Ligand Isomer Effect on the Formations of Supramolecular Lead(II), Mercury(II), and Copper(II)/Mercury(II) Complexes of Bis-O2S2-Macrocycle

Article abstract of DOI:10.1021/acs.cgd.8b00052

In addition to ortho-isomer (o-bis-L) and meta-isomer (m-bis-L) of bis-O₂S₂-macrocycle obtained previously, its para-isomer (p-bis-L) was newly isolated, and the complete isomer series were structurally characterized by single crystal X-ray analysis. In complexations, borderline (Pb²⁺) and soft (Hg²⁺ and Cu⁺) metal salts were employed to investigate the isomer effect on the coordination modes and topologies of the supramolecular complexes. Lead(II) perchlorate afforded an infinite one-dimensional (1-D) coordination polymer {[Pb₂(o-bis-L)(μ-ClO₄)₂(ClO₄)₂]}_n (1) and a discrete complex [Pb₂(m-bis-L)(CH₃CN)₂(H₂O)₂(ClO₄)₂](ClO₄)₂ (2), both of which are based on the endocyclic binuclear complexes mainly due to the oxophilicity of the lead(II) ion. Meanwhile, mercury(II) halides showed an endocyclic dinuclear complex [Hg₂(o-bis-L)I₂][Hg₃I₈] (3) and an exocyclic 1-D coordination polymer [Hg₃(m-bis-L)Br₆]_n (4) because the differences of sulfur-to-sulfur separation in the free ligand isomers might induce the different coordination modes. When a mixture of mercury(II) iodide and copper(I) iodide was used in the reaction with m-bis-L, a heterometallic 1-D coordination polymer [Cu₂Hg₂(m-bis-L)(μ-Cu₂I₂)(CH₃CN)₂I₆]_n (5) was obtained. In 5, exocyclic dicopper(I) complex units are linked by -Hg-Cu₂I₄-Hg- segments to form an infinite zigzag chain. Consequently, unlike the borderline metal, the soft metal ions show the sulfur-to-sulfur separation dependent coordination modes. These results demonstrate how small differences in the ligand isomers impact their self-assembled coordination products in terms of coordination mode and topological structure including dimensionality.

Full text of DOI:10.1021/acs.cgd.8b00052

Subscriber access provided by - Access paid by the | UCSB Libraries
Article
Ligand Isomer Effect on the Formations of Supramolecular Lead(II),
2
2
Mercury(II), and Copper(II)/Mercury(II) Complexes of Bis-OS-Macrocycle
Seulgi Kim, Arlette Deukam Siewe, Eunji Lee, Huiyeong Ju, In-
Hyeok Park, Jong Hwa Jung, Yoichi Habata, and Shim Sung Lee
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b00052 • Publication Date (Web): 27 Feb 2018
Downloaded from http://pubs.acs.org on March 4, 2018
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a service to the research community to expedite the dissemination
of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in
full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully
peer reviewed, but should not be considered the official version of record. They are citable by the
Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,
the “Just Accepted” Web site may not include all articles that will be published in the journal. After
a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web
site and published as an ASAP article. Note that technical editing may introduce minor changes
to the manuscript text and/or graphics which could affect content, and all legal disclaimers and
ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or
consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Crystal Growth & Design is published by the American Chemical Society. 1155
Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 9
Crystal Growth & Design
1
2
3
4
5
6
7
8
9
Ligand Isomer Effect on the Formations of Supramolecular
Lead(II), Mercury(II), and Copper(II)/Mercury(II) Complexes of
Bis-O2S2-Macrocycle
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Seulgi Kim,† Arlette Deukam Siewe,† Eunji Lee,† Huiyeong Ju,† InꢀHyeok Park,† Jong Hwa Jung,†
Yoichi Habata,*,‡ and Shim Sung Lee*,†
†Department of Chemistry and Research Institute of Natural Science, Gyeongsang National University, Jinju 52828, S. Korea
‡Department of Chemistry and Research Center for Materials with Integrated Properties, Toho University, 2ꢀ2ꢀ1 Miyama,
Funabashi, Chiba 274ꢀ8510, Japan
ABSTRACT: In addition to orthoꢀisomer (o-bis-L) and metaꢀisomer (mꢀbisꢀL) of bisꢀO2S2ꢀmacrocycle obtained previously, its
paraꢀisomer (pꢀbisꢀL) was newly isolated and the complete isomer series were structurally characterized by single crystal Xꢀray
analysis. In complexations, borderline (Pb2+) and soft (Hg2+ and Cu+) metal salts were employed to investigate the isomer effect on
the coordination modes and topologies of the supramolecular complexes. Lead(II) perchlorate afforded an infinite oneꢀdimensional
(1ꢀD)
coordination
polymer
{[Pb2(o-bis-L)(µꢀClO4)2(ClO4)2]}n
(1)
and
a
discrete
complex
[Pb2(mꢀbisꢀ
L)(CH3CN)2(H2O)2(ClO4)2](ClO4)2 (2), both of which are based on the endocyclic binuclear complexes mainly due to the oxophiꢀ
licity of lead(II) ion. Meanwhile, mercury(II) halides showed an endocyclic dinuclear complex [Hg2(o-bis-L)I2][Hg3I8] (3) and an
exocyclic 1ꢀD coordination polymer [Hg3(m-bis-L)Br6]n (4) because the differences of sulfurꢀtoꢀsulfur separation in the free ligand
isomers might induce the different coordination modes. When a mixture of mercury(II) iodide and copper(I) iodide was used in the
reaction with m-bis-L, a heterometallic 1ꢀD coordination polymer [Cu2Hg2(m-bis-L)(ꢀꢀCu2I2)(CH3CN)2I6]n (5) was obtained. In 5,
exocyclic dicopper(I) complex units are linked by ꢀHgꢀCu2I4ꢀHgꢀ segments to form an infinite zigzag chain. Consequently, unlike
the borderline metal, the soft metal ions show the sulfurꢀtoꢀsulfur separation dependent coordination modes. These results demonꢀ
strate how small differences in the ligand isomers impact their selfꢀassembled coordination products in terms of coordination mode
and topological structure including dimensionality.
