Ultrafast Size Expansion and Turn-On Luminescence of Atomically Precise Silver Clusters by Hydrogen Sulfide

Article abstract of DOI:10.1002/anie.202100006

The formation of high-nuclearity silver(I) clusters remains elusive and their potential applications are still underdeveloped. Herein, we firstly prepared a chain-like thiolated Ag^I complex {[Ag₁₈(S^tBu)₁₀(NO₃)₈(CH₃CN)₂(H₂O)₂] ? [Ag₁₈(S^tBu)₁₀(NO₃)₈(CH₃CN)₆]}_n (abbreviated as Ag₁₈) in which two similar Ag₁₈ clusters are assembled by NO₃^? anions. The solution containing Ag₁₈ reacted with hydrogen sulfide with controlled concentration, promptly producing another identifiable and bright red-emitting high-nuclearity silver(I) cluster, Ag₆₂(S)₁₃(S^tBu)₃₂(NO₃)₄ (abbreviated as Ag₆₂). We tracked the transformation using time-dependent electrospray ionization mass spectrometry (ESI-MS), UV/Vis absorption and photoluminescence spectra. Based on this cluster transformation, we further developed an ultra-sensitive turn-on sensor detecting H₂S gas with an ultrafast response time (30 s) at a low detection limit (0.13 ppm). This work opens a new way of understanding the growth of metal clusters and developing their luminescent sensing applications.

Full text of DOI:10.1002/anie.202100006

Angewandte
Communications
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How to cite: Angew. Chem. Int. Ed. 2021, 60, 8505–8509
International Edition: doi.org/10.1002/anie.202100006
German Edition: doi.org/10.1002/ange.202100006
Silver Clusters Hot Paper
Ultrafast Size Expansion and Turn-On Luminescence of Atomically
Precise Silver Clusters by Hydrogen Sulfide
Wei-Miao He, Zhe Zhou, Zhen Han, Si Li, Zhan Zhou,* Lu-Fang Ma, and Shuang-Quan Zang*
[
9]
Abstract: The formation of high-nuclearity silver(I) clusters
remains elusive and their potential applications are still
underdeveloped. Herein, we firstly prepared a chain-like
exchange ligands. Now, the rapid and visualized metal
cluster transformation under mild conditions is very scarcely
observed.
I
t
thiolated Ag complex {[Ag (S Bu) (NO ) (CH CN) (H O) ]
Sulfur ions often template synthesis of high-nuclearity
metal clusters, and sulfur ions come from the fracture of
carbon-sulfur bonds or the additional sulfur components
including the organosulfur compounds and the inorganic
sulfur source. However, to avoid the precipitate of metal-
sulfide and get nanosize metal clusters, the slow release of
sulfur ions from organosulfur compounds are preferably used
during preparation. Hydrogen sulfide, as a classical inor-
ganic sulfur source, has been successfully used in the
construction of small nuclear gold clusters or gold com-
1
8
10
3
8
3
2
2
2
t
[10]
·
[Ag (S Bu) (NO ) (CH CN) ]} (abbreviated as Ag ) in
1
8
10
3
8
3
6
n
18
À
[11]
which two similar Ag18 clusters are assembled by NO3 anions.
The solution containing Ag18 reacted with hydrogen sulfide
with controlled concentration, promptly producing another
identifiable and bright red-emitting high-nuclearity silver(I)
[
12]
t
cluster, Ag (S) (S Bu) (NO ) (abbreviated as Ag ). We
6
2
13
32
3
4
62
[
13]
tracked the transformation using time-dependent electrospray
ionization mass spectrometry (ESI-MS), UV/Vis absorption
and photoluminescence spectra. Based on this cluster trans-
formation, we further developed an ultra-sensitive turn-on
[14]
plexes,
are seldom used for directly preparing high-
sensor detecting H S gas with an ultrafast response time (30 s)
nuclearity silver clusters, probably because of the uncon-
trolled fast nucleation process in solution. Therefore, hydro-
gen sulfide-controlled high-nuclearity silver(I) cluster growth
is still challenging, and no one has reported till now.
