. Chem. XXXX, XXX, XXX−XXX