tetra(bromomethyl)benzene and corresponding dithiols.6 In
our recent work, the bisꢀcyclization reaction of 1,2,4,5ꢀ
tetra(bromomethyl)benzene with 3,6ꢀdioxaꢀ1,8ꢀoctanedithiol
led to the isolation of o-bis-L and m-bis-L which form the
INTRODUCTION
Structural isomers of multidentate ligands that have same
chemical formula but different chemical structures so often
play a key role in influencing the structures of their coordinaꢀ
controlled endoꢀ and exoꢀcoordinated 1ꢀD polymeric products,
tion products.1ꢀ12 In practice, changing the substitution position
respectively.11 More recently, we employed o-bis-L (Wꢀ
in the aromatic subunit in the ligand system can provide a
shaped exoꢀbinding site) and m-bis-L (Uꢀshaped exoꢀbinding
series of regioisomers not only in linear ligands1ꢀ5 but also in
site) that induce the adaptive formations of the polynuclear
cyclic analogues6ꢀ12. We have employed the above approach to
[CunIn] clusters as well as photoluminescence properties.12
NS2ꢀmacrocycles with a xylyl subunit in orthoꢁ, metaꢀ, and
This result shows that the exocyclic interdonor binding site
alteration (S···S) can play decisive roles in the selective selfꢀ
paraꢀpositions and their exocyclic soft metal complexes.8ꢀ10 In
this case, the variation of the macrocyclic ring flexibilities
assemblies of supramolecular materials including clusters. In
couples with the exocyclic coordination arising from the presꢀ
our previous works, however, no 1,4ꢀbisꢀcyclization product
ence of sulfur donors provides a useful and productive pathꢀ
(p-bis-L) was isolated nor observed in the NMR spectrum of
way to such new complexes displaying unusual topologies.13
the crude mixture.11 Thus, the detection and isolation of p-bis-
On the other hand, a bisꢀmacrocyclic scaffold is one of the
L have been one of the challenging tasks as a final puzzle in
host systems which can occupy two metal ions to form binuꢀ
the study of these bisꢀmacrocycle isomers to us.
clear complexes of interest in diverse area, such as electron
transport, charge transfer, and allosteric behavior in biochemiꢀ
Scheme 1. Three Regioisomers of bis-O2S2-Macrocycle via
1,2-, 1,3-, and 1,4-Cyclizations.
cal
systems.14,15
Practically,
1,2,4,5ꢀ
tetra(bromomethyl)benzene (see Scheme 1) might be considꢀ
ered as an interesting platform molecule to give a series of bisꢀ
macrocycle isomers depending on cyclization modes.6,11,12
Accordingly, it might be possible to obtain three regioisomers
(orthoꢁ, metaꢁ, and paraꢁfrom) via 1,2ꢀ, 1,3ꢀ, and 1,4ꢀ
cyclizations with linear diols or dithiols.11,12
Loeb et al reported metaꢀisomers of bisꢀthiaꢀ and bisꢀ
oxathia
macrocycles
derived
from
1,2,4,5ꢀ
ACS Paragon Plus Environment

Crystal Growth & Design
The continuing interest on the isomer effect of bisꢀ
Page 2 of 9
1
2
3
4
5
6
7
8
macrocycles and no research for p-bis-L have motivated us to
extend our synthetic works to the unexplored isomer as well as
their binuclear complexes with different topologies. Herein,
we report an extension of these studies that form diverse types
of complexes, with emphasis on the discriminated complexaꢀ
tion behaviors of the bisꢀmacrocycle isomers. Considering the
binding affinity to the metal ions with respect to their O2S2ꢀ
donors, we have employed lead(II), mercury(II), and copper(I)
salts as borderline and soft metal ions in present work. The
isolation of p-bis-L which came in the modified reaction conꢀ
dition and the solid structures of the complete isomers are also
reported.
(a)
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
RESULTS AND DISCUSSION
Synthesis and Separation of p-bis-L. In our previous work,11
the reaction in Scheme 1 gave a mixture of o-bis-L and m-bis-
L in a 1:4 ratio. When the reactant concentration was reduced
to 25% (0.55 mM), the coexistence of the three isomers (o-bis-
L, m-bis-L, and p-bis-L) was detected in a 1:1:4 ratio (Figure
S1), indicating the high dependency of the formation of p-bis-
L and the distribution of the isomers on the reactant concentraꢀ
tion. The pure p-bis-L was obtained by the twoꢀstep separation
process including the solubilityꢀdependent fractionation and
the column chromatography (yield 13%, see the details in the
Experimental Section). However, the overall yield for the
(b)
1
three isomers was decreased in this condition. The H NMR
spectra of p-bis-L exhibit the complicate coupling patterns due
to its intrinsic rigid conformation of the ring cavity via the 1,4ꢀ
cyclization (Figures S2 and S3). However, the 13C NMR specꢀ
trum shows a simple pattern (Figure S4).
(c)
Figure 1. Crystal structures of (a) o-bis-L, (b) m-bis-L, and (c)
p-bis-L. Torsion angles (deg) for o-bis-L: O1ꢀCꢀCꢀO2
55.77(9), O1ꢀCꢀCꢀS1 66.11(7), and O2ꢀCꢀCꢀS2 56.79(7)], for
m-bis-L: O1ꢀCꢀCꢀO2 69.93(19), O1ꢀCꢀCꢀS1 71.13(2), O2ꢀCꢀ
CꢀS2 69.85(18), for p-bis-L: O1ꢀCꢀCꢀO2 85.33(18), O1ꢀCꢀCꢀ
S1 169.83(1), O2ꢀCꢀCꢀS2 179.72(11), O3ꢀCꢀCꢀO4 83.71(6),
O3ꢀCꢀCꢀS3 173.38(9), and O4ꢀCꢀCꢀS4 174.53(8).
Crystal Structures of the Regio-isomers. Although the
crystal structures of some complexes of o-bis-L and m-bis-L
have been introduced,11,12 those of the free ligands have not
been reported. So, determinations of the crystal structures of
the complete isomers including newly isolated p-bis-L were
carried out in this work (Figure 1). Colorless crystals of o-bis-
L, m-bis-L, and p-bis-L were obtained by slow evaporation
from the solutions of dichloromethane. It is of interest to comꢀ
pare the structures of the three isomers which show the differꢀ
ent symmetries and conformations.
Asymmetric unit of o-bis-L and m-bis-L contains a half
molecule of the ligand due to an imposed inversion and a C2
axis, respectively. Meanwhile, the absence of symmetry in p-
bis-L is noted. In o-bis-L and m-bis-L, the oxygen donors are
orientated in an endodentate fashion but the sulfur donors are
orientated in an exodentate manner. Torsion angles of both Oꢀ
CꢀCꢀO and OꢀCꢀCꢀS segments are associated with a gauche
arrangement. Unlike o-bis-L and m-bis-L, the OꢀCꢀCꢀS segꢀ
ments in p-bis-L span an anti arrangement with characteristic
torsion angles. Notably, the adjacent sulfurꢀtoꢀsulfur distances
between two ring cavities are very different: 5.90 Å (S2···S2A)
in o-bis-L, 5.37 Å (S1···S1A) and 4.84 Å (S2···S2A) in m-
bis-L, and 4.03 Å (S2···S4) and 4.35 Å (S1···S3) in p-bis-L.
Lead(II) Complexes (1 and 2). As a borderline metal catiꢀ
on, lead(II) perchlorate was used for the complexation of oꢀ
bisꢀL and mꢀbisꢀL. In these reactions, a dichloromethane soluꢀ
tion of each macrocycle isomer was allowed to diffuse into
acetonitrile solution of two equivalents of Pb(ClO4)2·3H2O.
Slow evaporation of each solution afforded colorless crystalꢀ
line products 1 for oꢀbisꢀL and 2 for mꢀbisꢀL that proved suitꢀ
able for crystallography. In the crystal structures, it was found
that the orthoꢁ and metaꢀsubstitution induce the different coorꢀ
dination behaviors and topologies of the products as depicted
in Scheme 2. The preparation of the corresponding lead(II)
perchlorate complex with p-bis-L was not possible.
