Investigating the influence of a CrO42?/Cr2O72? template in the formation of a series of silver-chalcogenide clusters

Article abstract of DOI:10.1039/c8nj04965c

Three new silver-chalcogenide clusters protected by naphthyl ligands are described in this work, namely [Ag₁₄(SCH₂C₁₀H₇)₆(CF₃COO)₈(DMAc)₆] (1), [Ag₃₀(SCH₂C₁₀H₇)₁₈(CrO₄)₂(DMAc)₂ (CF₃COO)₈] (DMAc = dimethylacetamide) (2) and {Ag₁₂(SCH₂C₁₀H₇)₆(CF₃COO)₄(CH₃CN)₆(Cr₂O₇)}_n (3). Their crystal structures were studied by X-ray crystallography, and they show hollow-core-shell (1), template-core-shell (2) and 1D infinite (3) structures, respectively. The luminescence properties of cluster 1 were investigated, which showed interesting thermochromic variation from red to bright yellow. Moreover, the chromate ions were proven to act as templates in forming the silver clusters through a series of experiments to prepare compounds 2 and 3, which could be considered as derivatives of cluster 1.

Full text of DOI:10.1039/c8nj04965c

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2ꢀ
2ꢀ
Investigating the influence of a CrO /Cr O
4
2 7
template in the formation of a series of
Cite this: New J. Chem., 2019,
silver–chalcogenide clusters†
43, 115
Yan-Ling Li, Qing-Qing Xu, Si Li, Ren-Wu Huang, Xiao-Fei Liu, Yong-Li Wei* and
Shuang-Quan Zang
*
Three new silver–chalcogenide clusters protected by naphthyl ligands are described in this work, namely
Ag14(SCH (CF COO) (DMAc) (1), [Ag30(SCH 18(CrO (DMAc) (CF COO) (DMAc
dimethylacetamide) (2) and {Ag12(SCH (CF COO) CN) (Cr )} (3). Their crystal structures
were studied by X-ray crystallography, and they show hollow-core–shell (1), template-core–shell (2) and
D infinite (3) structures, respectively. The luminescence properties of cluster 1 were investigated, which
[
2
C
10
H
7
)
6
3
8
6
]
2
C
10
H
7
)
4
)
2
2
3
8
]
=
2
C
10
H
7
)
6
3
4
(CH
3
6
2 7 n
O
Received 30th September 2018,
Accepted 8th November 2018
1
showed interesting thermochromic variation from red to bright yellow. Moreover, the chromate ions
were proven to act as templates in forming the silver clusters through a series of experiments to prepare
compounds 2 and 3, which could be considered as derivatives of cluster 1.
DOI: 10.1039/c8nj04965c
rsc.li/njc
3
0,31
ꢀ
2ꢀ
2ꢀ
2ꢀ
sulfide
and polyatomic (NO3 , CrO4 , SO4 , CO3 , pyro-
Introduction
vanadate, and polyoxometalate) anions, have been found in high-
32–39
Coinage metal clusters have consistently attracted researchers’ nuclear silver clusters.
attention since F. A. Cotton introduced the term ‘cluster’ in the clusters has been summarized by Prof. Wang, who reported that
960s. Especially after the concept of Mꢁ ꢁ ꢁM metallophilic an anion template could not only control the size and shape of a
Their superiority in forming huge
26
1
1
–3
interactions was proposed in the 1980s, research in this field cluster, but could also stabilize it. Moreover, functionalized anions
4
,5
blossomed in the following decades, including studies of could also bring interesting physical properties to the system. For
6
–8
9–12
8ꢀ
alkynyl and chalcogenide based gold and silver clusters.
example, the [Mo
6
O
22
]
ion conferred electronic communication
t
32
Metallophilic interactions are well-established for gold(I) and behavior on the [Ag (Mo O ) (CRC Bu) ](CF SO )
and
silver(I) complexes, and have been proven to be efficient for [Ag (CRC Bu) (CF COO) (Mo O )]ꢁ2CH OH clusters, and the
6
0
6
22 2
38
3
3 6
6
t
4
0
20
3
12
6
22
3
6ꢀ
extra complexity, providing a high probability of forming high- [W O ] ion lent both luminescence and electrochemical proper-
6
21
1
2–16
ꢀ
t
nuclearity clusters.
