A {Ag17S8} cluster-based coordination polymer linked by bridging CO32? ligands

Article abstract of DOI:10.1016/j.ica.2019.119107

Cluster-based coordination frameworks superior to single metal-ion based coordination frameworks possess highly connected nets, large porous channels and enhanced stability. The carbonate anion (CO₃^2?), an excellent anion template, can also serve as a rigid ligand with planar triangular geometry. It is an effective means of utilizing renewable carbon resources by the fixation of atmospheric carbon dioxide. Therefore, pursuing complex functional cluster-based coordination framework materials bridging by CO₃^2? ligand is a sensible idea. Herein, compound {[Ag₃₄(SBu^t)₁₆(CF₃COO)₁₀(CO₃)₅(H₂O)₄][Et₃N⁺]₂}_n (1) (Ag₁₇S₈ dimer) consists of a [Ag₁₇(SBu^t)₈(CF₃COO)₆(CO₃)]⁺ cationic secondary building unit (SBU), a [Ag₁₇(SBu^t)₈(CF₃COO)₄(CO₃)₃(H₂O)₄]^? anionic SBU and a bridging CO₃^2? ligand in an asymmetric unit, which is extended into a 2D honeycomb network parallel to the bc plane with a simple topology symbol of {6³}. Compound 1 has been well defined and the luminescence properties of 1 have been investigated.

Full text of DOI:10.1016/j.ica.2019.119107

Inorganica Chimica Acta 497 (2019) 119107
Contents lists available at ScienceDirect
Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
2
−
A {Ag S } cluster-based coordination polymer linked by bridging CO
1
7 8
3
ligands
1
1
⁎
Ju-Feng Shi , Xiang-Ling Gao , Yu-Hui Feng, Kun Zhou , Jiu-Yu Ji, Yan-Feng Bi
School of Chemistry and Materials Science, Liaoning Shihua University, Fushun 113001, Liaoning, China
A R T I C L E I N F O
A B S T R A C T
Cluster-based coordination frameworks superior to single metal-ion based coordination frameworks possess
Keywords:
2
−
Silver clusters
highly connected nets, large porous channels and enhanced stability. The carbonate anion (CO
), an excellent
3
Coordination polymers
Bridging ligands
Topology
anion template, can also serve as a rigid ligand with planar triangular geometry. It is an effective means of
utilizing renewable carbon resources by the fixation of atmospheric carbon dioxide. Therefore, pursuing complex
2−
functional cluster-based coordination framework materials bridging by CO
3
S
ligand is a sensible idea. Herein,
Luminescence properties
t
+
t
compound {[Ag34(SBu )16(CF
3
COO)10(CO
3
)
5
(H
2
4
O) ][Et
3
N
]
2
}
n
(1) (Ag17
8
dimer) consists of a [Ag17(SBu )
8
+
t
−
(
CF
3
COO)
6
(CO
3
)] cationic secondary building unit (SBU), a [Ag17(SBu )
8
(CF
3
COO)
4
(CO
3
)
3
(H
2
4
O) ]
anionic
2
−
SBU and a bridging CO
3
ligand in an asymmetric unit, which is extended into a 2D honeycomb network
3
parallel to the bc plane with a simple topology symbol of {6 }. Compound 1 has been well defined and the
luminescence properties of 1 have been investigated.
1
. Introduction
High-nuclearity metal clusters have attracted increasing attention as
providing potentiality to facilitate complex functional cluster-based
coordination framework materials [9]. However, it is proved to be
difficult to isolate and character silver cluster-based coordination fra-
meworks [10].
an active area in inorganic chemistry not only because of their im-
portance in fundamental science [1], but also due to their various po-
tential applications in materials science and biomedicine fields [2].
Especially, high-nuclearity silver clusters are promising crystalline
materials, which have been studied widely owing to their variety of
properties depending on the nanoscale size, shape and composition [3].
