Construction of Silver Clusters Capped by Zwitterionic Ethynide Ligands

Article abstract of DOI:10.1021/acs.inorgchem.0c03790

A zwitterionic ligand 3-(triethylammonio)propyne (TAP) has been employed to construct nine silver ethynide compounds for the first time. Single-crystal X-ray analyses reveal that compounds 1 and 2 are silver ethynide assemblies based on the Ag3 subunits and clusters 3-8 are small discrete clusters of Ag3, Ag6, Ag8, and Ag12, respectively, ligated by the bulky TAP ligand with different auxiliary ligands. In addition, upon acquiring the tripod-like tBuPO32-, a unprecedented 80 nuclei silver ethynide cluster was isolated and determined to be [(CF3CO2)5@Ag80(TAP)14(tBuPO3)16(CF3CO2)24]19+ by crystallography and thermogravimetric analysis. The C1 symmetry of Ag80 was deconstructed to be two [Ag40(TAP)7(tBuPO3)8(CF3CO2)12]12+ secondary building subunits arranged in a cross way, with five CF3CO2- trapped in the center. These results highlight that the elaborate selection of ethynide ligands is of great importance in the synthesis of novel silver ethynide clusters.

Full text of DOI:10.1021/acs.inorgchem.0c03790

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Article
Construction of Silver Clusters Capped by Zwitterionic Ethynide
Ligands
Yang-Lin Shen, Jun-Ling Jin, Jun-Jie Fang, Zheng Liu, Jian-Lin Shi, Yun-Peng Xie,* and Xing Lu*
Cite This: Inorg. Chem. 2021, 60, 6276−6282
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sı Supporting Information
ABSTRACT: A zwitterionic ligand 3-(triethylammonio)propyne
TAP) has been employed to construct nine silver ethynide
(
compounds for the first time. Single-crystal X-ray analyses reveal
that compounds 1 and 2 are silver ethynide assemblies based on
the Ag subunits and clusters 3−8 are small discrete clusters of Ag ,
3
3
Ag , Ag , and Ag , respectively, ligated by the bulky TAP ligand
6
8
12
with different auxiliary ligands. In addition, upon acquiring the
t
2−
tripod-like BuPO3 , a unprecedented 80 nuclei silver ethynide
cluster was isolated and determined to be [(CF CO ) @
3
2 5
t
19+
Ag (TAP) ( BuPO ) (CF CO ) ]
by crystallography and
8
0
14
3 16
3
2 24
thermogravimetric analysis. The C1 symmetry of Ag was
80
t
12+
deconstructed to be two [Ag (TAP) ( BuPO ) (CF CO ) ]
40
7
3 8
3
2 12
secondary building subunits arranged in a cross way, with five
−
CF CO trapped in the center. These results highlight that the elaborate selection of ethynide ligands is of great importance in the
3
2
synthesis of novel silver ethynide clusters.
INTRODUCTION
Silver ethynide clusters have attracted great interest due to
their fantastic structures and potential applications.
{[Ag (TAP) ]·3PF } (2), [Ag (TAP)(dppm) (CF CO )]·
3 4 6 n 3 3 3 2
■
2
PF6 (3, dppm = bis(diphenylphosphino)methane),
[ A g 6 ( T A P ) 6 ( C H 3 C N ) 6 ] · 6 P F 6 ( 4 ) ,
Ag (TAP) (CF CO ) (CH CN) (H O) ]·6PF ·6CH OH
1
−8
[
(
1
2
6
3
2
6
3
6
2
2
6
3
However, compared with their analogous thiolated silver
clusters, the development of silver ethynide clusters has been
5), [Ag (TAP) (CH CN) (H O) ]·8PF ·CH OH (6),
8
8
3
4
2
2
6
3
9
−13
[Ag (TAP) (NO ) (H O) ]·4PF ·2CH OH (7),
8 6 3 4 2 2 6 3
lagging.
The easily available thiol ligands with different
[
Ag (TAP) (CF CO ) (H O) ]·4PF (8) and
8 6 3 2 4 2 2 6
t
sizes, structures, and properties promote the booming
advancement of thiolated silver clusters.
there is a class of zwitterionic thiol ligands for the extensive
synthesis of hydrophilic metal clusters,
1
4−18
[Ag (TAP) ( BuPO ) (CF CO ) ]·19PF ·177CH OH
(
80 14 3 16 3 2 29 6 3
Among them,
9). The zwitterionic ammonium ethynide ligand stabilizes
1
9,20
these small ethynide compounds with an interesting external
while similar
t
2−
charge layer. Furthermore, BuPO ligands act as a tripodal
3
zwitterionic ethynide ligands have not yet been explored.
The zwitterionic molecule has both cationic and anionic
strut to support the fusion of these small clusters to produce
the enlarged cluster Ag .
2
1−23
8
0
groups
and possesses an electric dipole moment within
the molecule, which has an important impact on the self-
24
assembly process of the cluster. In addition, the charge layer
formed by the zwitterionic ligand can effectively passivate the
surface of the silver cluster, thereby yielding a small silver
RESULTS AND DISCUSSION
■
X-ray Crystal Structures. X-ray structures of compounds
1
−9 were determined, and six types of coordination modes for
2
0,25
cluster.
Of note, ethynide ligands are known as both σ- and
1 1 1 2 1 1 1 1 1 2
TAP, namely, μ -η η , μ -η η , μ -η η η , μ -η η η , μ -
26,27
2
2
3
3
4
π-donors with silver ions and have various binding motifs.
1
1
1
2
1 1 2 2
η η η η , and μ -η η η η , occur in these compounds (Figure.
4
Therefore, we envisage that zwitterionic ethynide ligands may
provide an opportunity to further stabilize the embryo of silver
clusters. Moreover, such small silver ethynide clusters could
also be enlarged with help from the bridging ligand
phosphonate, which has been repeatedly proven by our
1
). Although the coordination modes of TAP and other
ethynide ligands are similar, the presence of the bulky
Received: December 30, 2020
Published: April 19, 2021
2
8,29
group.