Scheme 2. Lead(II) Complexes of the Regioisomers.
O
O
O
S
ClO4
Pb
S
O
S
o-bis-L
Pb
S
S
Pb
S
O
Pb
O4Cl
S
S
O
O
O
Pb(ClO4)2.6H2O
1
2
S
S
Solvent
O4Cl
ClO4
O
m-bis-L
O
Pb
Pb
O
O
Solvent
S
S
ACS Paragon Plus Environment

Page 3 of 9
Crystal Growth & Design
The Xꢀray analysis revealed that 1 crystallizes in the monoꢀ
mꢀbisꢀL adopting an overall Sꢀshape conformation. The reꢀ
maining sites are occupied by one bidentate perchlorate ion,
one water, and one acetonitrile to yield an overall metal coorꢀ
dination of eight. The bond lengths of PbꢀO [2.685(2) and
2.705(2) Å] and PbꢀS [3.005(7) and 3.059(7) Å] in 2 are longꢀ
er than those in 1 probably due to the larger cavity size and
more rigid structure of m-bis-L.
1
2
3
4
5
6
7
8
clinic space group P21/n and features a one dimensional (1ꢀD)
coordination polymer with the formula {[Pb2(o-bis-L)(µꢀ
ClO4)2(ClO4)2]}n (Figure 2 and Table S2). In 1, each o-bis-L
ligand forms a dilead(II) complex and these dinuclear complex
units are further doubly linked by two bridging perchlorate
ions, adopting the 1ꢀD polymeric array. Since there is an imꢀ
posed inversion at the center of the aromatic ring, the asymꢀ
metric unit of 1 contains a half molecule of oꢀbisꢀL, one
lead(II) ion, and two perchlorate ions which are monodentate
and bidentate. Each lead(II) ion in 1 is sevenꢀcoordinate being
bound to O2S2ꢀdonors from one macrocyclic cavity adopting a
dinuclear complex unit. The coordination environment is
completed by two bridging perchlorate ions and one terminal
perchlorate ion to yield the anionꢀlinked 1ꢀD coordination
polymer via Pbꢀ(µꢀClO4)2ꢀPb linkage. The PbꢀO bond lengths
[Pb1ꢀO1 2.572(5), Pb1ꢀO2 2.596(5) Å] in 1 are typical. While,
the PbꢀS bonds [Pb1ꢀS1 2.925(2), Pb1ꢀS2 2.962(2) Å] can be
considered as weak bonds due to the intermediate behavior of
the lead(II) ion between soft and hard acids. The Pb1···Pb1B
distance linked by the anions is 4.94 Å which is shorter than
that in the same ligand (Pb1···Pb1A 10.75 Å). This is a rare
example of a 1ꢀD coordination polymer in which dinuclear
macrocyclic complex units are linked by anions.16,17 It is also
noteworthy that on complexation a large conformational
change of the ligand from twist (S1···S2 5.07 Å in oꢀbisꢀL,
Figure 1a) to the stairway (S1···S2 4.05 Å in 1, Figure 2a) was
observed mainly due to the flexible nature of the orthoꢀform.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Figure 3. Lead(II) perchlorate complex of m-bis-L, [Pb2(m-
bis-L)(CH3CN)2(H2O)2(ClO4)2](ClO4)2 (2) showing a discrete
dinuclear structure. Nonꢀcoordinating anions are omitted.
The structural comparison of 1 and 2 reveals that two comꢀ
plexes show the similarity as well as the difference. Above all
both complexes are based on the endocyclic dinuclear comꢀ
plex unit. In silver(I) complexation,11 o-bis-L forms an endoꢀ
cyclic complex, while m-bis-L allowed to prepare an exocyꢀ
clic complex, due to the difference of the S···S distances.18,19
However, the same is not true for the lead(II) complexes 1 and
2. To explain this result, the borderline acidity of lead(II)
should be into account.20 In the divalent metal complexes of
1,10ꢀdithiaꢀ18ꢀcrownꢀ6 (L), for example, PbX2 (X = ClO4,
NO3) afforded endocyclic complexes [Pb(L)(ClO4)2] and
[Pb(L)(NO3)2], respectively.21 In both cases, the lead(II) ion
coordinates to four oxygen donors and two anions, while the
distances of Pb···S (3.09ꢀ3.13 Å) can be considered as weak
interactions. Similarly, the lead(II) complexations in this work
are also considered to be driven by the PbꢀO bond formation
rather than that of the PbꢀS. Consequently, the endoꢀ
coordination is enthalpically more favorable for both isomers.
Notably, the conformations of two isomers in 1 and 2 are
different. In 1, for example, o-bis-L ligand is less folded
adopting an elongated stairꢀshape. Thus, the resulting 1ꢀD
network 1 appears to be aided by the flexible and elongated oꢀ
bisꢀL units which seem to be more favorable for the intermoꢀ
lecular interaction on complexation. While, m-bis-L ligand in
2 is more folded giving a Sꢀshape configuration which is less
favorable for the intermolecular interaction. Consequently, the
1ꢀD infinite form in 1 and the discrete form in 2 are mainly
associated with the different ring rigidity of the isomers.
Mercury(II) Complexes (3 and 4). In the reactions of three
equivalents of mercury(II) halides with o-bis-L and m-bis-L,
colorless crystalline complexes 3 (iodide) and 4 (bromide)
were obtained, respectively. The yields in crystalline materials
were ca. 60ꢀ70%. Singleꢀcrystal Xꢀray diffraction analysis
revealed that two mercury(II) products feature different stoiꢀ
chiometry and topologies depending on their endoꢀ and exocyꢀ
clic coordination modes associated with the isomerism
(Scheme 3).
(a)
(b)
Figure 2. Lead(II) perchlorate complex of o-bis-L, {[Pb2(o-
bis-L)(µꢀClO4)2(ClO4)2]}n (1) showing a 1ꢀD polymeric strucꢀ
ture. (a) core dinuclear coordination unit and (b) 1ꢀD chain
linked with the anions.
The Xꢀray analysis revealed that 2 crystallizes in the monoꢀ
clinic space group C2/c. In marked contrast to the infinite
form in 1, compound 2 is a discreteꢀtype 2:1 (metalꢀtoꢀligand)
complex
of
the
formula
[Pb2(mꢀbisꢀ
L)(CH3CN)2(H2O)2(ClO4)2](ClO4)2 that involves both coordiꢀ
nating anions and solvent molecules (Figure 3 and Table S3).
Since there is an imposed inversion at the center of the aroꢀ
matic ring, the asymmetric unit of the complex part in 2 conꢀ
tains a half molecule of mꢀbisꢀL, one lead(II) ion, one perchloꢀ
rate ion, one acetonitrile, and one water molecule. The lead(II)
ion in 2 is bonded to O2S2 donors of one macrocyclic cavity in
Scheme 3. Mercury(II) Complexes of the Regioisomers.