Besides, the introduction of R–CH
2
S
ties to [Ag34(S Bu)26(W
6
9
O
21)(CF
3
COO)](CF
3
COO)ꢁEt
3
Nꢁ20CH
3
OH at
1
moieties into clusters may functionalize the resulting clusters, ambient temperature.
so that they not only possess appealing structures, but also
In previous studies, we successfully introduced the polyoxo-
1
7–19
12ꢀ
display new optical, electrical and chemical properties.
example, the dodecanuclear cluster Ag12(SCH (CF
For molybdate anion [Mo20
O
66
]
into Ag–S systems to obtain a
2
1
2 10
C
H )
7 6
3
CO giant peanut-like 62-core silver–thiolate nanocluster. In order
2 6
) -
2
0
(
CH CN)6 not only exhibits fascinating luminescence emission, to study the influence of the template on the structure and
3
but also shows thermochromic variation from red to bright yellow. properties of a cluster, we are willing to try other anions.
2
0–25
Our group has been committed to studies of Ag–S clusters.
We have found that the preparation of clusters with specific metal
numbers is hardly controlled, because such processes always anionic candidates, but their roles as templates for silver
Chromate anions show flexible coordination modes, such as
m -Z ,Z ,Z and m12-Z ,Z ,Z ,Z , which makes them perfect
6
2
2
2
3
3
3
3
26
involve the intricate assembly of multiple components. However, clusters are scarcely reported. To our knowledge, few silver
recent research progress shows that if anion templates are intro- clusters with chromate anion templates have been reported
2
7–29
28,35,40,41
duced, such preparations could be comparatively predictable.
to date.
Wang et al. reported two unprecedented
ꢀ
ꢀ
ꢀ
ꢀ
35
Various anion templates, such as halogen (F , Cl , Br , and I ), chromate-templated Ag22 and Ag35 silver–alkynyl clusters;
28
C. W. Liu et al. reported a Ag16 silver–dithiophosphate cluster.
College of Chemistry and Molecular Engineering, Zhengzhou University,
Herein, we report the syntheses and crystal structures of
Ag14(SCH (CF COO) (DMAc) (1) and its derivatives
2 10 7 18
based on the chromate and dichromate ions, Ag30(SCH C H ) -
Zhengzhou 450001, China. E-mail: zangsqzg@zzu.edu.cn
Electronic supplementary information (ESI) available. CCDC 1869846–1869848.
For ESI and crystallographic data in CIF or other electronic format see DOI:
0.1039/c8nj04965c
2
C
10
H
7
)
6
3
8
6
†
1
(CrO
4
)
2
(DMAc)
2
(CF
3
COO)
8
(DMAc = dimethylacetamide) (2) and
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New J. Chem., 2019, 43, 115--120 | 115

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Ag12(SCH
NJC
{
2 10
C
H
7
)
6
(CF
3
COO)
(CH CN) (Cr O )}
4 3 6 2 7 n
(3), respectively. respectively. Meanwhile, the [Ag14
S
6
] core is further stabilized
COO ligands, with Ag–O distances in the
ꢀ
The cluster 1 has a core–shell structure with a nanoscale size. In by the DMAc and CF
the presence of K Cr O , we obtained cluster 2 and polymer 3. range of 2.203(9)–2.582(9) Å. All the CF COO anionic ligands
Cluster 1 shows a peanut-shaped structure with two CrO4 ions have m -O :O bridging mode; as for the six DMAc molecules,
3
ꢀ
2
2
7
3
2ꢀ
0
00
2
at the core. Polymer 3 shows a 1D structure; the [Ag S ] clusters two have mono-O and the other four adopt a m -O mode. Taking
1
2 6
2
extend through the bridging dichromate. Dichromate ions play a into account the expansion of the ligands, the size of the
predominant template function in forming cluster 2 and polymer tetradecanuclear Ag–S cluster 1 can reach the nanoscale, with
3
3
. Studies of the luminescence properties of cluster 1 reveal that dimensions of ca. 15 ꢂ 20 ꢂ 20 Å , which has been proven by
cluster 1 shows interesting thermochromic variation from red to TEM experiments (Fig. S1, ESI†).
bright yellow.
