The solvent-induced isomerization of silver thiolate clusters with symmetry transformation

Article abstract of DOI:10.1039/d0cc01195a

A novel ligand-stabilized Ag12 nanocluster was synthesized as a model cluster to investigate the solvent-induced isomerization of Ag12 clusters. Another two novel Ag12 clusters as well as their related symmetry transformations were also successfully obtained through the above solvent-induced isomerization process.

Full text of DOI:10.1039/d0cc01195a

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The solvent-induced isomerization of silver thiolate clusters with
symmetry transformation
*Received 00th January 20xx,
Accepted 00th January 20xx
Xu-Ran Chen,a Ling Yang,a Yu-Ling Tan,a Hong Yu,*a Chun-Yan Ni,a Zheng Niu*a and Jian-Ping
Lang*a,b
DOI: 10.1039/x0xx00000x
A novel ligand-stabilized Ag12 nanocluster was synthesized as a generate different physicochemical properties and chemical
model cluster to investigate the solvent-induced isomerization of reactivities.9 However, the isomerization of the metal core of
Ag12 clusters. The other two novel Ag12 clusters as well as their the metal nanoclusters remains a significant challenge because
related symmetry transformations were successfully obtained the small changes in the assembly process can lead to a
through the above solvent-induced isomerization process.
significant change of the metal numbers in the metal
nanoclusters.10 To date, there have been a few reports about
the isomerization of the ligand-stabilized metal nanoclusters,
much less the isomerization of Ag(I) nanoclusters. The
reported examples about the isomerization of the Ag(I)
nanoclusters primarily based on the ligand-change method,
which employs the different ligands to obtain different Ag(I)
nanoclusters with the same nuclearity.11 However, the
symmetry of these Ag(I) cluster isomers generally almost keeps
no change. Therefore, it represents a tough job for the design
and synthesis of Ag(I) clusters that can exhibit the
isomerization with symmetry transformations upon mild outside
stimuli, such as solvent change.
The exchange reaction of coordinated solvent molecules is
one kind of fundamental reactions in the coordination
chemistry.12 In such coordination systems, the exchange of the
coordinated solvent molecules can make a remarkable change
on the structure.13 As illustrated in Scheme 1, the coordinated
solvent molecules on the nanocluster A not only stabilize the
metal cluster but also generate the interactions with the
neighbor atoms to reach a certain symmetry of the cluster.
Therefore, the change of the coordinated solvent molecules
may afford an isomer nanocluster B with a similar structure
but a different symmetry. In this regard, we prepared an Ag12
Increasing attention has been drawn to ligand-stabilized metal
nanoclusters in recent decades because of their intriguing
structures and broad applications in photoluminescence,
catalysis, biosensing and bioimaging.1,2 Most of the works in
this topic mainly focus on the transition metals, especially
noble metals, such as Au, Ag, Pd etc.3 Among them, ligand-
stabilized Ag(I) nanoclusters persist in attracting interest since
their fascinating structures and rich physicochemical
properties.4 In general, these Ag(I) nanoclusters can be
obtained from the self-assembly process between the ligands
including alkynyl, thiolate or organophosphorus compounds
and the Ag(I) salts with different anions.5 Through adjusting
the central template anions, auxiliary ligands or reaction
conditions, numerous ligand-stabilized Ag(I) nanoclusters with
different cores can be synthesized.6 The current study about
the ligand-stabilized Ag(I) clusters primarily focuses on the
construction of their novel diverse structures and
physicochemical properties,7 while it remains insufficient for
investigating the isomerization of the ligand-stabilized Ag(I)
clusters under external stimuli.
Isomerization is a fundamental transformation in nature,
and it plays a significantly important role in various biological
processes.8 The isomerization has attracted much attention in
synthetic chemistry and supramolecular chemistry since the
different arrangements of the same number of atoms would
nanocluster
with
an
octadecahedron
geometry,
Ag12(Tab)6(TFA)12(H2O)2·4CH3CN (TFA = trifluoroacetate, Tab = 4-
(trimethylammonio)benzenethiolate14) (Ag12a), as a model
cluster to explore the solvent-induced isomerization or rather
the symmetry transformation of the silver nanoclusters (Table
S1,ESI†). Ag12a can be readily converted to the other two
novel Ag12 nanocluster, Ag12(Tab)6(TFA)12·2DMF (Ag12b) and
a. College of Chemistry, Chemical Engineering and Materials Science, Soochow
University, Suzhou 215123, Jiangsu, People’s Republic of China. Fax: 86-512-
65880328; E-mail: jplang@suda.edu.cn; nkniuzheng@163.com
b. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic
Chemistry, Chinese Academy of Sciences, Shanghai, 200032, People’s Republic of
China.