In this work, we prepared the ethynide ligand TAPH with a
30
one-step reaction according to the reported method and it
has been used as protective ligands to assemble nine silver
ethynide compounds, which are {Ag (TAP)(CF CO ) } (1),
3
3
2 3 n
©
2021 American Chemical Society
https://doi.org/10.1021/acs.inorgchem.0c03790
6
276
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Article
polymeric chain. The asymmetric Ag unit contains three
3
−
silver atoms and four TAP ligands, with three PF6 serving as
counteranions. In detail, the four TAP ligands that exclusively
1
2
adopt the μ -η η mode cause one silver atom to be
2
disconnected from the other two silver atoms in the Ag unit
3
(
Figure 3). The Ag−C bond lengths in 2 vary from 2.070 to
Figure 1. Coordination modes of TAP with silver ions in 1−9. The
Figure 3. (a) 1D chain structure of {[Ag (TAP) ]·3PF } (2) and (b)
3
4
6 n
bulky quaternary N group in TAP is omitted for clarity.
the packing structure of 2 viewed along the c-axis direction. Color
codes are as follows: Ag, purple; C, gray; N, blue; F, light green; P,
orange; and O, red.
quaternary N-group in TAP significantly affects the arrange-
ment of these basic units, dictating the formation of
unprecedented structures in 1−9.
Single-crystal X-ray characterization reveals that compound
features a polymer-like layered structure composed of
2.628 Å. The Ag···Ag bond length is 2.936 Å, which is shorter
1
than 3.440 Å and twice the van der Waals radius of silver(I)
34,35
[
2
Ag (TAP)(CF CO ) ] as structure units. As shown in Figure
ion, indicating the presence of argentophilic interactions.
3
3
2 3 2
a, [Ag (TAP)(CF CO ) ] is yielded by connecting two
Polymeric silver ethynide compounds can be intercepted
with auxiliary ligands and often serve as the starting point
during the synthesis of discrete clusters. Further investigations
revealed that the addition of dppm and acetonitrile gives the
3
3
2 3 2
formation of the discrete clusters [Ag (TAP)-
3
(
6
dppm) (CF CO )]·2PF (3) and [Ag (TAP) (CH CN) ]·
3 3 2 6 6 6 3 6
36
1 1 1
PF (4), respectively. In 3, one TAP adopts the μ -η η η
6
3
mode, gripping the Ag unit with bulky dppm ligands that cap
3
the edges. In 4, six TAP ligands cover the six faces of the Ag
6
1
1 1
octahedron in the μ -η η η mode, and each vertex of the
3
octahedron is ligated by an acetonitrile molecule. Besides, the
Ag cluster shows a two-layer Ag −Ag arrangement, which is
6
3
3
consolidated as an integral group by argentophilic interactions
(
Figure S1). To the best of our knowledge, the discrete Ag6
octahedral molecule protected by a soft ligand has rarely been
prepared.
Cluster 5 was prepared by a reaction of TAP and AgCF CO
37−41
3
2
in a CH CN/CH OH mixed solvent using the solvothermal
3
3
m e t h o d
a n d
w a s
i d e n t i fi e d
a s
[
Ag (TAP) (CF CO ) (CH CN) (H O) ]·6PF ·6CH OH
12 6 3 2 6 3 6 2 2 6 3
by crystallography. As shown in Figure 4c, the structure of 5
can be described as the layered structure Ag −Ag -Ag −Ag ,
Figure 2. (a) Structure unit of [Ag (TAP)(CF CO ) ] and (b and c)
3
3
2 3 2
3
3
3
3
the layered structure and spacing of [Ag (TAP)(CF CO ) ] . Color
3
3
2 3 n
and there is a similar separation (∼ 2.9 Å) between the
codes are as follows: Ag, purple; C, gray; N, blue; F, light green; and
O, red.
adjacent Ag subunits. Besides, the two central and the two
3
−
outer Ag units are joined by six TAP and six CF CO
3
3
2
ligands, where the TAP ligands exclusively adopt the μ -
4
1
1 1 1
[
Ag (CF CO ) ] by two TAP ligands in a mixed σ- and π-type
η η η η mode with Ag−C bond lengths ranging from 2.235 to
3
3
2 3
1
1
1
2
−
bonding mode (μ -η η η η ), with Ag−C bond lengths of
2
carboxylic ligands to form a planar structure with 1.8 nm layer
spacing. Interestingly, such a polymer network structure shows
that the skeleton is negatively charged, and positively charged
quaternary N-groups are distributed on both sides of the
2.784 Å and each CF CO ligand coordinates with two silver
4
3
2
3
1
1 1
.224−2.626 Å; adjacent Ag units are further connected by
atoms in a μ -η η mode with Ag−O bond lengths varying
from 2.348 to 2.536 Å. Alternatively, as shown in Figure 4d,
6
2
cluster 5 can also be viewed as a Ag −Ag −Ag three-layer
3
6
3
structure. Considering the same position of TAP ligands in
clusters 4 and 5, cluster 5 is presumably formed via the fusion
of 4 and two [Ag (CF CO ) ] units upon a solvothermal
3
2,33
skeleton,
which is rarely observed in silver compounds.
3
3
2 3
The reaction of TAPH·PF with AgPF in methanol afforded
reaction. Moreover, the top and bottom surfaces of the Ag12
cylinder are covered by auxiliary water molecules. Such a
template-free cylinder structure is completely different from
6
6
{
[Ag (TAP) ]·3PF } (2). Compound 2 consists of a building
3 4 6 n
block of [Ag (TAP) ] units joined together to form a
3
4
6
277
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Article
2
+
6+
Figure 4. Overview structure of (a) [Ag (TAP)(dppm) (CF CO )]
[
in 3, (b) [Ag (TAP) (CH CN) ]
in 4, and (c)
3
3
3
2
6
6
3
6
6
+
Ag (TAP) (CF CO ) (CH CN) (H O) ] in 5. (d) Generation of cluster 5 from the fusion of 4 and [Ag (CF CO ) ] subunits. Some
12 6 3 2 6 3 6 2 2 3 3 2 3
auxiliary ligands are omitted for clarity. Color codes are as follows: Ag, purple; C, gray, black; N, blue; F, light green; P, orange; and O, red.