Crystal structure of [Ag (SCH C H ) (CrO ) (DMAc)
2
3
0
2
10 7 18
4 2
(
CF COO) ] (2)
3 8
Results and discussion
Crystal structure of [Ag14(SCH C H ) (CF COO) (DMAc) ] (1)
2 10 7 6 3 8 6
The addition of K
2 2 7
Cr O in the synthesis of cluster 2 produced
a peanut-shaped cage, which was templated by two in situ
2
ꢀ
ꢀ1
generated CrO4 ions. The IR vibration at 906 cm confirmed
Single-crystal X-ray diffraction analysis revealed that cluster 1
crystallizes in the orthorhombic space group Pbca, in which
fourteen silver(I) ions are aggregated through a linkage of six
2
ꢀ
ꢀ1
the presence of the CrO4 ions, and the band at 1656 cm was
assigned to the CF COO anion. The molecular structure of
ꢀ
3
cluster 2 determined by single-crystal X-ray diffraction data is
illustrated in Fig. 2(a). Selected bond lengths and angles are
presented in Table S2 (ESI†). Cluster 2 crystallizes in the
monoclinic space group P1%, and the cage is templated by two
ꢀ
ꢀ
2 3
SCH –naphthyl ligands and stabilized by eight CF COO and
six DMAc auxiliary ligands (Fig. 1(a)). All the S atoms come from
ꢀ
2
SCH –naphthyl ligands. As shown in Fig. 1(b), the S1 atoms
1
1
1
1
1
5
adopt a m -Z :Z :Z Z :Z coordination mode, linking Ag1, Ag2,
2
ꢀ
ꢀ
CrO
4
ions and protected by 18 peripheral SCH
2
–naphthyl
Ag3, Ag4 and Ag7 to build a compressed Ag S pentagonal
pyramid, which is made up of a silver pentagonal base and
5
ꢀ
ligands, eight CF COO ligands, and two DMAc molecules
3
ꢀ
1
(
Fig. 2(b)). The SCH –naphthyl ligands adopt two coordination
2
five Ag S triangle faces. The S2 and S3 atoms both adopt a
5
1
1
1
1
1
1
1
1
1
1
modes, m -Z :Z :Z and m -Z :Z :Z Z . In the m -Z :Z :Z mode,
1
1
1
3
4
3
m
4
-Z :Z :Z Z ligation mode, linking four silver(I) ions (Ag2,
Ag4, Ag5 and Ag6–S2; Ag1, Ag3, Ag5 and Ag6–S3) to build
compressed Ag S square pyramids. Layers also can be used to
sulfur atoms (S1, S3, S4 and S6) link three Ag(I) ions, forming a
compressed Ag S trigonal pyramid with a Ag triangle base and
three Ag S triangle faces. Sulfur atoms (S2, S5, S7, S8 and S9)
bind Ag(I) ions in the m
pressed Ag S square pyramid with four silver ions at the base.
3
3
4
2
describe the whole structure. As shown in Fig. 1(b), in the first
layer, there are three silver ions (Ag2, Ag3 and Ag6) arranged in
a triangle (with Agꢁ ꢁ ꢁAg distances of 2.915(2), 3.009(1) and
1
1
1 1
4
-Z :Z :Z Z mode, forming a com-
4
All these trigonal and square pyramids form the peanut-shape
cage by sharing their Ag-corners. The Ag–S distances fall in the
reasonable range of 2.413(2)–2.651(2) Å, which are comparable
3.103(2) Å), and the S atoms are shared by each pair of silver ions
on the side of the Ag-triangle like a traditional checkerboard.
The Ag–S distances fall in the range of 2.475(2)–2.599(2) Å.
Correspondingly, the other set of atoms (Ag2#, Ag3#, Ag6#
and S) forms another checkerboard in the opposite direction
with a distance of 3.745(2) Å to the first one. An eight-
3
5,42
ꢀ
to the reported values.
2
The SCH –naphthyl ligands stick
out of the [Ag30S18] shell with angles of ca. 161 and 241 with
ꢀ
respect to the Ag
3
4 3
and Ag bases. Additionally, eight CF COO
anions and two DMAc molecules finish the protection of the
2
membered (Ag1–Ag7–Ag4–Ag5) ring is inserted between these
two checkerboard-like layers, which are stabilized through Ag–S
2ꢀ
[
(CrO
4
2
) @Ag30S18] core by coordinating to Ag(I) ions with
Ag–O distances of 2.193(4)–2.555(5) Å. This shows that the
bonds (with Ag–S distances of 2.495(3)–2.756(2) Å) and Agꢁ ꢁ ꢁAg
ꢀ
presence of CF COO and DMAc in the system enhances the
3
argentophilic interactions (2.946(2)–3.390(2) Å). The diameter
2ꢀ
6
stability of the high-nuclear [(CrO4 ) @Ag S ] cage.