Consequently, the effective strategy of preparing giant silver clusters is
particularly important. Anion template is an important synthetic
strategy to prepare high-nuclearity silver clusters with core-shell
structure. Generally, inorganic anions, such as halogen anions [4] and
2
−
Above all, the carbonate anion (CO
3
), an excellent anion tem-
plate, can also serve as a bridging ligand [11,12]. It is a rigid ligand
with planar triangular geometry and shows different coordination
2
−
modes [13]. In recent years, CO
3
-template/ligand springing from the
fixation of atmospheric carbon dioxide has attracted continuing atten-
tion. Because CO is a renewable carbon resource [10]. Searching for a
simple approach to fix CO
2
2
−
2
by a metal cluster to bind CO
3
is a pro-
mising route. So far, several cage-like high-nuclearity silver clusters
2
−
wrapping CO
ample of CO
been reported [12].
3
3
template have been reported [11]. However, the ex-
2
−
2−
2−
2−
polyatom anions (CO
3
, CrO
4
, SO
4
, and polyoxoanions) [5] have
as a linker connecting two silver clusters has rarely
been chosen as the anion templates. In addition, molecular clusters as
discrete well-defined ‘macro molecules’ can serve as nano-sized SBU to
assemble ordered super structures [6]. Remarkably, cluster-based co-
ordination frameworks, a kind of promising crystalline materials, ben-
efit from the SBU synthetic strategy [7,8]. Cluster-based coordination
frameworks superior to single metal-ion based coordination frame-
works possess highly connected nets, large porous channels and en-
hanced stability. Therefore, pursuing cluster-based coordination fra-
meworks employing the molecular building cluster is a critical issue,
t
In this paper, AgSBu with CF
3
COOAg, AgBF
4
and (CH
3
4
) NBr in a
molar ratio of 5.08: 2.09: 1.28: 1.00 were dissolved in methanol to yield
t
a novel 2D layer compound {[Ag34(SBu )16(CF
3
COO)10(CO
3
)
5
(H
2
O) ]
4
+
[Et
3
N
]
2
}
n
(1) based on silver chalcogenide clusters. In addition,
compound 1 has been well defined and the luminescence properties of 1
have been investigated.
⁎
Corresponding author.
E-mail addresses: zhouk800@aliyun.com, zhouk800@nenu.edu.cn (K. Zhou).
1
These authors contributed equally.
https://doi.org/10.1016/j.ica.2019.119107
Received 28 May 2019; Received in revised form 14 August 2019; Accepted 26 August 2019
Available online 27 August 2019
0020-1693/ © 2019 Elsevier B.V. All rights reserved.

J.-F. Shi, et al.
Inorganica Chimica Acta 497 (2019) 119107
2
. Experimental
Table 1
Crystal data and structure refinements for compound 1.
2.1. Material and methods
Compound
1
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
C
101
6801.04
H
184Ag34
F
30
N O
2 39
S
16
All reagents and solvents for synthesis were obtained from com-
mercial sources and used without further purification, such as methanol
Orthorhombic
Pbca
(
Aladdin, > 95%). All other reagents were of analytical grade and used
t
as received. AgSBu was synthesized by using Et
3
N as organic solvent
22.5274 (10)
36.0661 (16)
45.294 (2)
90
t
and reacted with equivalent amounts of AgNO
3
with HSBu according to
b (Å)
c (Å)
the literature [14]. Elemental analyses (C, H, and N) were performed on
a Perkin-Elmer 2400 CHN elemental analyzer. Ag and S were analyzed
on a PLASMA-SPEC(I) ICP atomic emission spectrometer. The FT-IR
α (°)
β (°)
90
γ (°)
90
−1
3
spectrum was recorded from KBr pellets in the range of 4000–400 cm
V (Å )
36,801 (3)
8
on a Mattson Alpha-Centauri spectrometer. Luminescence was mea-
sured on a Hitachi F-4500.