8
+
4+
4+
Figure 5. Crystal structure of (a) [Ag (TAP) (CH CN) (H O) ] , (b) [Ag (TAP) (NO ) (H O) ] , (c) [Ag (TAP) (CF CO ) (H O) ] ,
8
8
3
4
2
2
8
6
3
4
2
2
8
6
3
2
4
2
2
6
−
and (d) [Ag (pfga) ] (NC-Ag ). (e) The box chart of Ag···Ag bond lengths of the Ag clusters.
8
6
8
8
the cuboctahedra Ag12 synthesized with the tert-butylacetylene
ligand by Orthaber et al.
The synthesis procedure of 6−8 is similar to that of 5 except
that different silver salts and solvents were selected in the
reaction. According to the single-crystal X-ray analysis, the
[Ag (TAP) (CH CN) (H O) ]·8PF ·CH OH (6),
8 8 3 4 2 2 6 3
31
[Ag (TAP) (NO ) (H O) ]·4PF ·2CH OH (7), and
8 6 3 4 2 2 6 3
4
2,43,44
[Ag (TAP) (CF CO ) (H O) ]·4PF (8).
As shown in
8
6
3
2 4
2
2
6
1
1
Figure 5, four of the eight TAP ligands in 6 adopt the μ -η η
2
mode to link two silver atoms, and the remaining four adopt
1
1 1
c o m p o u n d s
w e r e
d e t e r m i n e d
a s
the μ -η η η mode to coordinate to three silver atoms, leading
3
6
278
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Article
−
the eight silver atoms to form an irregular bipyramid with four
important role in enveloping the asymmetric CF CO
3
2
vertices capped by CH CN ligands (Figure S2). In contrast,
molecules to form the cluster 9.
3
two TAP ligands in 7 coordinate with silver atoms in the μ -
The external skeleton structure of Ag80 can be viewed as a
construction of two of the same Ag40 units. As shown in Figure
3
1
1 1
η η η mode, and the remaining four TAP ligands use the μ -
3
1
1
2
45
η η η mode to give a novel parallelepiped of Ag . Four
NO3 and two H O molecules each coordinate to only one
6 c ,
A g 4 0
w a s
d e t e r m i n e d
a s
8
−
2
silver atom in the vertices of the parallelepiped. Cluster 8
−
possesses a similar structure to that of 7 except the four NO
3
−
molecules in 7 are replaced by the four CF CO2 ligands. As
3
shown in Figure 5e, argentophilic interactions are prominent in
the formation of clusters 6−8 and consolidate their framework
as an integral group. It is believed that the attachment of an
electron-donating ligand will render silver(I) more electron-
rich, resulting in greater charge−charge repulsion and smaller
46
bonding interactions between the silver ions. As expected,
−
NO3 anionic ligands in 7 enhance the repulsive force between
the silver ions and result in longer Ag···Ag bond lengths than
those of 6, which is coordinated by the electroneutral
−
acetonitrile molecule. While CF CO ligands are bulkier
3
2
−
than NO , they causes cluster 8 to have longer Ag···Ag bond
lengths relative to those of 7. Therefore, we think that both the
3
electron-donating ability and the size of the ligand have a
47
significant influence on argentophilic interactions and further
affect the arrangement in these silver cages. Recently, Liu et al.
reported the synthesis and structure of the similar
parallelepiped-shaped superatomic silver nanocluster
6
−
[
5
Ag (pfga) ] (NC-Ag , pfga = perfluoroglutarate) (Figure
8
6
8
4
5
d). NC-Ag shows the shortest Ag···Ag bond length among
these four Ag8 clusters due to the shell closing of the
superatomic orbital (1S ), which presents a sharp contrast with
8
2
the van der Waals force of the argentophilic interactions in
clusters 6−8.
F i g u r e
6 .
( a )
C r y s t a l
s t r u c t u r e
o f
t
19+
The synthesis of 9 involves a solvothermal reaction where
[Ag (TAP) ( BuPO ) (CF CO ) ]
in 9. (b) The core−shell
8
0
14
3
16
3
2 29
t
TAPH and the auxiliary ligand BuPO H2 react with
structure of Ag . (c) Relative position of two Ag units in Ag . (d)
The skeleton structure of [Ag40(TAP) ( BuPO ) (CF CO ) ] .
3
80
40
80
t
12+
AgCF CO and triethylamine in methanol. The single-crystal
7 3 8 3 2 12
3
2
(
e−g) TAP⊃Ag and TAP⊃Ag synthons in the shell. Color codes are
X-ray result displays that cluster 9 crystallizes in the P2 /n
3
4
1
as follows: Ag, purple, green; C, gray, black; N, blue; F, light green;
space group. However, the poor crystal quality makes it
impossible to model all counterions and solvent molecules, and
voids among the crystal structure have been found in the
residual electron density in 9 that correspond to 4227 electrons
per cell, which were ascribed to 15 PF6− counterions and 177
and O, red. Some alkyl groups are omitted for clarity.
Ag (TAP) ( BuPO ) (CF CO ) ]12+, which consists of
t
[
40
7
3
8
3
2 12
one Ag14 and two same Ag13 subunits that are located on
both sides of the Ag14 in a centrosymmetric manner (Figure
4
8
CH OH molecules per formula unit. Accordingly, the
3
c o m p o s i t i o n o f
9
16
w a s d e t e r m i n e d t o b e
S4). The Ag13 is constructed by synthons of TAP⊃Ag and
t
3
[
Ag (TAP) ( BuPO ) (CF CO ) ]·19PF ·177CH OH,
−
8
0
14
3
3
2
29
6
3
TAP⊃Ag with six silver ions and five CF CO ligands. In
4
3
2
and the composition also has been confirmed by the results of
contrast, the Ag is composed of three TAP⊃Ag synthons
1
4
4
XPS and thermogravimetry (Figure S3). The XPS result shows
−
with two silver ions and two CF CO ligands. Each of 14 TAP
4
9
3
2
that the silver in the clusters is a +1 valence, and the
thermogravimetric curve illustrates a two-step weight loss
process that may be caused by a large amount of the
crystallization solvent. The total weight loss is similar to the
theoretical calculation result.