2
2
30 18
of the eight-membered Ag
with respect to the Ag5ꢁ ꢁ ꢁAg5# and Ag7ꢁ ꢁ ꢁAg7# distances,
8
ring is ca. 8.111(3) ꢂ 9.037(7) Å
The silver ions can be divided into 10 types according to their
coordination environment, taking into account the Agꢁ ꢁ ꢁAg
Fig. 1 (a) General description of cluster 1 protected by different ligands.
b) The inner core framework, [Ag14 ], in which all the protecting ligands
2
ꢀ
(
S
6
Fig. 2 (a) The framework of cluster 2 templated by two CrO
4
ions. (b) The
2ꢀ
are eliminated for clarity. The hydrogen atoms have been omitted for
clarity. Color legend: green, Ag; yellow, S; blue, N; red, O; turquoise, F;
gray, C.
inner core, [(CrO
4
2
) @Ag30
S18], in which all the protecting ligands are
eliminated for clarity. The hydrogen atoms have been omitted for clarity.
Color legend: green, Ag; yellow, S; blue, N; red, O; turquoise, F; gray, C.
116 | New J. Chem., 2019, 43, 115--120
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Paper
contacts. Ag1, Ag2, Ag3, Ag4, Ag9, Ag10, Ag11 and Ag12 have a
2 3 2 3
[Ag–S OAg ] coordination environment; Ag13 has a [Ag–S Ag ]
environment; the other Ag ions have Ag5, Ag6–[Ag–S OAg ];
3
3
Ag14, Ag15–[Ag–S O Ag ], Ag7–[Ag–S O ]; and Ag8–[Ag–SOAg ]
2
2
3
2
2
4
environments, respectively. These silver ions show diverse irregular
coordination geometries. The Ag–Ag distances (from 2.869(7) to
3.343(7) Å) show typical argentophilic interactions, which are
significantly shorter than twice the van der Waals radius (ca.
4
3,44
3
.44 Å) of the silver atom.
The whole cluster is completed by
ions with Ag(I) inside the silver core. Two
template CrO4 ions are encapsulated in the [Ag S ] cage, and
2ꢀ
the linkage of CrO
4
2ꢀ
30 18
1
1
1
coordinate to Ag(I) ions in the m -Z :Z :Z mode. The Ag8–O2,
3
Ag7–O4 and Ag7#–O1 distances are 2.205(7), 2.484(1) and
2
.457(2) Å, respectively, indicating strong contacts with the
2
ꢀ
[Ag30
S18] shell. The CrO
4
ions have tetrahedral geometry, as
they always appear to, but with a slight distortion with t = 0.8
4
5
(for an ideal tetrahedron, t
4
= 1), and the O–Cr–O angles
range from 96.542(7)1 to 136.727(8)1. Two template chromate Fig. 3 (a) The dodecanuclear cluster unit Ag12(SCH C H ) (CF COO) -
2
10 7 6
3
6
ions share two silver ions, forming an 8-membered ring with a (CH
3 6
CN) of polymer 3. (b) 1D chain formed by the extension of the
dodecanuclear cluster unit through dichromate ions. The hydrogen atoms
have been omitted for clarity. The turquoise tetrahedra represent the
dichromate ions. Color legend: green, Ag; yellow, S; blue, N; red, O;
turquoise, F; gray, C.
chair conformation. The whole structure has pseudo-twofold
symmetry, and the inversion center is situated at the center of
2
ꢀ
the 8-membered ring. The [(CrO
4
3
)
2
@Ag30
S
18] cage has an
ꢀ
outer diameter of ca. 22 ꢂ 26 ꢂ 19 Å , taking the SCH
2
–naphthyl
18] has a
2ꢀ
ligands into account. The inner core [(CrO
4
)
2
@Ag30S
3
diameter of ca. 13 ꢂ 8 ꢂ 10 Å with respect to the Ag14ꢁ ꢁ ꢁAg14#, Without the addition of K
S5ꢁ ꢁ ꢁS5# and Ag9ꢁ ꢁꢁAg9# distances, respectively. core–shell cluster 1, which indicates that the anionic CrO
Such Ag–O distances can be compared to the clusters [Ag - template is very important for the formation of 2. DMAc also
2 2 7
Cr O , we obtained the 14-nuclearity
2ꢀ
4
2
2
t
(
(
CRC Bu) (CrO )](BF ) , [Ag (CRCPh) (CrO ) (TMEDA) ]- plays an important role in the self-assembly. It not only
BF4)3 and [Ag (CrO ) {S P(OEt) } ] (PF ) . Such a condensed coordinates to Ag(I) as an auxiliary ligand to stabilize the final
1
8
4
4 2
35
28
28
4 2
4
3
5
16
4
2
2 12 2
6 4
2ꢀ
skeleton also benefits the stability of this huge [(CrO
4
2
) @Ag30
S
18
]
structure, but also acts as a weak base to favor the transformation
2
ꢀ
2ꢀ
cluster in air.