ACS Paragon Plus Environment

Crystal Growth & Design
Page 4 of 9
I
S
O
S
S
O
Hg
o-bis-L
Hg
1
2
3
4
5
6
7
8
O
O
S
[Hg3I8]2-
(X = I)
I
Endocyclic dinuclear complex (3)
Br
Hg
Br
Br
Hg
S
Hg
Br
HgX2
Br
Br
S
S
S
S
S
O
O
O
O
Br
Br
O
Hg
Hg
m-bis-L
O
O
Br
O
Br
O
O
(X = Br)
S
O
Br
O
Br
S
S
S
S
Br
S
Hg
Br
Hg
Hg
Br
9
Br
4
Exocyclic 1-D coordination polymer (
)
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
The Xꢀray analysis revealed that 3 crystallizes in the triclinꢀ
ic space group Pꢀ1 and features two separated parts with the
formula [Hg2(o-bis-L)I2][Hg3I8]: one part is a dinuclear macꢀ
rocyclic complex cation and another part is an octaiodotrimerꢀ
curate(II) cluster [Hg3I8]2− anion (Figure 4 and Table S4). In
the complex cation unit, each endocyclic mercury(II) atom is
fiveꢀcoordinate, being bound to O2S2 donors from one macroꢀ
cyclic unit of o-bis-L in a stairꢀlike arrangement. The fifth
coordination site is completed by one iodide ion with the merꢀ
cury(II) positioned 1.26 Å from the O2S2 plane toward the
coordinating anion, adopting a perching conformation. The
observed dislocation of the metal ion from the cavity center is
mainly due to a smaller cavity size (14ꢀmemberd ring) for the
mercury(II) ion. In the octaiodotrimercurate(II) anion cluster,
three consecutive mercury(II) ions linked by iodo ligands genꢀ
erate a ribbonꢀtype arrangement.22 In this, the coordination
geometry of the central mercury(II) ion (Hg3) is square planar
while two terminal mercury(II) ions (Hg2 and Hg2A) are tetꢀ
rahedrally coordinated.
Figure 5. Mercury(II) bromide complex of m-bis-L showing a
1ꢀD polymeric structure, [Hg3(m-bis-L)Br6]n (4).
Compared with the lead(II) complexes 1 and 2, the isomerꢀ
dependent mercury(II) complexes 3 and 4 are considered to
show more crystal engineering aspect. In practice, we have
established several strategies to control the endoꢀ and the exoꢀ
coordination modes of the macrocycles via ligand design17,24,25
and anions26ꢀ30. We have reported the regioisomersꢀdependent
endoꢀ and exocyclic coordination in which the expected difꢀ
ferences of sulfurꢀtoꢀsulfur separation might induce the differꢀ
ent coordination modes.11,12 In the present work, it is possible
to confirm this hypothesis more directly because we have
crystal structures of the free ligand isomers as well as their
complexes.
For o-bis-L, as can be seen in Figure 6, the sulfurꢀtoꢀsulfur
separation in one macrocycle ring (S1···S2 5.07 Å) is shorter
than that between two macrocyclic rings (S1···S2A 5.90 Å).
For m-bis-L, however, the sulfurꢀtoꢀsulfur separation in the
macrocycle ring (S1···S2 6.96 Å) is much longer than those
between two macrocyclic rings (S1···S1A 4.84 and S2···S2A
5.37 Å). In the preorganized host system, the observed shorter
endocyclic (o-bis-L) and exocyclic (m-bis-L) sulfurꢀtoꢀsulfur
distances are entropically favorable to induce the formations
of endoꢀ and exoꢀcoordination products, respectively. On
complexations with mercury(II) halides, as shown in Figure 6,
some conformational changes including the sulfurꢀtoꢀsulfur
separation were observed in both isomers but these are less
significant. Consequently, the preferred endocyclic coordinaꢀ
tion in 3 and the exocyclic coordination based polymeric
structure in 4 is a good example of the crystal engineering via
the softꢀsoft acidꢀbase interaction in which the coordination
modes might be controlled by the interdonor distances of the
regioisomers.
Figure 4. Mercury(II) iodide complex, [Hg2(o-bis-L)I2][Hg3I8]
(3), showing two separated units.
In the reaction of mercury(II) iodide with m-bis-L, an exoꢀ
cyclic 1ꢀD coordination polymer of the formula [Hg3(m-bis-
L)Br6]n (4) was obtained (Figure 5 and Table S5). The comꢀ
plex 4 crystallizes in the orthorhombic space group Pnnm with
Z = 2 where the asymmetric unit contains a quarter molecule
of m-bis-L, one and half mercury(II) ions, and three bromide
ions. In 4, there are two crystallographically different mercuꢀ
ry(II) atoms (Hg1 and Hg2). The intercyclic Hg1 atom which
lies between two macrocycle units in m-bis-L is bonded to
two sulfur donors from the two ring cavities and two bromo
ligands to form a dinuclear complex unit. Further, the dinucleꢀ
ar complex units are linked by [ꢀꢀHgBr4]2ꢀ via HgꢀBr bonds
[Hg2ꢀBr2 2.9952(19) Å] to form a wavy 1ꢀD polymeric strucꢀ
ture. The Hg2 atom in the anionic linker unit is also fourꢀ
coordinate, being bound to four bromo ligands adopting a
square planar geometry. In our previous work, m-bis-L reacts
with CuI to form a polymeric chain linked by Cu2I2 cluster.12
(a)
(b)
Figure 6. Comparison of sulfurꢀtoꢀsulfur distances (Å) before
and after dimercury(II) complexation for (a) o-bis-L and (b)
m-bis-L.
ACS Paragon Plus Environment

Page 5 of 9
Crystal Growth & Design
1
2
3
4
5
6
7
8
Considering the shorter S···S distances between two ring
cavities [4.03 Å (S2···S4) and 4.35 Å (S1···S3) in Figure 1c],
p-bis-L is expected to form exocyclic coordination products
rather than endocyclic ones with soft metal ions. However, our
repeated efforts to obtain such coordination products of p-bis-
L were not successful. In the electrostatic potential diagram of
p-bis-L based on the crystal structure (Figure S5), unlike those
of other isomers, the sulfur donors which locate outside the
ring cavities show a relatively poor electron density. Conseꢀ
quently, the lower reactivity of p-bis-L might be explained by
the low basicity of the soft donors together with the intrinsic
rigid conformation.
(a)
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Heteronuclear Mercury(II)/Copper(I) Complex (5). Afꢀ
ter obtaining some homonuclear complexes of the ligand isoꢀ
mers, we proceeded with the reactions to prepare heteronucleꢀ
ar complexes. When a mixture of mercury(II) iodide and copꢀ
per(I) iodide was used in a oneꢀpot reaction with m-bis-L, a
heterometallic 1ꢀD coordination polymer of the formula
[Cu2Hg2(m-bis-L)(ꢀꢀCu2I2)(CH3CN)2I6]n (5) was obtained
(Figure 7 and Table S6). The Xꢀray analysis revealed that 5
crystallizes in the hexagonal space group Rꢀ3 with Z = 18
where the asymmetric unit contains a half molecule of m-bis-
L, one mercury(II) ion, two copper(I) ions, four iodide ions,
and one acetonitrile molecule. The overall structural topology
and the connectivity pattern of 5 is similar to those of the merꢀ
cury(II) bromide complex 4. For example, two copper(I) (Cu1
and Cu1A) bind to the ligand in the exoꢀcoordination mode as
two mercury(II) bind in 4.