ligands is linked to either three or four silver atoms in the
1
1 1
following variant coordination mode: two μ -η η η , two μ -
3
3
1
1
2
1
1
1
2
1 1 2 2
η η η , seven μ -η η η η , and three μ -η η η η (Figure 6e−h,
4
4
21
respectively). Then, these subunits of Ag and Ag are
1
3
14
t
2−
connected by the tripodal BuPO ligands in μ or μ modes,
3
6
7
The skeleton structure of 9 contains 80 Ag ions and 14 TAP,
with the Ag−O bond length varying from 2.170 to 2.813 Å.
t
2−
−
1
6 BuPO , and 29 CF CO ligands and is identified as a
3 3 2
Both the Ag and Ag are further consolidated by the Ag···Ag
1
3
14
t
24+
[
Ag (TAP) ( BuPO ) (CF CO ) ] cage, which envelops
80 14 3 16 3 2 25
interactions with bond lengths ranging from 2.761 to 3.368 Å
−
five asymmetric CF CO2 molecules. To the best of our
knowledge, it is the first time CF CO2 molecules have been
enclosed in silver clusters. These five CF CO2 ligands evenly
occupy the internal space and connect to the wall of the super
3
(Table S2), and there is no significant difference compared to
−
3
the high-nuclearity silver clusters reported previously (Table
−
51−53
3
S1).
Considering the similar synthesis conditions of
clusters 9 and 5, the Ag13 and Ag14 subunits are probably
cage with Ag−F bond lengths that vary from 2.051 to 2.877 Å
derived from the structural evolution of Ag . Additionally,
1
2
50
t
2−
and Ag−O bond lengths in a range from 2.261 to 2.762 Å.
eight BuPO ligands join the three subunits together, giving
3
We assume that the hydrothermal conditions and the stable
the cambered shape of the Ag40 structures. Interestingly, the
two Ag40 units are combined with the aid of the tripodal
t
2−
shell formed by BuPO3 with the silver ions play an
6
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Article
Figure 7. UV−vis absorbance spectrum of 9 in (b) solid and (b) a methanol solution.
tBuPO32−ligands in a cross way instead of the most common
MHz, ACETON-D6, δ, ppm): 1.2−1.3 (t, (CH
CH
)
N), 3.3−3.4
3
2
3
(
m, (CH CH ) N), 4.02−4.04 (t, CCH), 4.31−4.35 (m, NCH C).
mirror symmetry, which may result from the influence of five
3
2
3
2
−
Synthesis of TAPH·PF . TAPH·Br (21.9 g, 0.1 mol) and KPF
6 6
20.2 g, 0.12 mol) were dissolved in 500 mLof acetonitrile with
inner asymmetric CF CO2 molecules.
3
(
Clusters 1−8 have very poor solubilities, but cluster 9 can be
dissolved in common organic solvents such as methanol,
ethanol, and acetonitrile, which may be due to the large
violent stirring for 48 h. A light yellow solution was collected by
filtration and dried with rotary evaporation. Yield: cal 97%.
Synthesis of 1. TAPH·Br (0.03 g, 0.14 mmol) and AgCF CO
(0.22 g, 1 mmol) were dissolved in 5 mL of methanol under vigorous
stirring at room temperature for 20 min. A clear solution was collected
by filtration, and the slow evaporation of the solution afforded the
3
2
−
t
2−
amount of CF CO2 and BuPO3 auxiliary ligands in 9. As
3
shown in Figure 7, the UV−vis spectrum of 9 displays an
absorption peak at ca. 410 nm in a methanol solution and
shows a wide absorption band ranging from 250 to 550 nm in
the solid state, which was assigned to O 2p to Ag 5s charge
−
1
product as colorless crystals. Yield: ca. 25%. IR (KBr, cm ): 2078
CC), 1681 (C = O), 1133 (C−F). Elemental analysis (%) calcd
for C H O NF Ag : C, 22.47; H, 2.12; N, 1.75. Found: C, 22.56; H.
(
5
4
transfer. Moreover, the fluorescent properties of 9 in solution
15 17
6
9
3
2
.47; N, 1.86.
and the solid state were also explored at room temperature,
55
Synthesis of 2. The synthetic process of 2 is quite similar to that
and no fluorescent emission was observed.
of 1 except that TAPH·Br and AgCF CO were replaced by TAPH·
3
2
In summary, we synthesized a new ethynide ligand through a
simple one-step reaction. Such a zwitterionic ethynide ligand
adopts a variety of coordination modes with silver atoms,
PF6 (0.057 g, 0.20 mmol) and AgPF (0.051 g, 0.2 mmol),
6
−1
respectively. Yield: ca. 43%. IR (KBr, cm ): 2082 (CC). Elemental
analysis (%) calcd for C H N F P Ag : C, 32.87; H, 5.17; N, 4.26.
3
6
68
4
18
3
3
1
1
1
2
1
1
1
1
1
2
1 1 1 2
including μ -η η , μ -η η , μ -η η η , μ -η η η , μ -η η η η ,
2
2
3
3
4
Found: C, 32.98; H, 5.41; N, 4.64.
1
1
2
2
−
and μ -η η η η . Together with the auxiliary ligands CF CO ,
Synthesis of 3. TAPH·PF (0.057 g, 0.20 mmol), dppm (0.153 g,
4
3
2
6
CH CN and dppm to protect the structure edges, two
0.40 mmol), and AgCF CO (0.11 g, 0.5 mmol) were dissolved in 5
3
3
2
polymeric species and six small silver clusters were prepared.
mL of methanol under vigorous stirring at room temperature for 20
min. A clear solution was collected by filtration, and the slow
evaporation of the solution afforded the product as colorless crystals.
t
2−
In addition, by introducing a tripod-like BuPO3 , we obtained
−
a rare irregular Ag80 structure that encloses five CF CO
3
2
−
1
Yield: ca. 52%. IR (KBr, cm ): 2091 (CC), 1673 (CO), 1125
inside with C symmetry. To our knowledge, this provides the
1
(
5
C−F). Elemental analysis (%) calcd for C H O NP F Ag : C,
8
6
83
2
8
15
3
first systematic study of the self-assembly of zwitterion
ethynide ligands and silver ions.