Ag12(Tab)6(TFA)10(CH3CN)2·2TFA (Ag12c), which show lower
symmetry, through changing the coordinated solvent
molecules. The main structures of Ag12b and Ag12c are similar
to that of Ag12a, but some symmetry elements in the
structure of Ag12a got disappeared in the transformation
c. Electronic Supplementary Information (ESI) available: Experimental procedures and
compound characterizations. CCDC 1974330, 1974470 and 1974488. For ESI and
crystallographic data in CIF or other electronic format See DOI: 10.1039/x0xx00000x
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process. Remarkably, the transformation from Ag12a to Ag12b solvent in Ag12b except two dissociative DMVFiewmAortilcelecOunlelinse,
and Ag12c can be realized by simply changing the solvents at which could be due to the big sDizOeI: 1a0n.1d039a/Dp0pCrCo0p1r1i9a5tAe
room temperature, thus exhibiting the solvent-induced coordination capability of DMF. The silver atoms are
isomerization of the silver nanoclusters.
coordinated with solvent and TFA in Ag12a but are
coordinated with TFA anion only in Ag12b, so the distance
between Ag4 and Ag6 is stretched to 4.017 Å. However, the
distance between Ag4 and Ag3 is shortened to 3.311(7) Å. The
six Tab ligands protecting the silver skeleton adopt the μ4-
η1:η1:η1:η1 ligation mode with Ag-S bonds being 2.464(12)-
2.672(13) Å (Fig. S2b, ESI†). Finally, the distance between Ag3
and Ag6 reaches 3.962 Å which is longer than that between
these two Ag atoms in Ag12a (Ag-Ag bond length is 3.100(14)
Å). The coordinated twelve TFA anions are arranged in two
types of coordination modes: four of them are coordinated in
the vertex of the cluster (μ1-η1:η0 mode) with Ag-O distances
being 2.205(5)-2.265(5) Å and remaining eight TFA anions
adopt a μ2-η1:η1 mode with Ag-O distances being 2.265(5)-
2.579(5) Å (Fig. S2c, ESI†). It is worth noting that the slight
change of the coordinated solvent molecules plays a crucial
role in the assembly process of the silver clusters.
Scheme
1
The solvent-induced nanocluster isomerization with symmetry
transformation. The purple and yellow balls stand for the different solvent molecules
while the blue ball stands for the coordinated ligands.
The model nanocluster Ag12a was synthesized at room
temperature according to the reaction of Tab and silver(I) salt
in DMF, CH3CN and H2O mixed solvent system. Colorless block
crystals of Ag12a were then obtained through the diffusion
method. Ag12a crystallizes in the orthorhombic space group
Pbca and its kernel is stabilized by 6 Tab, 12 TFA and 2 water
molecules (Fig. 1 and Fig. S1, ESI†). As shown in Fig. 1c, the
essence of Ag12a is an Ag12 skeleton welded by argentophilic
interactions formed a regular hollow octadecahedron with
Ag···Ag contacts being 2.943(6)-3.269(7) Å. The six Tab ligands
supporting the Ag12 skeleton adopt a quadruple coordination
mode, or more precisely, the ligands adopt a μ4-η1:η1:η1:η1
ligation mode where the Ag-S bond distances are in the range
of 2.451(13)-2.620(13) Å (Fig. S1b, ESI†). The twelve TFA
ligands can be classified into three groups: two of them
adopting a μ3-η2:η1 ligation mode, six adopting a μ2-η1:η1
ligation mode and the other four adopting a μ2-η1:η1 ligation
mode with Ag-O distances being 2.257(5)-2.867 Å (Fig. S1c,
ESI†). The coordinated water molecules adopting a μ2 ligation
mode bridge the two adjacent Ag atoms and get fixed by H-
bonding interactions between TFA anions and H2O molecules.
There are two H2O molecules coordinated with the silver in the
vertex of the core structure, thus producing a change to be
exchanged by other molecules. The weak interactions between
the coordinated H2O molecules and the TFA anions are
contributed to the certain kernel geometry with D2h symmetry.
