Synthesis and photophysical study of an octahedral silver(I) 1-D coordination polymer with thiocarboxylic-acid-based ligands

Article abstract of DOI:10.1016/j.poly.2017.08.035

We describe the synthesis of a unique 1-D silver coordination polymer, in which the silver metal center is, unusually, six-coordinated. The reaction of 2,3,5,6-tetrakis-(carboxymethylthio)-benzenediol (H₂L) and AgNO₃ in a 1:2 ratio r

Full text of DOI:10.1016/j.poly.2017.08.035

Accepted Manuscript
Synthesis and Photophysical Study of an Octahedral Silver(I) 1-D Coordination
Polymer with Thiocarboxylic-Acid-Based Ligands
Ume Farwa, Moumita Pait, Ji Yeon Ryu, Sunwoo Lee, Youngjo Kim, Hyoung-
Ryun Park, Junseong Lee
PII:
S0277-5387(17)30566-1
DOI:
http://dx.doi.org/10.1016/j.poly.2017.08.035
POLY 12799
Reference:
Polyhedron
To appear in:
Received Date:
Revised Date:
Accepted Date:
21 June 2017
22 August 2017
25 August 2017
Please cite this article as: U. Farwa, M. Pait, J. Yeon Ryu, S. Lee, Y. Kim, H-R. Park, J. Lee, Synthesis and
Photophysical Study of an Octahedral Silver(I) 1-D Coordination Polymer with Thiocarboxylic-Acid-Based
Ligands, Polyhedron (2017), doi: http://dx.doi.org/10.1016/j.poly.2017.08.035
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Synthesis and Photophysical Study of an Octahedral Silver(I) 1-D
Coordination Polymer with Thiocarboxylic-Acid-Based Ligands
Ume Farwa,a,1 Moumita Pait,a,1 Ji Yeon Ryu,a Sunwoo Lee,a Youngjo Kim, *, b Hyoung-Ryun Park,*,a
and Junseong Lee*,a
a Department of Chemistry, Chonnam National University, 77 Yongbong-ro, Buk-gu,
Gwangju 61186, Republic of Korea. Fax: 82 62 530 3389; Tel: 82 62 530 3371; E-mail:
hrpark@chonnam.ac.kr, leespy@chonnam.ac.kr
b Department of Chemistry and BK21+ Program Research Team, Chungbuk National
University, Cheongju, Chungbuk 361-763, Republic of Korea
E-mail: ykim@chungbuk.ac.kr
1These authors have contributed equally.

Abstract
We describe the synthesis of a unique 1-D silver coordination polymer, in which the silver
metal center is, unusually, six-coordinate. The reaction of 2,3,5,6-tetrakis-
(carboxymethylthio)-benzenediol (H2L) and AgNO3 in a 1:2 molar ratio resulted in the
esterification of the carboxylic acid groups and the oxidation of quinol to quinone. As a result,
a methylesterthioquinone ligand (L1) was obtained. By increasing the molar ratio of Ag to
four equivalents, a 1-D coordination polymer, [AgL1(NO3)]n (1), was obtained. The simple
reaction of L1 and AgNO3 in a 1:2 molar ratio also produced complex 1 in quantitative yield.
Both the esterified ligand L1 and the coordination polymer 1 were fully characterized by
1
infrared and H NMR spectroscopy, elemental analysis, electrospray ionization mass
spectrometry, and single crystal X-ray crystallography. The single crystal X-ray diffraction
measurements revealed that the Ag metal center has an octahedral geometry with 2-nitrate
ligands. The photophysical properties of complexes are also explored.
Keywords: Silver • Thiocarboxyl • 1-D • Coordination polymer • Octahedral coordination