of Cr
2
O
7
to CrO
4
. We also attentively added different sources
CrO , K CrO , (NH CrO ) to the reaction
of chromate (Na
2
4
2
4
)
4 2
4
Crystal structure of
mixture in the preparation of 2, but no crystals were obtained,
{Ag12(SCH
2
C
10
H
7
)
6
(CF
3
COO)
4
(CH
3
CN)
6
(Cr
2
O
7
)}
n
(3)
2ꢀ
which indicates that the slow introduction of CrO
4
into the
The X-ray structural analysis of 3 reveals the existence of a reaction system could avoid the formation of insoluble Ag CrO4
2
[
Ag S ] cluster connected by dichromate ions forming a 1D and is very important for the formation of 2.
12 6
2
ꢀ
2ꢀ
2ꢀ
polymer. The [Ag (SCH C H ) (CF COO) (CH CN) ] cluster
For cluster 3, Cr
2
O
7
but not CrO
4
ions exist as templates
1
2
2
10 7 6
3
4
3
6
(
(
2
Fig. 3(a)) in 3 greatly resembles Ag12(SCH
CH CN)
.960(1) to 3.239(1) Å, indicate argentophilicity.
The disordered trifluoroacetate groups display m
in association with two silver centers. Acetonitrile is a terminal (CH
2
C
10
H
7
)
6
(CF
3 6
COO) -
in the absence of DMAc, which indicates that the basic DMAc
3
6
.† The Ag–Ag distances in 3, which range from influences the form of the template. The template function of
the dichromate ions also can be proven by a comparison of
2
-bridging mode cluster 3 and the reported cluster Ag12(SCH
2
C
10
H
7
)
6
(CF
3
COO)
6
-
]
2
0
3
CN)
6
.
Both clusters contain a dodecanuclear [Ag12S
6
ꢀ
ꢀ
ligand in monodentate coordination mode. The dichromate ions cluster inner core protected by C H CH S , CF COO and
1
0
7
2
3
show m -mode. The terminal O atoms coordinate to two silver atoms acetonitrile, but cluster 3 forms a 1D polymer in the presence
6
2
ꢀ
2
2ꢀ
in one Ag S cluster; the other pair of O atoms in the dichromate of Cr
2
O
7
ions. In cluster 3, the Cr
2
O
7
ions adopt a
12 6
1
1
1
1
ion bind silver atoms in the neighboring Ag12
bridging O8 atom links two Ag12
Fig. 3(b)). The dichromate connectors join one Ag12S
6
two others in this way, thus developing a 1D coordination polymer free dichromate ions (1.62 Å), and the Cr–O
along the a axis. The S atoms in the SCH
S
6
cluster; and the
m
6
-Z :Z :Z :Z :Z coordination mode, and connect [Ag12
clusters simultaneously cluster units in an infinite chain. The Cr–O
S
6
]
S
6
t
distances fall into
(
cluster to the range of 1.588–1.597 Å, which are comparable to those in
4
6
b
distance of
ꢀ
2ꢀ
2
–naphthyl ligand all 1.777(8) Å is also a little shorter than that in free Cr
2
O
7
ions
adopt m -mode. The Ag–S distances in the Ag S cluster range from (1.80 Å).
4
12 6
2
ꢀ
2
.421(2) to 2.706(2) Å, which are in the normal interval for Ag(m -SR).
The O atoms of the encapsulated CrO
the intercluster Cr O
in cluster 2 and of
ions in polymer 3 show significant
interactions with the Ag atoms because of the high affinity of
In order to confirm the templating function and origin of the silver for O donors. The average Ag–O distances of 2.35 Å (in 2)
4
4
2
ꢀ
2 7
Dichromate ion templating
2
ꢀ
CrO
4
ions, several comparative experiments were performed. and 2.58 Å (in 3) show comparatively strong interactions.
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On one hand, chromate ions introduce new clusters; on the
NJC
other hand, the existence of chromate and dichromate ions
greatly enhances the stability of the resultant clusters, due to
their high capacities for extra electrons from the Ag-clusters.