Z
−
1
3
D/g cm
μ/mm
2.455
−
3.793
F(0 0 0)
25,920
241,624
32,623
1774
2
.2. Synthesis of {[Ag34(SBut)16(CF
3
COO)10(CO
3
)
5
(H
2
O)
4
][Et
3
N+
2
] }
n
Reflection collected
Unique reflections
Parameters
(
1)
R
int
0.0359
1.035
t
Compound 1 was obtained by one-pot synthesis, namely, AgSBu
GOF
(
0.0657 g, 0.3334 mmol) with CF
3
COOAg (0.0303 g, 0.1372 mmol),
R
1
a
[I > 2σ(I)]
0.0740
0.2137
b
AgBF
4
(0.0164 g, 0.0842 mmol) and (CH
3
)
4
NBr (0.0101 g,
wR
2
(all data)
0
.0656 mmol) were dissolved in methanol (15 mL) under stir at room
a
b
R
1
wR
= Σ||F
o
| − |F
c
||/Σ|F
o
|;
temperature to gain a white suspension. Then the white suspension was
uninterruptedly stirred at room temperature for 15 h and then was fil-
tered. The filtrate was evaporated slowly in air at room temperature.
Compound 1 deposited as colourless bulk crystals. Yield: ca. 17%
2
2 2
2)2]}1/2
.
2
= {Σ[w(F
o
− F ) ]/Σ[w(F
c
o
(
based
on
Ag).
Elemental
analysis
(%)
calcd
for
C
101
H
184Ag34
F
30
N
2
O S16, C, 17.84; H, 2.73; N, 0.41; S, 7.54; Ag,
39
5
3.93. Found: C, 17.82; H, 2.74; N, 0.40; S, 7.56; Ag, 53.89. IR (KBr):
−1 −1 −1
ν = 3443 cm
(OeH), 3016 cm
(CeH), 1684 cm
−1
(C]O),
−
1
−1
1
489 cm
(CeO), 1390 cm
(CeN), 1084 (CeF) cm , 951 (CeS)
−
1
cm
.
2.3. X-ray crystallography
Single-crystal X-ray diffraction data for 1 were recorded on a Bruker
D8 QUEST with graphite-monochromated Mo-Kα radiation
(
λ = 0.71073 Å) at 273(2) K. Absorption corrections were applied
using multi-scan technique and performed by using the SADABS pro-
gram. The crystal structure was solved by means of direct methods and
t
Fig. 1. Standard ball-and-stick model of the [Ag34(SBu )16(CF
3
COO)10
2
−
2
(CO
3
)
5
(H
2
4
O) ]
. All the hydrogen atoms and dissociative Et
3
N are omitted for
refined by employing full-matrix least squares on F (SHELXTL-2014)
clarity. Left: the {Ag17
S
8
} cationic cluster, right: the {Ag17S } anionic cluster.
8
[
15]. Crystal data and structure refinements for compound 1 are listed
Colour code: Ag, violet, pink and turquoise; S, yellow; F, bright green; O, red; C,
gray-50%. (For interpretation of the references to colour in this figure legend,
the reader is referred to the web version of this article.)
in Table 1. Selected bond lengths (Å) and bond angles (°) for compound
1
are listed in Table S1. All the Ag⋯Ag interactions (Å) for compound 1
are listed in Table S2. Hydrogen bond parameters (Å, °) of compound 1
are listed in Table S3.
shown in Fig. 2a. While the {Ag17
S
8
} anionic cluster consists of se-
3
. Results and discussion
t−
−
venteen silver atoms, eight SBu ligands, four CF
3
COO ligands, four
2
−
.1. Structure analysis of {[Ag34(SBut)16(CF
coordinated H
2
O molecules, two bridging CO
(O24, O25, O26) hung on the Ag17 core through weak Ag⋯O
interaction (2.888 Å), as shown in Fig. 2b.