Introduction
Interest in the development of molecular electronic devices [1]–[2] and redox substances
has increased. For this purpose, coordination polymers (CP’s) of d10 metal complexes have
attracted significant interest. These CP’s not only offer diverse topologies and remarkable
structural features but also have applications in sensing [3-8], gas storage [9-17], selective
heterogeneous catalysis [18-25], and magnetic devices [26-32]. In CP’s, the molecular
electronic characteristics of the ligands in combination with the coordination geometry of the
metal yield unique properties.
There are various factors controlling the synthesis of CP’s, such as the metal/ligand ratio,
concentration, temperature, and type of counterion used. However, the choice of metal and
the design of the ligand are the most important factors. Ag is widely employed for the
construction of CP’s because its CP’s have flexible geometries, variable coordination
numbers, π interactions, and unusual electronic and photophysical characteristics [6, 33-46].
To date, various multidentate organic ligands have been synthesized with different properties.
Sulfur-containing compounds, such as aromatic poly(phenylthio) ligands, have been explored
because of their electron-accepting and delocalizing electrochemical properties [2]. Many
thio-substituted benzene ligands have been studied for the construction of Ag(I) CP’s. The
soft nature of sulfur-containing ligands and silver results in interesting combinations for the
design of CP’s [47, 48].
In this work, we used a thiocarboxylic acid based ligand, 2,3,5,6-tetrakis-
(carboxymethylthio)-benzenediol, and studied its reactions with silver salts. In our work, we
found that the metal to ligand ratio is very important for the synthesis of the 1-D coordination
polymer. The use of ligand H2L with two equivalents of AgNO3 in MeOH led to the
oxidation of the quinol ligand to quinone with the simultaneous esterification of the
carboxylic acid groups present in the ligand. The reaction of AgNO3 and the ligand in a 4:1
molar ratio in MeOH resulted in the formation of dark red crystals of a nitrate-bridged AgI
coordination polymer. In this crystal, the geometry of silver metal center is octahedral, which
is very unusual [49]. Furthermore, we explored the photophysical properties of the octahedral
silver(I) 1-D coordination polymer.
Results and Discussion
Synthesis and Characterization

The synthesis of our target molecule was achieved as shown in Scheme 1. The quinol
ligand (2,4,5-tris-carboxymethylsulfanyl-3,6-dihydroxy-phenylsulfanyl)-acetic acid (H2L)
was synthesized following a literature procedure [50], and its reactions with AgI salts were
methodically explored to obtain the ligand L1 and coordination polymer AgL1 (Scheme 1).
The reaction of ligand H2L in MeOH with two equivalents of AgNO3 at 60 °C led to the
oxidation of the quinol ligand to quinone with the simultaneous esterification of the
carboxylate groups present in the ligand. The new ligand, L1, crystallized overnight directly
from the reaction mixture as a red solid suitable for X-ray analysis. The yield was ~46%.
Subsequently, we repeated the reaction with an excess of AgNO3 compared to the previous
reactions. The reaction of AgNO3 and the ligand in 4:1 molar ratio in MeOH at 60 °C
produced a reddish-brown solution and an ivory-colored powder. Dark-red crystals of nitrate-
bridged AgI coordination polymer (Scheme 1) were identified as the major product in ~42%
yield. In these reaction systems, two equivalents of AgNO3 were used for the oxidation of
quinol to quinone, and the remaining two equivalents of AgNO3 participated in the formation
of the complex. The reaction of AgNO3 and L1 in a molar ratio of 2:1 also produced the
desired product, 1. We further tried the reaction with excess AgNO3; however, we have failed
to isolate any characterizable product. Various synthetic conditions and reaction systems
were explored with different stoichiometries before a reproducible synthetic procedure was
established.
OH
HOOC
HOOC
COOH
COOH
S
S
S
S
OH
2 eq AgNO3
4eq AgNO3
H2L
COOMe
COOMe
O
O
O
O
N
COOMe
COOMe
MeOOC
O
S
S
S
S
S
Ag
2 eq AgNO3
MeOOC
S
S
S
O
O
MeOOC
COOMe
Ag-L1
n
L1
Scheme 1. Synthesis of quinone ligand L1 and complex AgL1.
Characteristic bands of the two ligands and the complex are present in the Fourier


COOH
transform infrared (FT-IR) spectra. The OH and
stretching frequencies for ligand
–1