2
at a low detection limit (0.13 ppm). This work opens a new way
of understanding the growth of metal clusters and developing
their luminescent sensing applications.
I
Here we report the first ultrafast size expansion of Ag
A
tomically precise metal clusters have attracted extraordi-
cluster, from Ag (Supporting Information, Figure S1) with-
1
8
2
À
2À
nary attention attributed to their fascinating structures and
wide applications in luminescence, sensors and biological
out S ions to Ag62 with 13S ions under room temperature
by using hydrogen sulfide, which is accompanied with a high-
contrast luminescence turn-on response (Figure 1). The
prompt structural transformation was investigated by time-
dependent mass spectrometry, UV/Vis absorption, photo-
luminescence spectra and crystal structure of the reactants
(Ag ) and the products (Ag ). Based on this reaction, a new
[1]
antibacterial. Silver clusters are considered as potential
substitutes for luminescent gold clusters due to their excellent
optical properties. However, the formation mechanisms of
high-nuclearity silver clusters have been a perplexing issue.
The structural transformation and/or nuclear expansion,
tailoring provide a unique platform to understand the
formation process of metal clusters by changing external
conditions, such as peripheral ligand exchange, doping of
metal atoms and the change of solvent molecules.
Although cluster transformation is an effective way to achieve
the control of cluster structure and properties, the process of
metal cluster transformation is mostly slow, the nuclear size in
[
2]
1
8
62
“turn-on” type photoluminescent probe can be developed for
ultrasensitive and highly selective sensing hydrogen sulfide.
[
3]
[4]
Compound {[Ag (C H S) (NO ) (CH CN) (H O) ]
·
1
8
4
9
10
3
8
3
2
2
2
[
5]
[6]
[Ag (C H S) (NO ) (CH CN) ]} (Ag ) crystallizes in the
18 4 9 10 3 8 3 6 n 18
ꢀ
triclinic space group P1 and adopts a one-dimensional
[
7]
À
structure composed of Ag18 clusters bridged by NO3 . Of
note, the adjacent clusters are distinct regarding to the
protecting shell and are alternately arranged in the chain. One
[8]
clusters generally changes slightly and can only happen
under the unusual conditions including heating and excessive
I
À
cluster contains eighteen Ag ions co-protected by ten C H S
4
9
[
*] W.-M. He, Z. Zhou, Z. Han, S. Li, Dr. Z. Zhou, Prof. S.-Q. Zang
Green Catalysis Center, and College of Chemistry, Zhengzhou
University
Zhengzhou 450001 (China)
E-mail: zhouzhan@lynu.edu.cn
zangsqzg@zzu.edu.cn
Dr. Z. Zhou, Prof. L.-F. Ma
Henan Key Laboratory of Function-Oriented Porous Materials,
College of Chemistry and Chemical Engineering, Luoyang Normal
University
[16]
Figure 1. The structure of Ag and Ag62 respectively. Color code: Ag,
1
8
t
2À
green and orange; S of S Bu, yellow; S , violet; O, red; N, blue; C,
gray; H atoms are omitted for clarity. Inserted digital photos: the fast
cluster transform is visualized by luminescent color: Ag18 (left, dark)
and Ag62 (right, bright red) methanol solution by the irradiation of
a 365 nm UV-lamp.
Luoyang 471934 (China)
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
https://doi.org/10.1002/anie.202100006.