Morphological studies
The morphologies of single crystals of clusters 1 and 2 in
ethanol were investigated using TEM images. Fig. S1 (ESI†)
shows that cluster 1 exists as discrete particles with an average
size of about 2 nm, which is close to the size described above.
The TEM image of cluster 2 reveals that discrete particles exist,
with an identified size of about 3.0 nm (Fig. S2, ESI†), which is
2
ꢀ
close to the above description of [(CrO4 ) @Ag S ]. Some
2
30 18
other bigger particles may be attributed to the aggregation of Fig. 4 The temperature-dependent luminescence spectra of cluster 1
excited at 360 nm in the solid state, showing prominent dual emission
characteristics.
several clusters.
Optical properties
The phase purity of 1 was confirmed by the corresponding On the other hand, the LE emission bands were constant at 660 nm
powder X-ray diffraction (PXRD) patterns (Fig. S3, ESI†). The with a comparatively slow increase in intensity, which is attributed
UV-vis spectrum of 1 in the solid state at room temperature to the S 3p - Ag 5s charge transfer in the cluster. Such
shows broad absorption from 200 nm to 450 nm (Fig. S4, ESI†), luminescence is very similar to that of our previously reported
2
0
where two distinct absorption peaks can be found at about cluster, Ag12(SCH
3
3
C
H
)
(CF
50 nm and 400 nm. The high-energy (HE) absorption at ca. shows interesting dual emission.
50 nm can be assigned to the transition of the ligand involving
COO)
(CH
CN)
,
which also
2
10
7
6
3
6
3
6
the p orbitals of the naphthyl ring. The low-energy (LE) absorption
at ca. 400 nm is assigned to the S 3p - Ag 5s transition, as a
Experimental
General procedures
47
similar assignment was made for a hypothetical Ag S monomer.
2
The broad absorption suggests that more than one excited state All the starting materials were of analytical grade as obtained
48
may be populated.
from commercial sources, and used without further purification.
Powder X-ray diffraction (PXRD) patterns (Fig. S5, ESI†) The ligand 2-(methylthio)naphthalene (HSCH C H ) was synthe-
2
10 7
20
showed the purity of cluster 2. The absorption spectrum of a sized by a reported procedure.
red powder sample of 2 was measured in the solid state at room
FT-IR spectra were recorded using KBr pellets in the range of
ꢀ1
temperature. As shown in Fig. S6 (ESI†), the broad higher 4000 to 400 cm on a Bruker VECTOR 22 spectrometer. Elemental
energy absorption band in the range of 200–400 nm could be analyses for C, H, N and S were performed on a Perkin-Elmer 240
ascribed to the intraligand p–p* transition of the naphthyl elemental analyzer. Transmission electron microscopy (TEM)
rings. The absorption peak from 400 to 600 nm is consistent measurements were performed on a JEM-2100 microscope. In
with the dark-red color of the crystals. The intense low-energy the preparation of samples 1 and 2 for TEM observation, the
band in the visible region can reasonably be assigned to the crystals were first dispersed in ethanol using an ultrasonic bath
charge transfer from the S 3p to the Ag 5s orbitals. As expected, and then dropped onto a copper grid, which was dried in air at
2
ꢀ
with the existence of the CrO
quenched for cluster 2.
4
species, the luminescence is room temperature and kept under vacuum for 20 min before
TEM observation. The software NANO MEASURER 1.2 was
In order to clarify the luminescence characteristics of cluster applied to calculate the particle sizes of the nanoclusters. Powder
1, we extended the test conditions from 293 K to 93 K. The X-ray diffraction (PXRD) data for 1 and 2 was collected on a
results show that no detectable luminescence emission was Rigaku D/Max-2500PC diffractometer with Cu-Ka radiation
observed at room temperature, while a slight dual emission (l = 1.5418 Å) over the 2y range of 3–501 at room temperature.
could be found at lower temperatures and the intensity UV-visible absorption spectra were recorded on a TU-1900 double-
increases with decreasing temperature. Upon cooling from beam UV-vis spectrophotometer. Luminescence spectra for the solid
293 K to 93 K under 360 nm excitation, the HE emission bands sample of 1 were recorded on a Hitachi 850 fluorescence
of cluster 1 show a slight blue-shift (from 590 and 540 nm to spectrophotometer.
5
60 and 530 nm, respectively) with a continuous increase in
Synthetic procedures
intensity, which becomes dominant at 93 K, as shown in Fig. 4.