H2L appear at 3304–3100 cm . The COOMe stretching frequencies appear at 1735 and 1737

cm–1 for ligand L1 and the Ag-L1 complex, respectively. For Ag-L1 a very strong
–
characteristic band at 1384 cm–1 is attributed to the ν3(E′) mode of the NO3 group.
1
The H NMR spectra of L1 shows two sets of peaks that can be attributed to the presence
of quinone forms in solution. The peaks at 3.717 and 3.561 ppm can be assigned to the –CH2
and -CH3 protons of the quinone form of the ligand. The 1H NMR results of the Ag-L1 crystal
also shows that only single complex is present in solution. The use of higher molar ratio
AgNO3 not only resulted in the complexation of Ag and L1 but also complete oxidation of
quinol to quinone.
Solid State Structures.
The esterified ligand L1 crystallizes in the monoclinic space group P21/c.(Figure 1) The
crystal structure of ligand L1 shows that the thiocarbonyl acid has been esterified and the
quinol group has been converted to quinone. Unlike the solution state 1H NMR results, which
indicate that both quinone and quinol are present in solution, the solid product contains only
the quinone form. This indicates that the quinone form of L1 is more energetically stable and
precipitates preferentially. The crystal structure shows that two of the four methylthioester
arms are directed inward, while the other two are directed outward. The bond angles between
the sulfur atoms and benzene carbon atoms range from 101.7(2)° to 104.6(2)° (Figure 1a).
(a)

(b)
Figure 1. Crystal structure of ligand L1: (a) Top view, (b) side view. Hydrogen atoms have
been omitted for clarity. Colors: S, yellow; O, red; C, black.
The [AgL1(NO3)]n CP crystallizes in the monoclinic space group P21/n. The asymmetric unit
of the complex consists of a ligand molecule, a silver atom, and a nitrate ion (Figure 2a). The
Ag atom is coordinated by six atoms, four S atoms from two molecules of L1 and two O from
the nitrate ion, thus exhibiting an octahedral geometry with bond angles around the Ag(1)
cation ranging from 51.8(3)° to 141.4(7)°. The coordination of Ag1 with the thioester group
of the ligand rather than the O from the quinone group present at the para position agrees well
with the “hard and soft acids and bases” (HSAB) theory. Interestingly, the Ag center in this
crystal has a rare octahedral geometry. The silver center is bonded to two S atoms from the
ligand and two oxygen atoms from nitrate ion. Figure 2b shows the helical 1D coordination
polymer chain for the Ag-L1. The additional SS (green dotted line) and SO (pink dotted
line) interactions assemble units of 1 into sheets in the (010) plane (Figures 2c–d). Additional
weak CHO interactions (Figure 2e) result in a 3-D network structure (Figure 2(e). The 2-
nitrate does not participate in the extended chains.
In order to investigate the bulk properties of L1 and complex 1, TGA experiments were
conducted and the thermograms were obtained as shown in Figure s7 and s8. The thermal
degradation of L1 consist of three weight loss steps, where the first and second weight loss
o
below 350 C could be ascribed to partial decomposition of ester groups. The third weight
loss could be attributed to the thermal decomposition of the remaining sulfur and quinone

part. The thermal degradation of 1 provides more complicated five step weigh loss. The first
weight loss below 150 oC seems to be the evaporation of solvents. The second, third and forth
weight loss steps could be attributed to the thermal decomposition of the ester groups and
remaining organic parts, respectively.
(a) Asymmetric unit.
(b) 1-D extended view along the c-axis.

(c) Connectivity of complex 1 in the (010) plane.
(d) Connectivity of complex 1 in the (101) plane.