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À
ligands, eight NO3 , two coordinated CH CN molecules and
1629.89 Da that was attributed to the Ag (C H S) (NO ) -
16 4 9 8 3 6
+
3
2
two H O molecules, while the neighboring one has six CH CN
(CH CN)(CH OH)(H O) (abbreviated as Ag16 , calcd =
3 3 2 2
2
3
molecules in the ligand shell but no H O (Supporting
1459.91), Ag (C H S) (NO ) (CH OH) (H O) (abbreviated
17 4 9 9 3 6 3 2 2
+
2
2
Information, Figure S2). Both clusters share a macrocyclic
as Ag17 , calcd = 1544.88), and Ag (C H S) (NO ) (H O)
18 4 9 10 3 6 2 3
8
+
2+
(
Ag S ) cationic ([Ag (C H S) ] ), which can be described
(abbreviated as Ag18 , calcd = 1629.84), respectively. These
1
8
10
18
4
9
10
as a three-layer sandwich structure: The interlayer is an Ag8
ring, and two bilevel inverted Ag5S5 pentagrams located
above and below the Ag ring. Ag S of two pentagonal rows
three groups of peaks were ascribed to the dissociation of the
bridged nitrate of chain-like Ag . As for the high-resolution
18
ESI-TOF-MS of Ag , it was obvious that only one group of
8
5
5
62
are constructed alternately by AgÀS bonds. Finally, the
intense peaks at about 2489.55 Da within the m/z 1500–
3500 Da range, which was perfectly aligned with the mass
spectra of the four positively charged Ag62 (calcd = 2489.52)
(Figure 2b).
bilayer inverted Ag S pentagrams connect with the Ag8
5
5
ring interlayer by AgÀAg interactions and AgÀS bonds, thus
creating a sandwich-shaped Ag S cluster. Powder X-Ray
1
8 10
Diffraction (PXRD) of Ag confirmed the phase purity of the
as-synthesized product, which is used directly in the next step
When the crystals are dissolved in methanol, the Ag62
solution portrays a bright red luminescence with the max-
imum emission band locates at near 603 nm (Supporting
Information, Figure S5), while the Ag18 solution has no
photoluminescence (Supporting Information, Figure S5)
under the excitation wavelength of 392 nm. And the quantum
yield of Ag62 solution was calculated to be 2.31%. Meanwhile
the UV/Vis spectrum of Ag62 divulges an absorption peak in
the visible region (around 540 nm) whereas the Ag18 has no
absorption peak under the same conditions (Supporting
Information, Figure S6). The great difference observed
between the emission and absorption of Ag62 and Ag18 will
significantly display promising potentials in future detection.
The high-resolution mass spectrometry titration was
performed to investigate the transformation mechanism
from Ag18 to Ag . The titration mass spectrometry of Ag
1
8
(
Supporting Information, Figure S3).
The rational choice of sulfur source and controlled release
of sulfur ion are the keys to prepare high-nuclearity metal
clusters. After sodium hydrosulfide was carefully added as
sulfur source into the Ag methanol solution, surprisingly, the
1
8
colorless solution was rapidly (30 s) turned to red along with
the appearance of red photoluminescence (Figure 1). Red
block crystals were obtained after slowly evaporating meth-
anol at room temperature. Single-crystal X-ray structural
analysis revealed that the red crystal was composed of sixty-
two silver(I) atoms, thirteen sulfur ions, thirty-two C H S and
4
9
four nitrate ions with a formula as Ag (S) (C H S) (NO )
3 4
6
2
13
4
9
32
À
(
Ag ). Except for the different two coordinated NO and
6
2
3
À
two NO3 counterions, the Ag62 was similar to the previously
62
18
À1
reported one prepared by using organic sulfur source at high
(1 mgmL in methanol) upon treatment with different
concentrations of NaHS (0, 0.5, 1.0, 1.2, 1.5, 2.0 and
2.5 mM) for 5 min (Supporting Information, Figure S7). The
[
11a]
temperature (658C) for 20 h.