1.16; H, 4.11; N, 0.69. Found: C, 51.33; H, 4.35; N, 0.83.
Synthesis of 4. TAPH·PF (0.057 g, 0.20 mmol) and AgPF (0.12
6
6
g, 0.5 mmol) were dissolved in 5 mL of acetonitrile. After adding 100
μL of trimethylamine and stirring for 30 min, a clear solution was
collected by filtration, and the slow evaporation of the solution
afforded the product as colorless crystals. Yield: ca. 34%. IR (KBr,
EXPERIMENTAL SECTION
■
All reagents and solvents employed are commercially available and
were used as received without further purification. Elemental analyses
for C, H, and N were performed using a PerkinElmer 2400 CHN
elemental analyzer. The Fourier transform infrared (FT-IR) spectra
−
1
cm ): 2082 (CC). Elemental analysis (%) calcd for
C H N F P Ag : C, 30.50; H, 4.62; N, 6.46. Found: C, 30.72;
66 120 12 36
6
6
−1
H, 4.88; N, 6.61.
Synthesis of 5. TAPH·PF (0.057 g, 0.20 mmol) and AgCF CO
2
were recorded from KBr pellets in the range 4000−400 cm on a
Bruker VERTEX 70 spectrometer. The UV-NIR experiments were
carried out on a PE Lambda 750S UV−vis-NIR spectrophotometer.
Crystal data of 1−9 were collected with Mo Kα radiation (λ =
6
3
(
0.17 g, 0.8 mmol) were dissolved in a mixed solution of methanol (8
mL) and acetonitrile (2 mL). After adding 100 μL of trimethylamine
and stirring for 30 min, the mixture was sealed in a 25 mL Teflon-
lined stainless steel autoclave and kept at 70 °C for 10 h. The light
yellow filtrate was left in dark, giving the product as colorless crystals.
IR (KBr, cm ): 2073 (CC), 1677 (CO), 1116 (C−F). Yield:
ca. 19%. Elemental analysis (%) calcd for C84 Ag12: C,
24.30; H, 3.56; N, 4.05. Found: C, 24.42; H, 3.68; N, 4.17.
Synthesis of 6. The synthetic process of 6 is similar to that of 5
except that AgCF CO was replaced with AgPF (0.12 g, 0.5 mmol).
Yield: ca. 37%. IR (KBr, cm ): 2132 (CC), 839 (P−F). Elemental
analysis (%) calcd for C81 Ag : C, 29.19; H, 4.56; N,
5.04. Found: C, 29.37; H, 4.69; N, 5.16.
0
.71073 Å) on a Bruker D8 Quest diffractometer equipped with a
Photon 100 CMOS detector. A multiscan method (SADABS) was
used for absorption corrections. The structures were solved by direct
methods and refined with SHELXL-2014. Crystallographic data
parameters for 1−9 are given in Tables S1−S11.
Caution! Silver ethynide complexes are highly potentially explosive
in the dry state when subjected to heating or mechanical shock and
should be handled in small amounts with extreme care.
Sythesis of TAPH·Br. Propargyl bromide (10 mmol, 0.78 mL)
and trimethylamine (12 mmol, 1.7 mL) were mixed in dichloro-
methane (50 mL) with stirring. After reacting for 30 min, the light
yellow precipitate was collected by filtration and washed with diethyl
ether. Please pay attention and choose a suitable container to avoid
−1
H O N F P
148 20 12 54 6
3
2
6
−
1
H
152ON12
F P
48
8
8
Synthesis of 7. The synthetic process of 7 is similar to that of 5
except that AgCF CO was replaced with AgNO (0.12 g, 0.5 mmol)
3
2
3
1
danger due to the violent reaction! Yield: cal 95%. H NMR (400
and the mixed solvent was replaced with methanol (10 mL). Yield: ca.
6
280
https://doi.org/10.1021/acs.inorgchem.0c03790
Inorg. Chem. 2021, 60, 6276−6282

Inorganic Chemistry
pubs.acs.org/IC
Article
−
1
2
5%. IR (KBr, cm ): 2069 (CC), 1376 (N−O). Elemental
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.inorgchem.0c03790
analysis (%) calcd for C H O N F P Ag : C, 30.50; H, 4.62; N,
5
6
114 16 10 24
4
8
6
.46. Found: C, 30.72; H, 4.88; N, 6.71.
Synthesis of 8. The synthetic process of 8 is similar to that of 5
except that the amount of AgCF CO was decreased from 0.8 to 0.5
Notes
3
2
The authors declare no competing financial interest.
mmol and the mixed solvent was replaced with methanol (10 mL).
−
1
Yield: ca. 31%. IR (KBr, cm ): 2078 (CC), 1672 (C = O), 1127
(
2
C−F). Elemental analysis (%) calcd for C H O N F P Ag : C,
6
2
106 10
6
36
4
8
ACKNOWLEDGMENTS
■
6.92; H, 3.83; N, 3.04. Found: C, 27.14; H, 3.97; N, 3.15.
Synthesis of 9. The synthetic process of 9 is quite similar to that
of 5 except that the amount of AgCF CO was increased to 1.3 mmol
We gratefully acknowledge financial support from the National
Natural Science Foundation of China (nos. 21771071,
51672093, and 21925104). We thank the Analytical and
Testing Center at the Huazhong University of Science and
Technology for all related measurements.
3
2
t
and BuPO H (0.01 g, 0.1 mmol) was added. Yield: ca. 28%. IR
3
2
−
1
(
KBr, cm ): 2084 (CC), 1675 (CO), 1129 (C−F), 1051 (P
O). Elemental analysis (%) calcd for C N F P Ag : C,
H
O
4
25 1084 283 14 201 35
80
2
0.87; H, 4.43; N, 0.80. Found: C, 22.61; H, 4.69; N, 1.02.
REFERENCES
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c03790.
■
■
(
1) Zhang, X.; Wang, J.-Y.; Huang, Y.-Z.; Yang, M.; Chen, Z.-N.