(e) 2-D extended view in the ac plane.
(f) 3-D extended view in the (101) plane.
Figure 2. Crystal structure of (a) the asymmetric unit of complex 1 with selected atom-
numbering scheme, (b) 1-D extended view along the c-axis, (c) connectivity of complex 1 in
the (010) plane, (d) connectivity of complex 1 in the (101) plane, (e) 2-D extended view in
the ac-plane, and (f) 3-D extended view in the (101) plane. Hydrogen atoms have been
omitted for clarity. Colors: Ag, light gray; N, blue; O, red; C, gray. Selected bond lengths (Å)
and angles (deg): Ag1S1 2.663(2), Ag1S2 2.778(2), Ag1S3 2.693(2), Ag1S4 2.763(2),
Ag1O11 2.417(7), Ag1O12 2.487(6), O1C1 1.207(8), O2C4, S1Ag1S2 74.58(6),

S2Ag1S3 90.70(7), O11Ag1O12 51.8(3), S1Ag1O11 93.8(2), S3Ag1O12
88.92(17), S1Ag1S4 92.95(7), S3Ag1S4 73.38(6), S2Ag1O11 114.7(2),
S2Ag1O12 87.4(2).
UV-Vis Spectra
To investigate the photophyscial properties of complexes, UV-Vis spectra were
obtained. (Figure 3) In the spectrum of ligand H2L, the absorption maximum peaks (λmax) are
found at 244 and 351 nm, having molar extinction coefficients of 67500 and 16300 M-1cm-1,
respectively (Table 1). These values can be attributed to the π-π* and n-π* electronic
transitions taking place in H2L. The esterified ligand, L1, which has a quinone group, has λmax
values at 228 and 370 nm, and the molar extinction coefficient values for L1 are 46300 and
30100 M-1cm-1, respectively. The λmax at 228 nm shows a hypsochromic shift of 16 nm with a
decrease in the absorption intensity compared to that of H2L. The value of λmax at 370 nm
shows a bathochromic shift of 19 nm with an increase in the absorption intensity in
comparison with that of H2L.The shift of λmax and change in absorption intensities can be
attributed to the new structural features in L1 [51], that is, the change of functional group
from an acid to ester group and the oxidation of quinol to quinone.
In the spectrum of Ag-L1, λmax are found at 211 and 378 nm, and the molar extinction
coefficients are 29500 and 12500 M-1cm-1, respectively. These values indicate an inter-ligand
electronic transition [52], i.e., π-π* and n- π*. The absorption maxima of Ag-L1 show a
hypsochromic shift of 17 nm and a bathochromic shift of 8 nm compared to those of L1. In
contrast, there is a clear decrease in the absorption intensity of the Ag-L1 spectra as compared
to that of L1. This could be because, in the solution state, L1 contains both quinone and
unoxidized quinol forms, as shown by NMR. However, in the case of complex 1, only the
quinone form of the ligand is present.
Table 1. Comparison of the absorption maxima of the complexes.
Sample
λmax (nm)
244
Ɛ (M-1cm-1)
67500
H2L
351
16300
L1
228
46300
370
30100

1(Ag-L1)
211
378
29500
12500
Figure 3. UV-Vis spectra of H2L, L1 and complex 1.
Conclusion
In this paper, we demonstrated that by using a 1:2 molar ratio of (H2L) and AgNO3, the
carboxylic acid group can be esterified and the quinol can be oxidized to a quinone, resulting
in the isolation of crystals of the methylesterthioquinone ligand (L1). We further doubled the
molar ratio of AgNO3, and, surprisingly, a 1-D coordination polymer, [AgL1(NO3)]n was
obtained. Unlike the typical low coordination numbers and related geometries of silver
coordination compounds, the Ag center was found to have an octahedral geometry.
Furthermore photphysical properties of (H2L), (L1) and complex 1 were investigated. The
results dictate that inter-ligand electronic transition takes place in complex 1 when exposed to
UV-visible light.