Obviously, both of the Ag17 cores in the cationic and anionic
clusters exhibit a sandwich structure, owing to their three parallel
macrocycles arranged layer by layer: an interlayer Ag ring (Ag, tur-
quoise) and bilevel inversion Ag quadrangles (Ag, pink) above and
below the Ag plane. Besides, one Ag atom (Ag, violet) is located on the
same plane of the Ag ring and also the centre of the Ag17 core. As
illustrated in Figs. 3 and S1, the two Ag quadrangles (Ag2–-
S1–Ag3–S2–Ag4–S3–Ag5–S4, Ag6–S5–Ag7–S6–Ag8–S7–Ag9–S8 in
3
ligands, and one free
3
3
COO)10(CO
3
)
5
(H
2
O) ]
4
2
−
+
CO
3
S
8
[
Et
3
N
]
2
n
} (1)
S
8
Single-crystal X-ray diffraction analysis reveals compound
t
+
{
[Ag34(SBu )16(CF
3
COO)10(CO
3
)
5
(H
2
O)
4
][Et
3
N
]
2
}
n
(1) (short for
8
{
Ag17
S
8
} dimer) crystallizes in space group Pbca and features a co-
S
4 4
ordination
polymer
COO) (CO
by
the
assembly
of
a
t
+
8
[
Ag17(SBu )
8
(CF
3
6
3
)]
SBU (short for {Ag17
S
8
}
cationic
t
−
8
S
8
cluster, Fig. 1, left) and a [Ag17(SBu )
8
(CF
3
COO)
4
(CO
3
)
3
(H
2
O)
4
]
SBU
S
4 4
(
short for {Ag17
S
8
} anionic cluster, Fig. 1, right) benefiting from the
2
−
4
4
a
bridging CO
3
in the μ
2
-ƞ , ƞ mode. In details, the {Ag17S } cationic
8
t
−
head–tail
arrangement
(a)
and
Ag19–S9–Ag20–S10–Ag21–-
cluster is comprised of seventeen silver atoms, eight BuS ligands, five
−
−
S11–Ag22–S12, Ag23–S13–Ag24–S14–Ag25–S15–Ag26–S16 in a head-
tail arrangement (b)) are built from alternant Ag–S bonds. Meanwhile
CF
3
3
COO ligands, and one free CF
3
COO ligand along with one free
2
−
CO
hung on the upper and lower sides of the Ag17
S core through
8
an Ag
4
quadrangle is formed among the four silver atoms in each Ag
S
4 4
weak Ag⋯O interaction (Ag6⋯O11 (2.646 Å), Ag9⋯O11 (2.606 Å),
quadrangle. The Ag
8
ring is built by eight silver atoms
Ag8⋯O12 (2.633 Å) and Ag3⋯O13 (2.670 Å), Ag5⋯O12 (2.750 Å)), as
2

J.-F. Shi, et al.
Inorganica Chimica Acta 497 (2019) 119107
Fig. 2. Side view of standard ball-and-stick model of the {Ag17
S
8
} cationic cluster (a), the {Ag17
S
8
} anionic cluster (b). Colour code: Ag, violet, pink and turquoise; S,
yellow; F, bright green; O, red; C, gray-50%. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this
article.)
(
Ag10–Ag11–Ag12–Ag13–Ag14–Ag15–Ag16–Ag17 in a head–tail ar-
rangement (Fig. 3a) and Ag27–Ag28–Ag29–Ag30–Ag31–A-
g32–Ag33–Ag34 in a head–tail arrangement (Fig. 3b)), which is at-
tributed to the Ag⋯Ag interactions. Then, the two inversion Ag
quadrangles are attached to the interlayer Ag ring and the central Ag
atom across the Ag–S bonds and Ag⋯Ag interactions [16] to construct
the sandwich-like structure of the Ag17 core. There is a slight dif-
ference in the Ag⋯Ag interactions (2.9623(16)–3.3788(13) Å in Fig. 3a
and 2.9817(16)–3.2920(14) in Fig. 3b) and Ag-S distance
2.400(3)–2.548(3) Å in Fig. 3a and 2.416(3)–2.594(3) Å in Fig. 3b)
Furthermore, the {Ag17
cluster fuse into
(H O)
S
8
} cationic cluster and the {Ag17
S
8
} anionic
t
the
{Ag17
S
8
}
dimer
([Ag34(SBu )16
2
−
4
2−
(CF
3
COO)10(CO
3
)
5
2
4
]
) by sharing the same CO
3
(O30, O31,
4
4
S
4
and O32 in the
μ
2
-ƞ ,
ƞ
mode). The charge of the
t
2−
8
[Ag34(SBu )16(CF
3
COO)10(CO
3
)
(H
5 2
O)
4
]
is balanced by two proto-
2−
nated Et
3
N. Interestingly, the two bridging CO
3
ligands (O27, O28,
t
S
8
O29 and O33, O34, O35) crosslink adjacent [Ag34(SBu )16(CF
3
COO)10
2
−
(CO ) (H O) ]
3
3
5
4
2
4
clusters, leading to the formation of a 2D
+
t
Å
{[Ag (SBu ) (CF COO) (CO ) (H O) ][Et N ] } honeycomb net-
16
3
10
3 5
2
4
3
2 n
(
work parallel to the bc plane with Ag–O bond length range from
2.463(17) to 2.525(15) Å (Fig. S2). As shown in Fig. 4, it contains six
{Ag S } clusters which are two couples of {Ag S } dimers and ad-
between the {Ag17
S
8
} cationic cluster and the {Ag17
S
8
} anionic cluster.