The major difference between 4 and 5 is a bridging part
which links the dinuclear complex units. In 5, the dicopper(I)
macrocyclic units are linked by heteronuclear IꢀHgꢀIꢀ(Cu2I2)ꢀIꢀ
HgꢀI units via CuꢀI bonds (Cu1ꢀI1 2.6438(18) Å) resulting in
the formation of a wavy 1ꢀD polymeric structure which are
also linked by Cu2I2 square via CuꢀS bond (Cu2ꢀS1 2.309(3)
Å). In 5, the intercyclic Cu2 atom is bonded to two sulfur doꢀ
nors, one acetonitrile molecule, and one bridging bromo ligand
adopting a distorted tetrahedral environment. The distance
between two intercyclic cations in 5 (Cu1···Cu1A 8.33 Å) is
shorter than that in 4 (Hg1···Hg1B 9.00 Å). The Cu1 atom in
the squareꢀtype [Cu2I2] cluster is also fourꢀcoordinate, being
bound to three iodo ligands and one sulfur atom of the macroꢀ
cycle. The Hg1 atom which links two different copper(I) ions
is threeꢀcoordinate, being bound to two bridging iodo ligands
and one terminal iodo ligand.
(b)
Figure 7. Heteronuclear Hg(II)/Cu(I) complex of m-bis-L,
[Cu2Hg2(m-bis-L)(ꢀꢀCu2I2)(CH3CN)2I6]n (5): (a) 1ꢀD polymerꢀ
ic structure and (b) packing structure showing a pseudoꢀ3D
framework with hexagonal channels along the cꢀaxis.
CONCLUSION
Since the coordination modes of the proposed bisꢀO2S2ꢀ
macrocycle isomers are expected to be dictated by the donor
arrangement in each isomer, it is challenging to isolate the
complete isomer series as well as their complexes. In addition
to orthoꢀisomer (o-bis-L) and metaꢀisomer (mꢀbisꢀL), the
paraꢀisomer (pꢀbisꢀL) was isolated and the complete isomers
were structurally characterized in the solid state. In complexaꢀ
tions with lead(II) and mercury(II) salts, the different isomers
not only alter the coordination modes but also the topologies.
A new type of the heteronuclear infinite complex of mꢀbisꢀL
was also isolated but no complexes of p-bis-L were obtained.
The present study demonstrates how small changes in the
structural isomerism impact their overall topological. In parꢀ
ticular, the exoꢀcoordination mode has been utilized as a powꢀ
erful tool to link the complex units to prepare not only the
homonuclear infinite complexes but also the heteronuclear
ones.
The exoꢀcoordination mode has been utilized as a powerful
tool to link the macrocycles or their complex units to prepare
not only the homonuclear infinite complexes but also the hetꢀ
eronuclear ones.13 For instance, our group have reported sevꢀ
eral heteronuclear type [Na(I)/Cu(I)30, K(I)/Cu(I)31,32
,
EXPERIMENTAL SECTION
K(I)/Hg(II)31,33,34, K(I)/Cd(II)31, and Ag(I)/Pd(II)35] infinite
complexes with a range of macrocyclic ligands. To the best of
our knowledge, 5 is the first characterized infinite heteronuꢀ
clear macrocyclic complex of these two metal ions. As shown
in Figure 7b, the 1ꢀD chains are arranged in a parallel manner
with the cross section of hexagonal channels to give a pseudo
3ꢀD structure. In 5, total potential solvent area volꢀ
ume obtained by PLATON36ꢀ38 is 2750.3 Å3 which is 20.2% of
the unit cell volume 13610.1 Å3.
General. All chemicals and solvents used in the syntheses
were of reagent grade and were used without further purificaꢀ
tion. NMR spectra were recorded on a Bruker 300 spectromeꢀ
ter (300 MHz). The FTꢀIR spectra were measured with a Niꢀ
colet iS10 spectrometer. The elemental analysis was carried
out on a LECO CHNSꢀ932 elemental analyzer. The elecꢀ
trospray ionization (ESI) mass spectra were obtained on a
Thermo Scientific LCQ Fleet spectrometer.
Synthesis, Separation, and Characterization of p-bis-L.
1,2,4,5ꢀtetra(bromomethyl)benzene (0.50 g, 1.11 mmol) and
3,6ꢀdioxaꢀ1,8ꢀoctanedithiol (0.51 g, 2.80 mmol) were disꢀ
solved in DMF (50 mL) and added over one day, to a suspenꢀ
ACS Paragon Plus Environment

Crystal Growth & Design
sion of Cs2CO3 (2.17 g, 6.67 mmol) in DMF (2000 mL) stirꢀ
Page 6 of 9
evaporation of the solution afforded a colorless crystalline
product 4 suitable for Xꢀray analysis. Mp: 219ꢀ220 °C. IR
(KBr pellet) 3036, 2952, 2899, 2862, 1475, 1443, 1399, 1385,
1295, 1278, 1157, 1134, 1106, 1080, 1023, 966, 857, 780 cmꢀ1;
Anal. Calcd for [C22H34Br6Hg3O4S4]: C, 16.81; H, 2.18; S, 8.16.
Found: C, 16.62; H, 2.51; S, 8.25%.
1
2
3
4
5
6
7
8
ring at 55 °C. Upon completion of addition, the DMF was
removed and the resulting yellow residue was dissolved in
CH2Cl2 (100 mL) and filtered. The CH2Cl2 solution was
washed with 0.1 M NaOH (2 × 100 mL) and deionized water
1
(100 mL) then dried over anhydrous MgSO4. The HꢀNMR
spectrum of the crude product revealed the presence of the
three isomers (o-bis-L, m-bis-L, and p-bis-L) in a 1:1:4 ratio.
However, it was not possible to separate p-bis-L from other
isomers by the column chromatography on silica gel (40%
ethyl acetate /hexane) directly due to the very similar Rf values
(especially with m-bis-L): o-bis-L (0.30), m-bis-L (0.44), and
p-bis-L (0.41). So the following twoꢀstep process was emꢀ
ployed. First, by using the lower solubility of m-bis-L than
other isomers in CH2Cl2, the solid mixture was filtrated on the
glass filter to separate the CH2Cl2ꢀsoluble and insoluble comꢀ
ponents. The soluble component proved to be a mixture of o-
bis-L and p-bis-L together with a trace amount of m-bis-L (by
means of combined TLC and NMR analysis). After m-bis-L
was removed from the mixture, then the gradient elution (from
10% ethyl acetate/hexane to 40% ethyl acetate/hexane) of the
column chromatography of this mixture on silica gel led to the
isolation of pure p-bis-L (70 mg, 13%) as a colorless solid.