Experimental Section
General Considerations. All experimental manipulations were carried out in air. The
chemicals and solvents were reagent grade materials and used as received without further
1
purification. The H NMR and 13C spectra were recorded in DMSO-d6 using a Bruker
Advance 300 NMR spectrometer at 300.13 MHz and 75.47 MHz, respectively, at KBSI
Gwangju. The IR spectra were recorded on a Bruker Tensor 27 equipped with an attenuated
total reflectance (ATR) Harricks apparatus. Thermogravimetric analysis (TGA)
measurements were performed in a nitrogen atmosphere using a mettler toledo TGA/DSC
instrument with star system at a scanning rate of 10 oC /min.
Synthesis
Ligand H2L. The ligand was prepared following a modified literature procedure [50]. p-
Benzoquinone (2g, 20 mmol) was placed in 10 mL of water, and thioglycolic acid (5.41 mL,
80 mmol) in water was added very slowly, as mentioned in the literature, over 30 min.
Immediately after the complete addition of thioglycolic acid, the brown solution became
white. The product, a white powder, was obtained and separated by filtration and
recrystallized from hot water. Yield 56%, IR peaks: 3340 (br), 1701 (s), 1431 (m), 1382 (m),
1310 (m), 1198 (m), 865 (w). 1H NMR DMSO-d6: 3.72 (s, -CH2).
Ligand L1. Ligand H2L (47.05 mg, 0.1 mmol), silver nitrate (34 mg, 0.2 mmol), and MeOH
(5mL) were charged into a 50-mL round bottom flask. The color of the reaction mixture
became ivory. The reaction mixture was refluxed at 60 C for 6 h. A blood red solution
formed along with white colored ppt. The solution was filtered and left to slowly evaporate
by ether diffusion. Red block-shaped single crystals were obtained overnight in moderate
yield. Anal. Calc. for C18H20O10S4 C, 41.21; H, 3.84. Found: C, 40.82; H, 4.06. IR peaks
1
(cm-1): 3433 (br), 1735 (s), 1667 (m), 1435 (s), 1284 (s), 1173 (m), 1108 (m). H NMR
DMSO-d6 (ppm): δ = 3.72 (s, -CH3), 3.56 (s, -CH2). 13C NMR DMSO-d6 (ppm): δ = 172.72,
169.15, 125.91, 52.37, 34.36.
Complex AgL1. Ligand H2L (47.05 mg, 0.1 mmol), silver nitrate (68 mg, 0.4 mmol) and
MeOH (5mL) were charged into a 50-mL round bottom flask, and the reaction was carried
out as mentioned above. A reddish brown solution was formed with an ivory colored
precipitate. Maroon needle-like crystals suitable for X-ray analysis were obtained by the slow

evaporation of the mother liquor overnight with moderate yield. Anal. Calc. for C18H20O10S4
(524.61) C, 31.13; H, 2.90. Found: C, 30.85; H, 2.53. Selected IR peaks (cm-1): 3438 (br),
1737 (s), 1662 (m), 1384 (s) (nitrate group), 1301 (m), 1108 (m). 1H NMR DMSO-d6 (ppm):
δ 3.93 (s, -CH3), 3.66 (s, -CH2). ESI-MS: m/z calcd for [1-NO3]+: 630.90, found 632.84.
Physical Measurements. Elemental analyses (CHN) were performed with a Perkin-Elmer
model 240C elemental analyzer. FT-IR spectra were recorded on a Perkin-Elmer 883
spectrometer. A solute concentration of 10-3 M was used, and a Shimadzu UV 3100 UV-vis-
NIR spectrophotometer was used to record the electronic absorption spectra.
X-ray Crystallography. Suitable single crystals of L and Ag-L were examined using a
Bruker SMART APEX-II CCD diffractometer, equipped with a fine focus 1.75-kW sealed-
tube Mo-Kα radiation generator (λ) 0.71073 Å. The data were collected at 298 K, by scanning
ω in steps of 0.3° at a scan speed of 5 s per frame. The APEX2 software was used for data
acquisition and data integration and reduction [53]. Structures were solved by direct methods
using SHELXS-2014 and refined with full-matrix least squares on F2 using SHELXL-2014
[54]. The locations of the heaviest atoms (Ag) were easily determined, and the O, N, and C
atoms were subsequently determined from the difference Fourier maps. The non-H atoms
were refined anisotropically. The H atoms were introduced in calculated positions and refined
with fixed geometries and riding thermal parameters with respect to their carrier atoms. A
summary of the crystal data and relevant refinement parameters are given in Table 2.