Ag62 nanocluster can be
divided into an Ag S core and an Ag48S32 shell connected by
1
4 13
2
+
AgÀAg and AgÀS bonds. (Supporting Information, Fig-
peaks at about 1629.89, 1544.92, and 1459.97 Da (Ag
,
8
1
2
+
2+
ure S4). Ag S core can be regarded as a face-centered
Ag17 , and Ag16 ) were gradually decreased with the
1
4 13
cube constructed by fourteen silver ions. One of the thirteen
increasing concentration of NaHS, while the peaks at about
2
À
4+
3+
S
ions in Ag S is located in the center of the cube bonding
2489.55 and 3340.10 Da (Ag62
and Ag62
Supporting
1
4 13
to six face-centered Ag atoms with the AgÀS distances in the
Information, Figure S8) were formed with the 1.2 mM of
NaHS and gradually enhanced with higher concentration of
NaHS. Therefore, sodium hydrosulfide can react with Ag18 to
produce Ag62 rapidly. To study the whole conversion process
2
À
range of 2.506–2.696 ꢀ. The other twelve S ions bridges
three Ag atoms in the same facet. The Ag S shell consists of
4
8 32
forty-eight Ag atoms and thirty-two C H S assembled
4
9
through AgÀAg and AgÀS bonds. Two exposed Ag atoms in
between Ag18 and Ag , the time-dependent high-resolution
mass spectrometry was conducted (Figure 3). When adding
62
À
the shell are protected by two NO3
.
The chemical composition of Ag18 and Ag62 in solution
was determined by high-resolution ESI-TOF-MS with the
positive ion mode. As shown in Figure 2a, the mass curve of
Ag18 had three main peaks at about 1459.97, 1544.92, and
Figure 2. Mass spectra of Ag18 (a) and Ag62 (b), the measured (black
trace) and simulated (red trace) isotopic distribution patterns of the
corresponding the molecular ion peaks.
Figure 3. Time-dependent high-resolution mass spectrometry of Ag18
solution with the treatment of NaHS (1.2 mM).
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À1
NaHS (1.2 mM) to the Ag18 solution (1 mgmL ), the time-
tracking mass spectrometry analysis found that the peaks of
Ag18 (1459.97, 1544.92, and 1629.89 Da) were almost disap-
peared within 30 s, wihle some new peaks located at 1700–
reached a plateau within 30 s (Supporting Information,
Figure S9), which was consistent with the previous result of
high-resolution mass spectrometry (Figure 3). When sodium
À1
hydrogen sulfide was added to Ag18 solution (0.1 mgmL ),
2
300 Da were appeared, which was possible attributed to the
the photoluminescence intensity increased gradually with
increasing concentrations of NaHS from 0 to 150 mM (Fig-
ure 4a). The color of the solution immediately changed from
colorless to pale yellow, accompanied with red photolumi-
nescence under the excitation of a 365 nm UV light (Fig-
ure 4a, inset photo). Moreover, there was a good linear
relationship between the photoluminescence intensity of Ag18
solution at 603 nm and the concentration of sodium hydro-
sulfide (Figure 4b). However, the addition of the other
formation of the small core silver clusters after the destruction
of Ag18 by S . Meanwhile, a new small peak at about
2
2
À
4
+
489.55 Da (Ag62 ) was observed and growing as time goes
on, which was proved that some of the above mentioned small
core silver clusters are continued reassemble to the new silver
cluster (Ag ) by the stimulation of S . Furthermore, we took
videos to record the significant changes of photoluminescence
and color from the Ag18 solution with or without the addition
of sodium hydrosulfide. The strong red emission and light red
color were rapidly observed after adding sodium hydrosulfide
to the Ag18 solution (video 1 and video 2).
2
À
6
2
+
+
+
+
interferences including some ions (Ag , K , NH , Na ,
4
2
+
2+
2+
2+
2+
2+
2+
2+
2+
3+
Cu , Ba , Mg , Zn , Cd , Hg , Co , Cd , Mn , Gd ,
3
+
À
À
À
À
À
À
À
2À
Fe , NO , NO2 , ClO4 , F , BF4 , PF6 , CH COO , SO
,
3
3
4
À
2À
As we all know, H S is a kind of air pollutant, but play
HSO3 , and SO3 ), oxidizing substance (H O ), some amino
2 2
2
[
15]
a crucial role in many physiological processes. Therefore, it
is urgent to develop a highly sensitive hydrogen sulfide probe.