For p-bis-L. Mp: 188ꢀ189 °C. 1H NMR (300 MHz, CDCl3): δ
7.12 (s, 2 H, Ar), 4.30ꢀ3.68 (dd, 8 H, ArCH2S), 3.32 (s, 8 H,
OCH2CH2O), 3.16ꢀ2.99 (m, 8 H, OCH2CH2S), 2.61ꢀ2.44 (m, 8
H, SCH2CH2O); 13C NMR (75 MHz, CDCl3) 136.2, 134.0,
70.6, 70.5, 34.1, 30.5; IR (KBr pellet): 3009, 2862, 1500, 1471,
1429, 1369, 1351, 1293, 1228, 1193, 1112, 1033, 977, 917,
907cmꢀ1; Anal. Calcd for [C22H34O4S4]: C, 53.84; H, 6.98; S,
26.13. Found: C, 54.11; H, 7.07; S, 26.17%. ESI Mass specꢀ
trum m/z: 394.08 [M+H]+.
Preparation
of
5,
[Cu2Hg2(m-bis-L)(ꢁ-
Cu2I2)(CH3CN)2I6]n. HgI2 (35.2 mg, 0.077 mmol) in methanol
(0.7 mL) and CuI (14.8 mg, 0.078 mmol) acetonitrile (0.7 mL)
was added to a solution of m-bis-L (15.0 mg, 0.031 mmol) in
chloroform (1 mL). Slow evaporation of the solution afforded
a yellow crystalline product 5 suitable for Xꢀray analysis. Mp:
226ꢀ227 °C (decomp.). IR (KBr pellet) 2858, 1655, 1638,
1459, 1439, 1398, 1350, 1130, 1100, 1068, 1030, 860, 805,
733 cmꢀ1; Anal. Calcd for [C13H20Cu2HgI4NO2S2]: C, 13.92; H,
1.80; N, 1.25; S, 5.72. Found: C, 13.68; H, 1.80; N, 1.25; S,
5.72%.
X-Ray Crystallographic Analysis. Crystal data were colꢀ
lected on a Bruker SMART APEX II ULTRA diffractometer
equipped with graphite monochromated Mo Kα radiation (λ =
0.71073 Å). Data collection, data reduction, and semiꢀ
empirical absorption correction were carried out using the
software package of APEX2.39 All of the calculations for the
structure determination were carried out using the SHELXTL
package.40 In 4, some ghost peaks were found close to the Hg
atoms. Since the lattice water molecule in 5 is highly disorꢀ
dered, the contribution of solvent electron density was reꢀ
moved by the SQUEEZE routine in PLATON.41 Relevant
crystal data collection and refinement data for the crystal
structures are summarized in Table S1.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ASSOCIATED CONTENT
Supporting Information
Preparation of 1, {[Pb2(o-bis-L)(µ-ClO4)2(ClO4)2]}n.
Pb(ClO4)2·3H2O (31.5 mg, 0.078 mmol) in acetonitrile (1 mL)
was added to a solution of o-bis-L (15.0 mg, 0.031 mmol) in
chloroform (1 mL). Slow evaporation of the solution afforded
a colorless crystalline product 1 suitable for Xꢀray analysis. IR
(KBr pellet): 2937, 2889, 1618, 1459, 1450, 1381, 1296, 1247,
NMR spectra and crystal structural data. CCDC reference numꢀ
bers 921860 (o-bis-L), 921861 (m-bis-L), 1588397 (p-bis-L),
1588398 (1), 1588399 (2), 1588400 (3), 1588401 (4), 1588402 (5).
These materials are available free of charge via the Internet at
http://pubs.acs.org.
1127 (ClO4 ), 1111, 1044, 1001, 973, 959, 916, 627 cmꢀ1 Anal.
ꢀ
Calcd for [C22H34Cl4O20Pb2S4]: C, 20.28; H, 2.63; S, 9.84.
Found: C, 20.54; H, 2.61; S, 9.90%. (Explosive!)
AUTHOR INFORMATION
Corresponding Authors
Preparation
of
2,
[Pb2(m-bis-
L)(CH3CN)2(H2O)2(ClO4)2](ClO4)2. Pb(ClO4)2·3H2O (31.5
mg, 0.078 mmol) in acetonitrile (1 mL) was added to a soluꢀ
tion of m-bis-L (15.0 mg, 0.031 mmol) in chloroform (1 mL).
Slow evaporation of the solution afforded a colorless crystalꢀ
line product 2 suitable for Xꢀray analysis. IR (KBr pellet)
2914, 2887, 1595, 1509, 1469, 1351, 1248, 1129 (ClO4), 1105,
1030, 908, 874, 798, 735, 627 cmꢀ1; Anal. Calcd for
[C26H44Cl4N2O22Pb2S4]: C, 21.98; H, 3.12; N, 1.97; S, 9.02.
Found: C, 21.79; H, 3.12; N, 2.01; S, 8.97%. (Explosive!)
Preparation of 3, [Hg2(o-bis-L)I2][Hg3I8]. HgI2 (35.2 mg,
0.077 mmol) in methanol (1 mL) was added to a solution of o-
bis-L (15.0 mg, 0.031 mmol) in chloroform (1 mL). Slow
evaporation of the solution afforded a yellow crystalline prodꢀ
uct 3 suitable for Xꢀray analysis. Mp: 212ꢀ213 °C. IR (KBr
pellet) 2883, 2863, 1655, 1397, 1366, 1287, 1243, 1134, 1118,
1100, 1026, 1008, 908, 751 cmꢀ1; Anal. Calcd for
[C22H34Hg5I10O4S4]: C, 9.56; H, 1.24; S, 4.64. Found: C, 9.21;
H, 1.34; S, 4.36%.
*Eꢀmail: sslee@gnu.ac.kr (S.S.L.)
*Eꢀmail: habata@chem.sci.tohoꢀu.ac.jp (Y.H.)
ORCID
Shim Sung Lee: 0000ꢀ0002ꢀ4638ꢀ5466
Yoichi Habata: 0000ꢀ0003ꢀ0712ꢀ6231
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
This work was supported by NRF (2016R1A2A205918799 and
2017R1A4A1014595), S. Korea, and the Support Program for
Strategic Research Foundation at Private Universities (2012ꢀ2016)
and JSPS KAKENHI Grant Number JP17K05844, Japan.
REFERENCES
Preparation of 4, [Hg3(m-bis-L)Br6]n. HgBr2 (27.9 mg,
0.077 mmol) in methanol (1 mL) was added to a solution of
m-bis-L (15.0 mg, 0.031 mmol) in chloroform (1 mL). Slow
(1) Bhagwat, U. A.; Mukhedkar, V. A.; Mukhedkar, A. J. Study of
Ligand Isomeric Complexes of NꢀFurfurylsalicylaldimine. J. Chem.
Soc., Dalton Trans. 1980, 2319ꢀ2322.
ACS Paragon Plus Environment

Page 7 of 9
Crystal Growth & Design
(2) Mukherjee, S.; Samanta, D.; Mukherjee, P. S. New Structural
and Pb) complexes of 1,10ꢀdithiaꢀ18ꢀcrownꢀ6: structural versatility.
Dalton Trans. 2010, 39, 9696ꢀ9704.