Table 2. Crystallographic data and parameters for L1 and compound 1.
Compound
CCDC #
L1
1
1555905
C18H20O10S4
524.58
Monoclinic
P2(1)/c
8.7253(4)
31.2090(14)
9.1641(4)
90
1555906
Formula
Formula weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
α (°)
C18H20AgNO13S4
694.46
Monoclinic
P2(1)/n
16.932(6)
9.380(3)
16.978(6)
90
β (°)
γ (°)
109.945(2)
90
114.005(18)
90
V (Å3)
Z
2345.78(18)
4
1.485
0.456
1088
2463.4(15)
4
1.872
1.226
1400
ρcalc (g cm-3)
μ (mm-1)
F(000)
T (K)
296
100
Scan mode
 and 
 and 
10 <=h<=10,
20 <=h<= +16,
9 <=k<= +10,
16 <=1<= +20
11001
hkl range
36 <=k<= +36,
11 <=l<= +11
27431
Measured reflns
Unique reflns [Rint]
Reflns used for
refinement
4381 [0.0814]
4225 [0.0766]
2410
3173
Refined parameters 293
339
R1a (I > 2σ(I))
wR2b all data
GOF on F2
ρfin (max/min)
(eÅ-3)
0.0615
0.1443
0.995
0.0446
0.1044
1.008
0.642, 0.382
0.758, 0.570
a R1 = ∑||Fo| − |Fc||/∑|Fo|. b wR2 = {[∑w(Fo2 − Fc2)2]/[∑w(Fo2)2]}1/2.

Supplementary Material
Mass spectrometry data, spectroscopic data and crystallographic data in CIF format are
available in the Supporting Information. CCDC 1555905 and 1555906 contain supplementary
crystallographic data for ligand L1 and complex 1, respectively. These data can be obtained
free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-
336-033; or e-mail: deposit@ccdc.cam.ac.uk.
Acknowledgements
We acknowledge financial support from the Basic Science Research Program
(2016R1D1A1B03930507) and BRL Program (2015R1A4A1041036) through the National
Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT & Future
Planning. This study was also supported by a 2016 Research Grant from Chonnam National
University.
[1] J.-M. Lehn, (1st Eds.), Supramolecular Chemistry: Concepts and Perspective,VCH,
Weinheim, 1995, Ch.8.
[2] Y. Suenaga, T. Kuroda-Sowa, M. Munakata, M. Maekawa, H. Morimoto, Polyhedron, 18
(1998) 429-436.
[3] J. Jia, F. Xu, Z. Long, X. Hou, M.J. Sepaniak, Chem. Commun., 49 (2013) 4670-4672.
[4] X. Zhu, H. Zheng, X. Wei, Z. Lin, L. Guo, B. Qiu, G. Chen, Chem. Commun., 49 (2013)
1276-1278.
[5] .s. errando- oria, P. erra-Crespo, . de ange, . ascon, . Kaptei n, . ulve, .
Cano, . loret, . Pas n, C. uiz-P rez, J. Am. Chem. Soc., 134 (2012) 15301-15304.
[6] P.L. Feng, K. Leong, M.D. Allendorf, Dalton Trans., 41 (2012) 8869-8877.
[7] L.E. Kreno, K. Leong, O.K. Farha, M. Allendorf, R.P. Van Duyne, J.T. Hupp, Chem. Rev,
112 (2012) 1105-1125.
[8] M. Allendorf, C. Bauer, R. Bhakta, R. Houk, Chem. Soc. Rev., 38 (2009) 1330-1352.