Silver(I) nanoclusters of carbazole-1,8-bis(acetylide): from visible to
*
near-infrared emission. Chem. Commun. 2019, 55, 6281−6284.
(
2) Zhang, S.-S.; Alkan, F.; Su, H.-F.; Aikens, C. M.; Tung, C.-H.;
t
Sun, D. Ag (C≡C Bu) (CrO ) : An atomically precise silver
X-ray crystallography data and additional figures (PDF)
48
20
4 7
nanocluster co-protected by inorganic and organic ligands. J. Am.
Chem. Soc. 2019, 141, 4460−4467.
3) Wang, T.; Zhang, W.-H.; Yuan, S.-F.; Guan, Z.-J.; Wang, Q.-M.
Accession Codes
(
CCDC 2031013−2031021 contain the supplementary crys-
tallographic data for this paper. These data can be obtained
free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by
emailing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
An alkynyl-protected Au40 nanocluster featuring PhC≡C-Au-P^P
motifs. Chem. Commun. 2018, 54, 10367−10370.
(
4) Jin, J.-L.; Shen, Y.-L.; Xie, Y.-P.; Lu, X. Silver ethynide clusters
constructed with fluorinated β-diketonate ligands. CrystEngComm
018, 20, 2036−2042.
5) Shen, H.; Mizuta, T. An atomically precise alkynyl-protected
2
(
PtAg42 superatom nanocluster and its structural implications. Chem. -
Asian J. 2017, 12, 2904−2907.
AUTHOR INFORMATION
Corresponding Authors
Yun-Peng Xie − State Key Laboratory of Materials Processing
and Die & Mould Technology, School of Materials Science
and Engineering, Huazhong University of Science and
Technology (HUST), Wuhan 430074, China; orcid.org/
■
(6) Wu, H.-B.; Huang, Z.-J.; Wang, Q.-M. Unprecedented solution-
stable silver(I) ethynediyl clusters. Chem. - Eur. J. 2010, 16, 12321−
2323.
7) Xie, Y.-P.; Mak, T. C. W. Silver(I)-ethynide clusters constructed
with phosphonate-functionized polyoxovanadates. J. Am. Chem. Soc.
011, 133, 3760−3763.
8) Koshevoy, I. O.; Karttunen, A. J.; Kritchenkou, I. S.; Krupenya,
D. V.; Selivanov, S. I.; Melnikov, A. S.; Tunik, S. P.; Haukka, M.;
1
(
2
(
0
000-0002-4065-9809; Email: xieyp@hust.edu.cn
Xing Lu − State Key Laboratory of Materials Processing and
Die & Mould Technology, School of Materials Science and
Engineering, Huazhong University of Science and Technology
I
I
Pakkanen, T. A. Sky-blue luminescent Au -Ag alkynyl-phosphine
clusters. Inorg. Chem. 2013, 52, 3663−3673.
(9) Xie, Y.-P.; Jin, J.-L.; Duan, G.-X.; Lu, X.; Mak, T. C. W. High-
(
2
HUST), Wuhan 430074, China; orcid.org/0000-0003-
741-8733; Email: lux@hust.edu.cn
nuclearity silver(I) chalcogenide clusters: A novel class of supra-
molecular assembly. Coord. Chem. Rev. 2017, 331, 54−72.
(10) Lei, Z.; Wan, X.-K.; Yuan, S.-F.; Wang, J.-Q.; Wang, Q.-M.
Alkynyl-protected gold and gold-silver nanoclusters. Dalton Trans.
Authors
Yang-Lin Shen − State Key Laboratory of Materials Processing
2
(
017, 46, 3427−3434.
and Die & Mould Technology, School of Materials Science
and Engineering, Huazhong University of Science and
Technology (HUST), Wuhan 430074, China
11) Jin, R.; Zeng, C.; Zhou, M.; Chen, Y. Atomically precise
colloidal metal nanoclusters and nanoparticles: fundamentals and
opportunities. Chem. Rev. 2016, 116, 10346−10413.
Jun-Ling Jin − Henan Key Laboratory of Functional Salt
Materials, Center for Advanced Materials Research,
Zhongyuan University of Technology, Zhengzhou 450007,
China
Jun-Jie Fang − State Key Laboratory of Materials Processing
and Die & Mould Technology, School of Materials Science
and Engineering, Huazhong University of Science and
Technology (HUST), Wuhan 430074, China
(12) Yang, J.; Jin, R. New advances in atomically precise silver
nanoclusters. ACS Materials Lett. 2019, 1, 482−489.
(13) Hau, S. C. K.; Cheng, P.-S.; Mak, T. C. W. Enlargement of
globular silver alkynide cluster via core transformation. J. Am. Chem.
Soc. 2012, 134, 2922−2925.
(14) Ren, L.; Yuan, P.; Su, H.; Malola, S.; Lin, S.; Tang, Z.; Teo, B.
K.; Hakkinen, H.; Zheng, L.; Zheng, N. Bulky surface ligands promote
3
+
surface reactivities of [Ag141X (S-Adm) ] (X = Cl, Br, I)
12
40
nanoclusters: models for multiple-twinned nanoparticles. J. Am.
Zheng Liu − State Key Laboratory of Materials Processing and
Die & Mould Technology, School of Materials Science and
Engineering, Huazhong University of Science and Technology
Chem. Soc. 2017, 139, 13288−13291.
(15) Desireddy, A.; Conn, B. E.; Guo, J.; Yoon, B.; Barnett, R. N.;
Monahan, B. M.; Kirschbaum, K.; Griffith, W. P.; Whetten, R. L.;
Landman, U.; Bigioni, T. P. Ultrastable silver nanoparticles. Nature
(
HUST), Wuhan 430074, China
Jian-Lin Shi − State Key Laboratory of Materials Processing
and Die & Mould Technology, School of Materials Science
and Engineering, Huazhong University of Science and
Technology (HUST), Wuhan 430074, China
2
(
013, 501, 399−402.
16) Joshi, C. P.; Bootharaju, M. S.; Alhilaly, M. J.; Bakr, O. M.
−
[Ag (SR) ] : The ″golden″ silver nanoparticle. J. Am. Chem. Soc.
2015, 137, 11578−11581.