(23) Pickardt, J.; Wiese, S.; von Chrzanowski, L.; Borowski, M.
Investigations on Iodomercurates: Crystal Structures of Bis[di(12ꢀ
crownꢀ4)lithium]octaiodotrimercurate(II) and catenaꢀPoly{di[(benzoꢀ
15ꢀcrownꢀ5)potassium]pentaiododimercurate(II)} with new Iodomerꢀ
Topologies in a Series of 3d Metal Complexes with Isomeric Pheꢀ
nylenediacetates and 1,3,5ꢀTris(1ꢀimidazolyl)benzene Ligand: Synꢀ
theses, Structures, and Magnetic and Luminescence Properties. Cryst.
Growth Des. 2013, 13, 5335ꢀ5343.
(3) Lee, E.; Kim, J.ꢀY.; Lee, S. S.; Park, K.ꢀM. MolarꢀRatioꢀ
Dependent Supramolecular Isomerism: AgI Coordination Polymers
with Bis(cyanobenzyl)sulfides. Chem. Eur. J. 2013, 19, 13638ꢀ13645.
(4) Cui, F.ꢀY.; Huang, K.ꢀL.; Xu, Y.ꢀQ.; Han, Z.ꢀG.; Liu, X.; Chi,
Y.ꢀN.; Hu, C.ꢀW. Structural variability of Cd(II) and Co(II) mixedꢀ
ligand coordination polymers: effect of ligand isomerism and metalꢀ
toꢀligand ratio. CrystEngComm 2009, 11, 2757ꢀ2769.
(5) Plonka, A. M.; Banerjee, D.; Parise, J. B. Effect of Ligand
Structural Isomerism in Formation of Calcium Coordination Netꢀ
works. Cryst. Growth Des. 2012, 12, 2460ꢀ2467.
(6) Loeb, S. J.; Shimizu, G. K. H. Ditopic Crown Thioethers. Synꢀ
thesis and Structures of antiꢀ[Cu2(L)(PPh2Me)2][C1O4]2, synꢀ
[Cu2(L)(ꢀ ꢀPPh2CH2CH2PPh2)][PF6]2, and antiꢀ[Ag2(L)(PPh3)2][BF4]2
1
2
3
4
5
6
7
8
curate Anions and
a
Lanthanum(III) tetraidomercurate(II),
[La6(OH)8(O)(H2O)24][HgI4]4 with a Hexanuclear Complex Cation. Z.
Anorg. Allg. Chem. 2000, 626, 2096ꢀ2102.
(24) Kang, E.ꢀJ.; Lee, S. Y.; Lee, H.; Lee, S. S. SulfurꢀContaining
MixedꢀDonor TribenzoꢀMacrocycles and Their Endoꢀ and Exocyclic
Supramolecular Silver(I) and Copper(I) Complexes. Inorg. Chem.
2010, 49, 7510ꢀ7520.
(25) Kim, H. J.; Sultana, K. F.; Lee, J. Y.; Lee, S. S. Endoꢀ and/or
exocyclic silver(I) and mercury(II) complexes of an NO2S2ꢀ
macrocycle: effect of ligand ratio and anion. CrystEngComm 2010,
12, 1494ꢀ1500.
(26) Lee, S. J.; Jung, J. H.; Seo, J.; Yoon, I.; Park, K.ꢀM.; Lindoy,
L. F.; Lee, S. S. A Chromogenic Macrocycle Exhibiting Cationꢀ
Selective and AnionꢀControlled Color Change: An Approach to Unꢀ
derstanding StructureꢀColor Relationships. Org. Lett. 2006, 8, 1641ꢀ
1643.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(L
=
2,5,8,17,20,23ꢀHexathia[9](1,2)[9](4,5)cyclophane). Inorg.
Chem. 1993, 32, 1001ꢀ1006.
(7) 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. ExoꢀCoordinationꢀ
Based Supramolecular Silver(I) Complexes of S2O Macrocycles:
Effect of Ligand Isomerism on the Structural Diversity. Inorg. Chem.
2006, 45, 952ꢀ954.
(27) Kim, H. J.; Lee, S. S. AnionꢀControlled Endoꢀ and Exocyclic
Disilver(I) Complexes of an S2O3 Macrocycle. Inorg. Chem. 2008, 47,
10807ꢀ10809.
(8) Park, S.; Lee, S. Y.; Jo, M.; Lee, J. Y.; Lee, S. S. Molecular boꢀ
tanical garden: assembly of supramolecular silver(I) and mercury(II)
complexes of NS2ꢀdonor macrocycles with flowerꢀ, leafꢀ and treeꢀ
shaped structures. CrystEngComm 2009, 11, 43ꢀ46.
(9) Park, S.; Lindoy, L. F.; Lee, S. S. Assembly of Silver(I) Comꢀ
plexes of Isomeric NS2ꢀMacrocycles Displaying Cyclic Oligomer,
Helix, and Zigzag Structures. Cryst. Growth Des. 2012, 12, 1320ꢀ
1329.
(10) Park, S.; Lee, S. S. Copper complexes of two isomeric NS2ꢀ
macrocycles. J. Inclusion Phenom. Macrocyclic Chem. 2011, 71, 429ꢀ
434.
(11) Siewe, A. D.; Kim, J.ꢀY.; Kim, S.; Park, I.ꢀH.; Lee, S. S. Regiꢀ
oisomerꢀDependent Endoꢀ and Exocyclic Coordination of Bisꢀ
Dithiamacrocycles. Inorg. Chem. 2014, 53, 393ꢀ398.
(12) Kim, S.; Siewe, A. D.; Lee, E.; Ju, H.; Park, I.ꢀH.; Park, K.ꢀM.;
Ikeda, M.; Habata, Y.; Lee, S. S. LigandꢀInduced Formation of Copꢀ
per(I) Iodide Clusters: Exocyclic Coordination Polymers with Bisꢀ
dithiamacrocycle Isomers. Inorg. Chem. 2016, 55, 2018ꢀ2022.
(13) Park, S.; Lee, S. Y.; Park, K.ꢀM.; Lee, S. S. Supramolecular
Networking of Macrocycles Based on ExoꢀCoordination: From Disꢀ
crete to Continuous Frameworks. Acc. Chem. Res. 2012, 45, 391ꢀ403.
(14) Lehn, J.ꢀM. Dinuclear Cryptates: Dimetallic Macropolycyclic
Inclusion Complexes Concepts ꢀ Design ꢀ Prospects. Pure Appl.
Chem. 1980, 52, 2441ꢀ2459.
(28) Lee, H.ꢀH.; Park, I.ꢀH.; Lee, S. S. Cooperative Effect of Anion
and Mole Ratio on the Coordination Modes of an NO2S3ꢀDonor Macꢀ
rocycle. Inorg. Chem. 2014, 53, 4763ꢀ4769.
(29) Lee, E.; Ju, H.; Kim, S.; Park, K.ꢀM.; Lee, S. S. Anionꢀ
Directed Coordination Networks of a Flexible S‑Pivot Ligand and
Anion Exchange in the Solid State. Cryst. Growth Des. 2015, 15,
5427ꢀ5436.