Based on the above experiments, it has been verified that the
Ag solution is very sensitive to hydrogen sulfide, and it could
acids (GSH and Cys), and some common thiols (2-Propene-1-
thiol, tert-butyl mercaptan, benzyl mercaptan, 4-tert- butylbe-
nethiol, and [4-(tert-butyl)phenyl]methanethiol) did almost
not change the photoluminescence in Ag solution (Figure 4c
1
8
18
be visually monitored by photoluminescence and UV/Vis
spectrum, which provide good opportunities to quantitatively
analyze hydrogen sulfide.
and d), which indicated that Ag could be used as a “turn-on”
1
8
type of probe for selectively sensing hydrogen sulfide with
excellent stability against various ions and highly oxidation
and reduction substances. Moreover, it can also be found that
the characteristic UV/Vis peak of Ag62 at 540 nm gradually
increased upon adding the increasing concentration of NaHS
from 0 to 150 mM (Figure 4e). Both photoluminescence and
The photoluminescence kinetic spectrum was firstly
conducted to investigate the response time between hydrogen
sulfide and Ag , and the photoluminescence intensity of
1
8
solution at 603 nm increased with the growing time and
Figure 4. Photoluminescence diagram of NaHS titration (a), the linear relationship of NaHS titration (b), photoluminescence spectra of Ag
1
8
+
À
+
2+
2+
solution before and after adding different substances (c), selectivity of Ag solution to NaHS (1 blank, 2 NH , 3 PF6 , 4 Na , 5 Ba , 6 Cu , 7
1
8
4
À
À
2+
+
À
3+
2+
2+
À
À
2À
À
ClO4 , 8 F , 9 Mg , 10 Ag , 11 NO , 12 Fe , 13 H O , 14 Co , 15 Mn , 16 CH COO , 17 NO , 18 Cys, 19 GSH, 20 SO3 , 21 HSO3 , 22
SO4 , 23 BF4 , 24 HCO3 , 25 Cd , 26 Zn , 27 Gd , 28 Hg , 29 Cd , 30 K , 31 2-Propene-1-thiol, 32 tert-Butyl Mercaptan, 33
BenzylMercaptan, 34 4-tert-Butylbenethiol, 35 [4-(tert-Butyl)phenyl]methanethiol and 36 HS , respectively) (d), UV/Vis spectra of Ag titrated by
3
2
3+
2
3
2
2
À
À
À
2+
2+
2+
2+
+
À
1
8
NaHS (e), photoluminescence diagram of H S gas (f).
2
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UV/Vis spectra show that Ag18 could be able to serve as the
fluorescent and colorimetric probe to detect hydrogen sulfide
quantitatively.
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sulfide gas, various amounts of H S gas were injected into the
2
À1
Ag18 solution (0.1 mgmL ) carefully, and the photolumines-
cence and UV/Vis spectra were recorded. The photolumines-
cence relative intensity at 603 nm increased gradually with the
increasing concentration (0–114 ppm) of H S gas, and showed
2
a good linear relationship with a certain concentration range
[
(
from 24.4 to 105.8 ppm) of H S gas (Supporting Information,
2
Figure S10). The LOD for H S gas was calculated as
2
20426 – 20433; b) S. C. Hau, P.-S. Cheng, T. C. Mak, J. Am.
0
.13 ppm. Similar to that of sodium hydrosulfide, the UV/
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sulfide gas (Supporting Information, Figure S11). Therefore,
the transformation process between Ag18 to Ag62 can be used
2
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as a rapid, sensitive and selective probe for the real H S gas.
2
In summary, we prepared a new chain-like thiolated-
silver(I) complex built from two alike Ag18 clusters assembled
by nitrate. An ultrafast size expansion of silver clusters
stimulated by hydrogen sulfide was observed and investigated
by time-dependent ESI-MS, UV/Vis and photoluminescence
spectra. The expansion process is accompanied by an effective
1
1
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2
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for Innovative Research Team (in Science and Technology) in
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The authors declare no conflict of interest.
[
Keywords: cluster to cluster transformation · fluorescent probe ·
hydrogen sulfide · silver(I) clusters
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Manuscript received: January 1, 2021
Accepted manuscript online: January 23, 2021
Version of record online: March 3, 2021
Angew. Chem. Int. Ed. 2021, 60, 8505 –8509
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