2
5
18
6
281
https://doi.org/10.1021/acs.inorgchem.0c03790
Inorg. Chem. 2021, 60, 6276−6282

Inorganic Chemistry
pubs.acs.org/IC
Article
(
17) Dhayal, R. S.; Lin, Y. R.; Liao, J. H.; Chen, Y. J.; Liu, Y. C.;
nanowheel encapsulating a subvalent Ag64+ kernel. Sci. China: Chem.
2020, 63, 16−20.
(38) Wang, Z.; Su, H.-F.; Kurmoo, M.; Tung, C.-H.; Sun, D.; Zheng,
Chiang, M. H.; Kahlal, S.; Saillard, J. Y.; Liu, C. [Ag {S P(OR) } ]:
A superatom complex with a chiral metallic core and high potential
2
0
2
2 12
for isomerism. Chem. - Eur. J. 2016, 22, 9943−9947.
L.-S. Trapping an octahedral Ag kernel in a seven-fold symmetric
Ag56 nanowheel. Nat. Commun. 2018, 9, 2094−2111.
(39) Wang, Z.; Yang, F.-L.; Yang, Y.; Liu, Q.-Y.; Sun, D. Hierarchical
6
(
18) Wang, Z.; Su, H.-F.; Tan, Y.-Z.; Schein, S.; Lin, S.-C.; Liu, W.;
Wang, S.-A.; Wang, W.-G.; Tung, C.-H.; Sun, D.; Zheng, L.-S.
Assembly of silver Trigons into a buckyball-like Ag180 nanocage. Proc.
Natl. Acad. Sci. U. S. A. 2017, 114, 12132−12137.
multi-shell 66-nuclei silver nanoclusters trapping subvalent Ag
6
kernels. Chem. Commun. 2019, 55, 10296−10299.
(19) Bao, S.-J.; Liu, C.-Y.; Zhang, M.; Chen, X.-R.; Yu, H.; Li, H.-X.;
(40) Han, Z.; Dong, X.-Y.; Luo, P.; Li, S.; Wang, Z.-Y.; Zang, S.-Q.;
Mak, T. C. W. Ultrastable atomically precise chiral silver clusters with
more than 95% quantum efficiency. Sci. Adv. 2020, 6, No. eaay0107.
(41) Deng, C.; Sun, C.; Wang, Z.; Tao, Y.; Chen, Y.; Lin, J.; Luo, G.;
Lin, B.; Sun, D.; Zheng, L. A sodalite-type silver orthophosphate
cluster in a globular silver nanocluster. Angew. Chem., Int. Ed. 2020,
59, 12659−12663.
Braunstein, P.; Lang, J.-P. Metal complexes with the zwitterion 4-
trimethylammonio)benzenethiolate: Synthesis, structures and appli-
cations. Coord. Chem. Rev. 2019, 397, 28−53.
20) Huo, S.; Jiang, Y.; Gupta, A.; Jiang, Z.; Landis, R. F.; Hou, S.;
(
(
Liang, X.-J.; Rotello, V. M. Fully zwitterionic nanoparticle
antimicrobial agents through tuning of core size and ligand structure.
ACS Nano 2016, 10, 8732−8737.
(42) Wang, Z.; Su, H.-F.; Gong, Y.-W.; Qu, Q.-P.; Bi, Y.-F.; Tung,
(21) Li, Z.; Cai, W.; Yang, X.; Zhou, A.; Zhu, Y.; Wang, H.; Zhou,
C.-H.; Sun, D.; Zheng, L.-S. A hierarchically assembled 88-nuclei
silver-thiacalix [4] arene nanocluster. Nat. Commun. 2020, 11, 308−
X.; Xiong, K.; Zhang, Q.; Gai, Y. Cationic metal−organic frameworks
2−
3
(
15.
based on linear zwitterionic ligands for Cr O
and ammonia
2
7
43) Yuan, P.; Zhang, R.; Selenius, E.; Ruan, P.; Yao, Y.; Zhou, Y.;
sensing. Cryst. Growth Des. 2020, 20, 3466−3473.
Malola, S.; Häkkinen, H.; Teo, B. K.; Cao, Y.; Zheng, N. Solvent-
mediated assembly of atom-precise gold−silver nanoclusters to
semiconducting one-dimensional materials. Nat. Commun. 2020, 11,
(22) Blackman, L. D.; Gunatillake, P. A.; Cass, P.; Locock, K. E. S.
An introduction to zwitterionic polymer behavior and applications in
solution and at surfaces. Chem. Soc. Rev. 2019, 48, 757−770.
2
(
229−2236.
(23) Shao, Q.; Jiang, S. Molecular understanding and design of
44) Kephart, J. A.; Boggiano, A. C.; Kaminsky, W.; Velian, A.
zwitterionic materials. Adv. Mater. 2015, 27, 15−26.
Inorganic clusters as metalloligands: Ligand effects on the synthesis
and properties of ternary nanopropeller clusters. Dalton Trans. 2020,
(24) Yi, M.; Lau, C. H.; Xiong, S.; Wei, W.; Liao, R.; Shen, L.; Lu,
A.; Wang, Y. Zwitterion−Ag complexes that simultaneously enhance
biofouling resistance and silver binding capability of thin film
composite membranes. ACS Appl. Mater. Interfaces 2019, 11,
4
(
9, 16464−16473.
45) Liu, K.-G.; Gao, X.-M.; Liu, T.; Hu, M.-L.; Jiang, D.-e. All-
carboxylate-protected superatomic silver nanocluster with an un-
precedented rhombohedral Ag Core. J. Am. Chem. Soc. 2020, 142,
1
(
5698−15708.
25) Gong, T.; Yang, X.; Sui, Q.; Qi, Y.; Xi, F.-G.; Gao, E.-Q.
8
1
(
6905−16909.
Magnetic and photochromic properties of a manganese(II) metal-
46) Wing-Wah Yam, V.; Chung-Chin Cheng, E.; Zhu, N. Synthesis,
zwitterionic coordination polymer. Inorg. Chem. 2016, 55, 96−103.
photophysics, and electrochemistry of hexanuclear silver(I) chalcoge-
(
26) Tang, J.; Zhao, L. Polynuclear organometallic clusters:
nolate complexes. X-Ray crystal structures of [Ag (μ-dppm) (μ -
synthesis, structure, and reactivity studies. Chem. Commun. 2020,
6, 1915−1925.