(30) Ju, H.; Chang, D. J.; Kim, S.; Ryu, H.; Lee, E.; Park, I.ꢀH.;
Jung, J. H.; Ikeda, M.; Habata, Y.; Lee, S. S. CationꢀSelective and
AnionꢀControlled Fluorogenic Behaviors of a BenzothiazoleꢀAttached
Macrocycle That Correlate with Structural Coordination Modes. Inꢁ
org. Chem. 2016, 55, 7448ꢀ7456.
(30) Ryu, H.; Park, K.ꢀM.; Ikeda, M.; Habata, Y.; Lee, S. S. A Diꢀ
topic O4S2 Macrocycle and Its Hard, Soft, and Hard/Soft Metal Comꢀ
plexes Exhibiting Endoꢀ, Exoꢀ, or Endo/Exocyclic Coordination:
Synthesis, Crystal Structures, NMR Titration, and Physical Properties.
Inorg. Chem. 2014, 53, 4029ꢀ4038.
(31) Park, I.ꢀH.; Kim, J.ꢀY.; Kim, K.; Lee, S. S. Homonuclear and
Heteronuclear Complexes of Calix[4]ꢀbismonothiacrownꢀ5 with Oliꢀ
gomer and Polymer Structures. Cryst. Growth Des. 2014, 14, 6012ꢀ
6023.
(32) Lee, J. Y.; Kim, H. J.; Jung, J. H.; Sim, W.; Lee, S. S. Netꢀ
working of Calixcrowns: From Heteronuclear Endo/Exocyclic Coorꢀ
dination Polymers to A Photoluminescence Switch. J. Am. Chem. Soc.
2008, 130, 13838ꢀ13839.
(33) Kim, J.ꢀY.; Park, I.ꢀH.; Lee, J. Y.; Lee, J.ꢀH.; Park, K.ꢀM.; Lee,
S. S. Hard and Soft Metal Complexes of Calix[4]ꢀbisꢀmonothiacrownꢀ
5: Xꢀray and NMR Studies of Discrete Homodinuclear Complexes
and a Heteromultinuclear Network. Inorg. Chem. 2013, 52, 10176ꢀ
10182.
(34) Park, I.ꢀH.; Kim, J.ꢀY.; Lee, E.; Ju, H.; Kim, S.; Lee, J.ꢀH.;
Lee, S. S. Calix [4]ꢀbisꢀmonothiacrownꢀ5 as a versatile building block
for homo and heterometallic coordination polymers. Inorg. Chem.
Commun. 2016, 70, 205ꢀ209.
(15) Lindoy, L. F. Heavy metal ion chemistry of linked macrocyꢀ
clic systems incorporating oxygen and/or sulfur in their donor sets.
Coord. Chem. Rev. 1998, 174, 327ꢀ342.
(16) Jung, D.; Chamura, R.; Habata, Y.; Lee, S. S. Extra Large
Macrocycle: 40ꢀMembered Macrocycle via 2:2 Cyclization and Its
Dimercury(II) Complex. Inorg. Chem. 2011, 50, 8392ꢀ8396.
(17) Lee, S.ꢀG.; Park, K.ꢀM.; Habata, Y.; Lee, S. S. Endoꢀ and Exꢀ
ocyclic Supramolecular Complexes of MixedꢀDonor Macrocycles via
[1:1] and [2:2] Cyclizations. Inorg. Chem. 2013, 52, 8416ꢀ8426.
(18) Jo, M.; Seo, J.; Seo, M. L.; Choi, K. S.; Cha, S. K.; Lindoy, L.
F.; Lee, S. S. DonorꢀSetꢀInduced Coordination Sphere and Oxidationꢀ
State Switching in the Copper Complexes of O2S2X (X = S, O and
NH) Macrocycles. Inorg. Chem. 2009, 48, 8186ꢀ8191.
(19) Lee, S. Y.; Park, S.; Kim, H. J.; Jung, J. H.; Lee, S. S. Ligandꢀ
and AnionꢀDirected Assembly of ExoꢀCoordinated Mercury(II) Halꢀ
ide Complexes with O2S2ꢀDonor Macrocycles. Inorg. Chem. 2008,
47, 1913ꢀ1915.
(20) Pearson, R. G. Hard and Soft Acids and Bases. J. Am. Chem.
Soc. 1963, 85, 3533ꢀ3539.
(35) Park, S.; Lee, S. Y.; Lee, S. S. Discrete Mercury(II) Complexꢀ
es, OneꢀDimensional and Palladium(II)ꢀMediated TwoꢀDimensional
Silver(I) Coordination Polymers of NS2ꢀMacrocycle: Synthesis and
Structural Characterization. Inorg. Chem. 2010, 49, 1238ꢀ1244.
(36) Spek, A. L. Singleꢀcrystal structure validation with the proꢀ
gram PLATON. J. Appl. Crystallogr. 2003, 36, 7ꢀ13.
(37) Spek, A. L. Structure validation in chemical crystallography.
Acta Crystallogr., Sect. D: Biol. Crystallogr. 2009, D65, 148ꢀ155.
(38) van der Sluis, P.; Spek, A. L. BYPASS: an effective method
for the refinement of crystal structures containing disordered solvent
regions. Acta Crystallogr., Sect. A: Found. Crystallogr. 1990, A46,
194ꢀ201.
(21) Park, I.ꢀH.; Park, K.ꢀM.; Lee, S. S. Preparation and characteriꢀ
sation of divalent hard and soft metal (M= Ca, Co, Cu, Zn, Cd, Hg
ACS Paragon Plus Environment

Crystal Growth & Design
Page 8 of 9
(39) Bruker, APEX2 Version 2009.1ꢁ0 Data Collection and Proꢁ
cessing Software; Bruker AXS Inc., Madison, Wisconsin, U.S.A.,
2008.
(40) Sheldrick, G. M. Crystal structure refinement with SHELXL.
Acta Crystallogr. 2015, C71, 3ꢀ8.
(41) Spek, A. L. PLATON, A Multipurpose Crystallographic Tool;
University of Ultrecht, Ultrecht, The Netherlands, 2003.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment

Page 9 of 9
Crystal Growth & Design
For Table of Contents Use Only
1
2
3
4
5
6
7
8
9
Ligand Isomer Effect on the Formations of Supramolecular
Lead(II), Mercury(II), and Copper(I)/Mercury(II) Complexes of Bis-
O2S2-Macrocycle
Seulgi Kim,† Arlette Deukam Siewe,† Eunji Lee,† Huiyeong Ju,† InꢀHyeok Park,† Jong Hwa Jung,†
Yoichi Habata,*,‡ and Shim Sung Lee*,†
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
In order to investigate the ligand isomer effect on the complexations, three regioisomers of bisꢀO2S2ꢀ
macrocycle (o-bis-L, mꢀbisꢀL, and p-bis-L) were employed. The structural characteristics of the resultꢀ
ing homonuclear and heteronuclear supramolecular complexes of the isomers were discussed in terms of
controlling factors and coordination modes.
9
ACS Paragon Plus Environment