[9] J.E. Mondloch, W. Bury, D. Fairen-Jimenez, S. Kwon, E.J. DeMarco, M.H. Weston, A.A.
Sarjeant, S.T. Nguyen, P.C. Stair, R.Q. Snurr, O.K. Farha, J.T. Hupp, J. Am. Chem. Soc., 135
(2013) 10294-10297.
[10] J. Park, Z.U. Wang, L.-B. Sun, Y.-P. Chen, H.-C. Zhou, J. Am. Chem. Soc., 134 (2012)
20110-20116.
[11] Y.S. Bae, C.Y. Lee, K.C. Kim, O.K. Farha, P. Nickias, J.T. Hupp, S.T. Nguyen, R.Q.
Snurr, Angew. Chem. Int. Ed., 51 (2012) 1857-1860.
[12] M.P. Suh, H.J. Park, T.K. Prasad, D.-W. Lim, Chem. Rev., 112 (2011) 782-835.
[13] K. Sumida, D.L. Rogow, J.A. Mason, T.M. McDonald, E.D. Bloch, Z.R. Herm, T.-H.
Bae, J.R. Long, Chem. Rev., 112 (2011) 724-781.
[14] R.B. Getman, Y.-S. Bae, C.E. Wilmer, R.Q. Snurr, Chem. Rev., 112 (2011) 703-723.
[15] Z. Guo, H. Wu, G. Srinivas, Y. Zhou, S. Xiang, Z. Chen, Y. Yang, W. Zhou, M.
O'Keeffe, B. Chen, Angew. Chem. Int. Ed., 50 (2011) 3178-3181.
[16] J.-R. Li, R.J. Kuppler, H.-C. Zhou, Chem. Soc. Rev., 38 (2009) 1477-1504.
[17] M. Kondo, T. Yoshitomi, H. Matsuzaka, S. Kitagawa, K. Seki, Angew. Chem. Int. Ed.,
36 (1997) 1725-1727.
[18] D.T. Genna, A.G. Wong-Foy, A.J. Matzger, M.S. Sanford, J. Am. Chem. Soc., 135
(2013) 10586-10589.
[19] M. Yoon, R. Srirambalaji, K. Kim, Chem. Rev., 112 (2011) 1196-1231.
[20] K.K. Tanabe, S.M. Cohen, Angew. Chem., 121 (2009) 7560-7563.
[21] S. Hasegawa, S. Horike, R. Matsuda, S. Furukawa, K. Mochizuki, Y. Kinoshita, S.
Kitagawa, J. Am. Chem. Soc., 129 (2007) 2607-2614.
[22] S.-H. Cho, B. Ma, S.T. Nguyen, J.T. Hupp, T.E. Albrecht-Schmitt, Chem. Commun.,
(2006) 2563-2565.
[23] C.-D. Wu, A. Hu, L. Zhang, W. Lin, J. Am. Chem. Soc., 127 (2005) 8940-8941.
[24] S.S.-Y. Chui, S.M.-F. Lo, J.P. Charmant, A.G. Orpen, I.D. Williams, Science, 283
(1999) 1148-1150.
[25] M.E. Davis, Acc. Chem. Res., 26 (1993) 111-115.
[26] E. Coronado, G. Minguez Espallargas, Chem. Soc. Rev., 42 (2013) 1525-1539.
[27] R. Sibille, T. Mazet, B. Malaman, M. François, Chem. Eur. J., 18 (2012) 12970-12973.
[28] S. Bureekaew, S. Horike, M. Higuchi, M. Mizuno, T. Kawamura, D. Tanaka, N. Yanai,
S. Kitagawa, Nat. Mater., 8 (2009) 831-836.