In the {Ag17
S
8
} cationic cluster, the Ag17
S
8
core is supported by
1
7
8
17 8
t−
2
2
3
4
2
2
4
4
eight SBu ligands (in the μ
4
-ƞ , ƞ , ƞ , ƞ mode, μ
4
-ƞ , ƞ , ƞ , ƞ mode,
jacent two {Ag S } cationic clusters in the smallest structural unit of
1
7 8
2
2
3
3
−
and μ
4
-ƞ , ƞ , ƞ , ƞ mode), five CF
3
COO ligands (in the μ
2
-O, O′
the honeycomb network. Each couple of {Ag S } dimers respectively
1
7 8
−
2−
mode), and further stabilized by one overhead CF
3
COO and one
connected with one {Ag S } cationic cluster by the bridging CO
1
7
8
3
2
−
overhead CO
3
. All silver atoms are 2-, 3- and 4-coordinated except
ligand (O27, O28, O29), meanwhile the adjacent two {Ag S } cationic
1
7 8
2−
the central Ag1 atom. In the {Ag17
S
8
} anionic cluster, the Ag17
S
8
core
clusters interconnected by the bridging CO
ligand (O33, O34, O35).
3
t
−
4
3
3
3
3
4
3
3
is supported by eight BuS ligands (in the μ
4
-ƞ , ƞ , ƞ , ƞ mode, μ
4
4
-ƞ ,
Furthermore, the two couples of {Ag S } dimers share one bridging
1
7 8
2
2
4
3
2
3
4
−
3
3
2
2−
ƞ , ƞ , ƞ mode, μ
4
-ƞ , ƞ , ƞ , ƞ mode, μ
4
-ƞ , ƞ , ƞ , ƞ mode, and μ
-ƞ ,
CO
ligands (O33, O34, O35) to fabricate the close honeycomb
3
3
4
ƞ , ƞ , ƞ mode), four CF
3
COO ligands (in the μ
2
-O, O′ mode and syn-
structure [17]. The average Ag···Ag separation connected by the brid-
2
−
μ
3
-O, O′ mode), four coordinated H
2
O molecules (in the μ
1
-O mode),
ging CO
ligands is 5.886 Å [18]. From the topological point of view,
3
2
−
two bridging CO
3
ligands (O27, O28, O29 and O33, O34, O35 in the
each {Ag S } cationic cluster or {Ag S } anionic cluster is stabilized
1
7
8
17 8
4
4
4
2−
2−
μ
3
-ƞ , ƞ , ƞ mode), and further stabilized by one overhead CO
3
. All
by three 3-connected CO
ligands, which is a planar triangular linker.
3
silver atoms are 2-, 3- and 4-coordinated except the central Ag18 atom.