The emission of 1 at low temperatures may be caused by the
Preparation of [Ag (SCH C H ) (CF COO) (DMAc) ] (1). A
1
4
2
10 7 6
3
8
6
enhanced rigidity, which effectively reduces the loss of energy mixture of 2-(methylthio)naphthalene (0.017 g, 0.10 mmol) and
4
2
by non-radiative decay. The HE emissions at 530 nm and AgCF
3
COO (0.044 g, 0.10 mmol) in ethanol–DMAc (v : v = 1 : 1,
5
60 nm can be ascribed to the excimer-like emission from a 6.0 mL) gave pale-yellow crystals of 1 by evaporation in the dark
20
naphthyl-based excited state that is involved in aromatic stacking.
at room temperature. The crystals were manually isolated
118 | New J. Chem., 2019, 43, 115--120
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and washed with ethyl ether and dried at room temperature. (No. 21671175); Program for Science & Technology Innovation
Yield: 82% (based on HSCH ). Calcd for C106 Talents in Universities of Henan Province (164100510005);
F Ag (Fw: 3976.52): C, 32.02; H, 2.74; N, 2.11; O, 8.85; S, Program for Innovative Research Team (in Science and Technology)
2
C
10
H
7
108 6 22 6
H N O S -
2
4
14
4
.84%. Found: C, 32.46; H, 2.53; N, 2.32; O, 8.49; S, 4.32%. IR in Universities of Henan Province (19IRTSTHN022).
ꢀ1
(KBr, cm ): 3050 (m), 2940 (w), 1670 (s), 1420 (m), 1210 (s),
840 (s), 721 (s).
2 10 7 4 2 2 3 8
Preparation of [Ag30(SCH C H )18(CrO ) (DMAc) (CF COO) ]
Notes and references
(
2). Cluster complex 2 was obtained under ambient conditions. A
mixture of ethanol (3.0 mL), DMAc (3.0 mL), 2-(methylthio)-
naphthalene (0.017 g, 0.10 mmol) and AgCF COO (0.044 g,
.10 mmol) was treated with K Cr O (0.029 g, 0.01 mmol). After
1 M. Jansen, Angew. Chem., Int. Ed. Engl., 1987, 26, 1098
(Angew. Chem., 1987, 99, 1136).
2 F. Scherbaum, A. Grohmann, B. Huber, C. Kr u¨ ger and
H. Schmidbaur, Angew. Chem., Int. Ed. Engl., 1988, 27, 1544
(Angew. Chem., 1988, 100, 1600).
3
0
2
2 7
stirring for 15 min, the resultant solution was kept in the dark.
Red crystals of 2 were obtained by evaporation at room temperature.
Yield: 73% (based on HSCH
Cr Ag30 (Fw: 7664.86): C, 34.79; H, 2.37; N, 0.36; O, 5.43; S, 7.53%.
Found: C, 34.36; H, 2.53; N, 0.42; O, 5.69; S, 7.32%. IR (KBr, cm ):
056 (w), 2916 (w), 1656 (s), 1201 (s), 1130 (s), 906 (m), 836 (m), 823
m), 748 (m).
Preparation of {Ag (SCH C H ) (CF COO) (CH CN) (Cr O )}
2
C
10
H
7
). Calcd for C222
H
180
N
2
O
26
S
18
F
24
-
3 F. Scherbaum, A. Grohmann, G. M u¨ ller and H. Schmidbaur,
Angew. Chem., Int. Ed. Engl., 1989, 28, 463 (Angew. Chem.,
1989, 101, 464).
4 H. Schmidbaur, Chem. Soc. Rev., 1995, 24, 391.
5 H. Schmidbaur and A. Schier, Chem. Soc. Rev., 2012, 41, 370.
6 G. G. Gao, P. S. Cheng and T. C. W. Mak, J. Am. Chem. Soc.,
2009, 131, 18257.
2
ꢀ
1
3
(
12
2
10 7 6
3
4
3
6
2 7 n
(3). Polymer 3 was prepared by a similar procedure to cluster 2,
except using acetonitrile instead of DMAc. A solution of EtOH–
MeCN (3 mL : 3 mL) containing 2-(methylthio)naphthalene
7 L. L. Wen, H. Wang, C. Q. Wan and T. C. W. Mak, Organo-
metallics, 2013, 32, 5144.