27) He, X.; Liu, H.-X.; Zhao, L. Integration of acetylenic carbon
6
4
3
SC H Me-p) ](PF ) and [Ag (μ-dppm) (μ -SeC H Cl-p) ](PF ) .
5
(
6
4
4
6
2
6
4
3
6
4
4
6 2
New J. Chem. 2002, 26, 279−284.
(47) Shen, Y.-L.; Jin, J.-L.; Xie, Y.-P.; Lu, X. tert-Butyl thiol and
clusters and silver clusters: template synthesis and stability enhance-
pyridine ligand co-protected 50-nuclei clusters: the effect of pyridines
ment. Chem. Commun. 2016, 52, 5682−5685.
on Ag−SR bonds. Dalton Trans. 2020, 49, 12574−12580.
(28) Xie, Y.-P.; Jin, J.-L.; Lu, X.; Mak, T. C. W. High-nuclearity silver
(48) Sheldrick, G. M. Crystal structure refinement with SHELXL.
thiolate clusters constructed with phosphonates. Angew. Chem., Int.
Ed. 2015, 54, 15176−15180.
Acta Crystallogr., Sect. C: Struct. Chem. 2015, 71, 3−8.
(49) Wu, T.; Yin, D.; Hu, X.; Yang, B.; Liu, H.; Xie, Y.-P.; Liu, S.-X.;
(29) Jin, J.-L.; Xie, Y.-P.; Cui, H.; Duan, G.-X.; Lu, X.; Mak, T. C.
Ma, L.; Gao, G.-G. A disulfur ligand stabilization approach to
construct a silver(I)-cluster-based porous framework as a sensitive
SERS substrate. Nanoscale 2019, 11, 16293−16298.
Structure-directing role of phosphonate in the synthesis of high-
nuclearity silver (I) sulfide-ethynide-thiolate clusters. Inorg. Chem.
2
(
017, 56, 10412−10417.
(50) Guan, Z.-J.; Zeng, J.-L.; Yuan, S.-F.; Hu, F.; Lin, Y.-M.; Wang,
30) Zhao, B.; Gao, Z.; Zheng, Y.; Gao, C. Scalable synthesis of
Q.-M. Au Ag (C≡CPh) Br : A large nanocluster with C
5
7
53
40 12
1
positively charged sequence-defined functional polymers. J. Am. Chem.
Soc. 2019, 141, 4541−4546.
symmetry. Angew. Chem., Int. Ed. 2018, 57, 5703−5707.
51) Liu, K.-G.; Chen, S.-K.; Lin, Y.-M.; Wang, Q.-M. An organic
(
(
31) Gupta, A. K.; Orthaber, A. The self-assembly of
t
n+
anion template: a 24-nucleus silver cluster encapsulating a squarate
[
{Ag (C≡C Bu) } ] building units into a template-free cuboctahe-
3
2 n
dimer. Chem. Commun. 2015, 51, 9896−9898.
dron and anion-encapsulating silver cages. Inorg. Chem. 2019, 58,
6236−16240.
32) Aulakh, D.; Varghese, J. R.; Wriedt, M. A new design strategy to
(52) Liu, K.-G.; Liu, X.-Y.; Guan, Z.-J.; Shi, K.; Lin, Y.-M.; Wang, Q.-
1
(
M. The transformation of polyoxometalates in the formation of
t
intercluster compound [Ag (α-SiW10O )( BuC≡C) (CH CN) ]-
4
1
37
27
3
3
access zwitterionic metal−organic frameworks from anionic viologen
[
β-SiW O ]. Chem. Commun. 2016, 52, 3801−3804.
53) Qiao, J.; Shi, K.; Wang, Q.-M. A giant silver alkynyl cage with
1
2
40
derivates. Inorg. Chem. 2015, 54, 1756−1764.
(
(33) Zhan, N.; Palui, G.; Safi, M.; Ji, X.; Mattoussi, H. Multidentate
sixty silver(I) ions clustered around polyoxometalate templates.
zwitterionic ligands provide compact and highly biocompatible
Angew. Chem., Int. Ed. 2010, 49, 1765−1767.
quantum Dots. J. Am. Chem. Soc. 2013, 135, 13786−13795.
(54) Liu, K.-G.; Bigdeli, F.; Li, H.-J.; Li, J.-Z.; Yan, X.-W.; Hu, M.-L.;
(34) Schmidbaur, H.; Schier, A. Argentophilic interactions. Angew.
Morsali, A. Hexavalent octahedral template: a neutral high-nucleus
silver alkynyl nanocluster emitting infrared light. Inorg. Chem. 2020,
Chem., Int. Ed. 2015, 54, 746−784.
(35) Su, Y. M.; Wang, Z.; Schein, S.; Tung, C. H.; Sun, D. A
5
(
9, 6684−6688.
Keplerian Ag90 nest of Platonic and Archimedean polyhedra in
55) Zhang, S.-S.; Su, H.-F.; Wang, Z.; Wang, L.; Zhao, Q.-Q.; Tung,
different symmetry groups. Nat. Commun. 2020, 11, 3316−3325.
C.-H.; Sun, D.; Zheng, L.-S. Anion-templated nanosized silver alkynyl
clusters: cluster engineering and solution behavior. Chem. - Eur. J.
(36) Jin, J.-L.; Xie, Y.-P.; Lu, X. High-nuclearity silver ethynide
clusters containing polynucleating oxygen donor ligands. Dalton
Trans. 2018, 47, 12972−12978.
2017, 23, 3432−3437.
(37) Wang, Z.; Qu, Q.-P.; Su, H.-F.; Huang, P.; Gupta, R. K.; Liu,
Q.-Y.; Tung, C.-H.; Sun, D.; Zheng, L.-S. A novel 58-nuclei silver
6
282
https://doi.org/10.1021/acs.inorgchem.0c03790
Inorg. Chem. 2021, 60, 6276−6282