Topological analysis reveals that the 2D layer of 1 shows a 3-nodal 2D
Fig. 3. Top view of standard ball-and-stick model of the Ag17
S
8
core: in the {Ag17
S
8
} cationic cluster (a), in the {Ag17S } anionic cluster (b). Colour code: Ag, violet,
8
pink and turquoise; S, yellow; F, bright green; O, red; C, gray-50%. (For interpretation of the references to colour in this figure legend, the reader is referred to the
web version of this article.)
3

J.-F. Shi, et al.
Inorganica Chimica Acta 497 (2019) 119107
Fig. 4. Two couples of {Ag17
S
8
} dimers and adjacent two {Ag17
S
8
} cationic clusters in the smallest structural unit of the honeycomb network of 1; dissociative Et N,
3
all the fluorine atoms and hydrogen atoms are omitted for clarity. Colour code: Ag, violet, pink and turquoise; S, yellow; O, red; C, gray-50%. (For interpretation of
the references to colour in this figure legend, the reader is referred to the web version of this article.)
investigated (Fig. 7a). The maximum emission peak λmax is located at
4
00 nm and several weaker shoulder peaks at 474 nm, 488 nm, 520 nm
and 550 nm upon excitation at 244 nm at 298 K [20]. The emission of 1
at 298 K is assigned to a ligand to-metal-charge-transfer (LMCT) tran-
sition along with a cluster-centered (CC) transition strengthened by
I
I
Ag ⋯Ag interactions [13]. In order to get better insight into its pho-
tophysical property, the photoluminescence spectra at 77 K of 1 in the
solid state was measured. Compound 1 emits intense green-yellow light
emission (λmax = 550 nm) at 77 K upon excitation at 365 nm. The
emission of 1 at 77 K can be attributable to the CC excited state, and the
CC emission was strengthened and the maximum emission peak of 1 has
undergone red shift from 298 K to 77 K. The temperature-sensitive lu-
minescence behavior is reversible when the temperature changes back
and forth between 298 K and 77 K. Thus compound 1 will be hoped to
be a good temperature probe giving the credit to its reversible ther-
mochromic luminescence behavior.
Fig. 5. Simplified representations of the 2D layer in 1; colour code: the
2
−
{Ag17S
8
} cationic cluster, pink; the {Ag17
S
8
} anionic cluster, yellow; the CO
3
4. Conclusions
linker, blue. (For interpretation of the references to colour in this figure legend,
t
the reader is referred to the web version of this article.)
In summary, a novel 2D layer structure {[Ag34(SBu )16(CF
COO)10
3
+
(
CO
3
)
5
(H
2
O)
4
][Et
3
N
]
2
}
n
(1) based on {Ag17
S
8
} silver chalcogenide
t
+
3
clusters, namely [Ag17(SBu )
8
(CF
3
COO)
6
(CO )] cationic cluster and
3
net with a point symbol of {6 } (Fig. 5) [19]. Furthermore, adjacent 2D
t
−
[
Ag17(SBu )
8
(CF
3
COO)
4
(CO
3
)
3
(H
2
O)
4
]
anionic cluster, has been ob-
layers are extended into a 3D supramolecular structure through hy-
2−
t
−
drogen bonds CeH···F (H⋯F 2.51 Å) between the BuS ligands and
tained and well-defined. Interestingly, the CO
3
serving as the brid-
−
ging ligand plays an extremely important role in the 2D layer structure.
In addition, luminescence properties of 1 were investigated. The cur-
rent work will extend the way to prepare functional high-nuclearity
silver-thiolate clusters.
CF
3
COO auxiliary ligands (Fig. 6).
3.2. Luminescence property
The photophysical luminescence of 1 in the solid state has been
4

J.-F. Shi, et al.
Inorganica Chimica Acta 497 (2019) 119107
t
]2−
Fig. 6. Wires/sticks representation of the crystal packing of 1. Hydrogen atoms are omitted for clarity. Colour code: [Ag34(SBu )16(CF
3
COO)10(CO
3
)
5
(H
2
O)
4
,
bright green, red and yellow. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
for 1. 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.
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.ica.2019.119107.
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