(
0.017 g, 0.10 mmol) and AgCF
added dropwise with an ethanol solution of K
.01 mmol). The resultant solution was kept in the dark for
several days. Red-orange crystals were obtained in a yield of 65%
3
COO (0.044 g, 0.10 mmol) was
8 D. Rais, J. Yau, D. Michael, P. Mingos, R. Vilar, A. J. P. White
and D. J. Williams, Angew. Chem., Int. Ed., 2001, 40, 3464.
9 H. Y. Yang, Y. Wang, H. Q. Huang, L. Gell, L. Lehtovaara,
S. Malola, H. H ¨a kkinen and N. F. Zheng, Nat. Commun.,
2013, 4, 2422.
2
Cr (0.029 g,
2 7
O
0
(based on HSCH C H ). Calcd for C H N O S F CrAg (Fw:
2 10 7 43 36 3 8 3 6 6
1
3
3
632.15): C, 31.64; H, 2.22; N, 2.57; O, 7.84; S, 5.89%. Found: C, 10 H. Y. Yang, Y. Wang and N. F. Zheng, Nanoscale, 2013, 5, 2674.
ꢀ1
1.36; H, 2.53; N, 2.42; O, 7.69; S, 5.62%. IR (KBr, cm ): 11 G. Li, Z. Lei and Q. M. Wang, J. Am. Chem. Soc., 2010, 132, 17678.
046 (w), 2926 (w), 1664 (s), 1209 (s), 1030 (s), 846 (m), 738 (m). 12 C. E. Anson, A. Eichh o¨ fer, I. Issac, D. Fenske, O. Fuhr,
P. Sevillano, C. Persau, D. Stalke and J. T. Zhang, Angew.
Chem., Int. Ed., 2008, 47, 1326.
Conclusions
1
3 X. J. Wang, T. Langetepe, C. Persau, B. S. Kang, G. S. Sheldrick
and D. Fenske, Angew. Chem., 2002, 114, 3972 (Angew. Chem. Int.
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4 D. Fenske, C. Persau, S. Dehnen and C. E. Anson, Angew.
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5 D. Fenske, C. E. Anson, A. Eichh o¨ fer, O. Fuhr, A. Ingendoh,
C. Persau and C. Richert, Angew. Chem., 2005, 117, 5376
This work is focused on a series of newly designed and prepared
silver–chalcogenide clusters. We systematically described their
preparation, structures, and optical properties. Cluster 1 was
prepared under ambient conditions, and it forms a cage-like
cluster with tetradecanuclearity and shows slight dual emission
fluorescence at lower temperatures. In order to explore the
influence of the synthesis conditions on cluster 1, we obtained
other two compounds, 30-nuclearity cluster 2 and 1D polymer 3,
by making use of the templating agent dichromate. Chromate
ions act as intracluster and intercluster templates in 2 and 3,
respectively. Clusters 2 and 3 exhibit significantly greater stabi-
lity in air than cluster 1. Our experiments prove the importance
of templates in the construction of diverse clusters.
1
1
(Angew. Chem. Int. Ed., 2005, 44, 5242).
1
6 Z. Wang, H.-F. Su, Y.-Z. Tan, S. Schein, S.-C. Lin, W. Liu,
S.-A. Wang, W.-G. Wang, C.-H. Tung, D. Sun and L.-S. Zheng,
PNAS, 2017, 114, 12132.
1
1
1
7 J. F. Corrigan, O. Fuhr and D. Fenske, Adv. Mater., 2009,
21, 1867.
8 E. N. Hooley, V. Paolucci, Z. Y. Liao, M. R. C. Temboury and
T. Vosch, Adv. Opt. Mater., 2015, 3, 1109.
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Conflicts of interest
48, 5844.
There are no conflicts to declare.
2
0 Q. Q. Xu, X. Y. Dong, R. W. Huang, B. Li, S. Q. Zang and
T. C. W. Mak, Nanoscale, 2015, 7, 1650.
2
1 R. W. Huang, Q. Q. Xu, H. L. Lu, X. K. Guo, S. Q. Zang, G. G. Gao,
M. S. Tang and T. C. W. Mak, Nanoscale, 2015, 7, 7151.
Acknowledgements
The National Science Fund for Distinguished Young Scholars 22 B. Li, R. W. Huang, J. H. Qin, S. Q. Zang, G. G. Gao,
No. 21825106); the National Natural Science Foundation of China H. W. Hou and T. C. W. Mak, Chem. – Eur. J., 2014, 20, 12416.
(
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20 | New J. Chem., 2019, 43, 115--120
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