[29] M. Kurmoo, Chem. Soc. Rev., 38 (2009) 1353-1379.
[30] Y.-Q. Wang, K. Wang, Q. Sun, H. Tian, E.-Q. Gao, Y. Song, Dalton Trans., (2009)
9854-9859.
[31] A.M. Kutasi, D.R. Turner, P. Jensen, B. Moubaraki, S.R. Batten, K.S. Murray,
CrystEngComm, 11 (2009) 2089-2095.
[32] W.-L. Meng, G.-X. Liu, T.-a. Okamura, H. Kawaguchi, Z.-H. Zhang, W.-Y. Sun, N.
Ueyama, Cryst. Growth Des., 6 (2006) 2092-2102.
[33] R. Toyoda, M. Tsuchiya, R. Sakamoto, R. Matsuoka, K.-H. Wu, Y. Hattori, H. Nishihara,
Dalton Trans., 44 (2015) 15103-15106.
[34] M.A. Haj, C.B. Aakeröy, J. Desper, New Journal of Chemistry, 37 (2013) 204-211.
[35] C.A. Hollis, S.R. Batten, C.J. Sumby, Cryst. Growth Des., 13 (2013) 2350-2361.
[36] J.-Y. Wu, T.-C. Chao, M.-S. Zhong, Cryst. Growth Des., 13 (2013) 2953-2964.
[37] A. Béziau, S.A. Baudron, M.W. Hosseini, Dalton Trans., 41 (2012) 7227-7234.
[38] S. Park, L.F. Lindoy, S.S. Lee, Cryst. Growth Des., 12 (2012) 1320-1329.
[39] K. Chainok, S.M. Neville, C.M. Forsyth, W.J. Gee, K.S. Murray, S.R. Batten,
CrystEngComm, 14 (2012) 3717-3726.
[40] W.M. Bloch, C.J. Sumby, Chem. Commun., 48 (2012) 2534-2536.
[41] P.J. Steel, C.M. Fitchett, Coord. Chem. Rev., 252 (2008) 990-1006.
[42] C.-L. Chen, B.-S. Kang, C.-Y. Su, Aust. J. Chem., 59 (2006) 3-18.
[43] M. Sarkar, K. Biradha, CrystEngComm, 6 (2004) 310-314.
[44] L. Brammer, C.S. Rodger, A.J. Blake, N.R. Brooks, N.R. Champness, J.W. Cunningham,
P. Hubberstey, S.J. Teat, C. Wilson, M. Schröder, Dalton Trans., (2002) 4134-4142.
[45] N.R. Brooks, A.J. Blake, N.R. Champness, J.W. Cunningham, P. Hubberstey, S.J. Teat,
C. Wilson, M. Schröder, Dalton Trans., (2001) 2530-2538.
[46] A.J. Blake, N.R. Brooks, N.R. Champness, J.W. Cunningham, P. Hubberstey, M.
Schroeder, CrystEngComm, 2 (2000) 41-45.
[47] X.-P. Zhou, Z. Xu, M. Zeller, A.D. Hunter, S.S.-Y. Chui, C.-M. Che, J. Lin, Inorg.
Chem., 49 (2010) 7629-7631.
[48] K. Kobayashi, O. Takahashi, K. Namatame, O. Kikuchi, N. Furukawa, Chem. Lett., 27
(1998) 515-516.
[49] J. Jimenez, I. Chakraborty, A.M. Del Cid, P.K. Mascharak, Inorg. Chem., 56 (2017)
4784-4787.

[50] M. Schtjbe, J. Am. Chem. Soc., 69 (1947) 712.
[51] A.C. Lane, M.V. Vollmer, C.H. Laber, D.Y. Melgarejo, G.M. Chiarella, J.P. Fackler, X.
Yang, G.A. Baker, J.R. Walensky, Inorg. Chem., 53 (2014) 11357-11366.
[52] H.-C. Wu, P. Thanasekaran, C.-H. Tsai, J.-Y. Wu, S.-M. Huang, Y.-S. Wen, K.-L. Lu,
Inorg. Chem., 45 (2006) 295-303.
[53] Bruker-AXS (2014). APEX2. Version 2014.11-0. Madison, Wisconsin, USA.
[54] G. Sheldrick, Acta Cryst. C, 71 (2015) 3-8.

Pictograms
OH
HOOC
HOOC
COOH
COOH
S
S
S
S
OH
2 eq AgNO3
4eq AgNO3
H2L
COOMe
COOMe
O
O
O
N
O
COOMe
COOMe
MeOOC
O
S
S
S
S
S
Ag
2 eq AgNO3
MeOOC
S
S
S
O
O
MeOOC
COOMe
Ag-L1
n
L1
Synopsis: Whereas the reaction of 2,3,5,6-tetrakis-(carboxymethylthio)-benzenediol (H2L) and
AgNO3 in a 1:2 molar ratio resulted in the esterification of the carboxylic acid groups and the
oxidation of quinol to quinone, the reaction in a 1:4 molar ratio produced a 1-D coordination
polymer, [AgL1(NO3)]n.