The structure analysis of Ag12a encourages us to adjust the
nanocluster structure based on the classic hard-soft-acid-base
(HSAB) theory.15 If the hardness of the solvent molecule was
adjusted, competition between the solvent, TFA and Tab could
influence the whole structure rather than partial distortion.
Based on the above consideration, the solvent system was
changed to the mixture solvent of CH3OH and DMF, and a new
Ag12 isomer, Ag12b, was obtained. It crystallizes in monoclinic
space group C2/c and its kernel is stabilized by 6 Tab and 12
TFA (Fig. S2, ESI†). Compared to that of Ag12a, the core of
Ag12b is a distorted hollow octadecahedron structure with
Ag···Ag contacts being 2.990(6)-3.364(7) Å and the symcenter
is the only symmetry element (Fig. 2). There is no coordinated
Fig. 1 (a) and (b) View of the crystal structures of Ag12a along with two
orthogonal directions. Free solvent molecules and H atoms are omitted for
clarity. (c) and (d) View of the Ag12 kernel in a polyhedron mode. Color codes:
green, Ag; yellow, S; red, O; blue, N; grey, C; sky blue, F.
The above experimental results confirmed that the solvent
strategy could influence the assembly process greatly and
silver nanocluster isomers could be formed when the different
solvents were chosen. A one-step strategy originated from the
above results was used again: the silver salts and thiolate
ligands were dissolved in CH3CN. After five days, some
colorless block crystals can be observed by the diffusion of
Et2O into the mixture. The following X-ray analysis reveals that
another new Ag12 isomer, Ag12c, crystallizes in the monoclinic
space group P21/n and its kernel is stabilized by 6 Tab and 10
TFA (Fig. S3, ESI†). Ag12c has
a
hollow distorted
cuboctahedron structure constructed by sparse argentophilic
interactions with Ag···Ag contacts being 2.916(12)-3.418 Å (Fig.
2), whose symmetry is totally different from those of Ag12a
2 | J. Name., 2012, 00, 1-3
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and Ag12b. The six Tab ligands supporting the Ag12 skeleton A similar procedure was applied to transformVieAwgA1rt2icale Oinnlitnoe
adopt the same quadruple coordination mode with the Ag-S Ag12c if the solvent was changed to CDHO3CI:N10.(1F0i3g9./DS06CcC, 0E1S19I†5)A.
distances being 2.478(3)-2.583(3) Å (Fig. S3b, ESI†). Ten TFA When Ag12b was re-crystallized in CH3CN, pure Ag12c crystals
anions which protect the silver skeleton as well adopt two were afforded (Fig. S6d†). When the re-generated Ag12c was
types of coordination modes: two adopting the μ1-η1:η0 re-crystallized in DMF, its PXRD patterns could be recovered to
ligation mode and eight adopting the μ2-η1:η1 ligation mode those of Ag12b, thus implying that Ag12b can readily
with the Ag-O bonds being 2.232(4)-2.551(2) Å (Fig. S3c, ESI†). isomerize into Ag12c reversibly (Fig. S5c†). The PXRD patterns
In particular, the two coordinated CH3CN molecules which of Ag12c could also correspond to the changes of those of
exhibit strong coordination ability, protect the vertex of the Ag12a (Fig. S4, ESI†) and Ag12b (Fig. S5, ESI†), thus further
silver kernel and occupy the place supposed to TFA anions. confirming the isomerization of Ag12a, Ag12b and Ag12c.
Notably, only a small amount of Ag atoms are coordinated by
the CH3CN molecules in each silver cluster, but the structure
and symmetry of the entire isomer were affected prodigiously.
Fig. 3 View of the crystal structures of Ag12a, Ag12b and Ag12c. Anions, free
solvent molecules and H atoms are omitted for clarity. Color codes: green, Ag;
yellow, S; red, O; blue, N; grey, C; sky blue, F.
Fig. 2 The ball-stick representation of Ag12S6 core (left, color code: Ag, green; S, yellow)
and view of the corresponding Ag12 kernels in a polyhedron mode with different
symmetry.
Although the crucial role of solvent molecules in the
isomerization can be illustrated through the detailed structural
analysis, more insight into the assembly process of the
nanoclusters in solution still needs obtained. The mother
liquors in the isomerization experiments were examined by
using electrospray ionization mass spectrometry (ESI-MS) (Fig.
S7-S11†). The Ag12c solution (obtained from dissolving Ag12a
We are curious about the solvent effect and the three Ag12
isomers inspire us to investigate the isomerization of them by
similar methods. To dissolve 20 mg crystals of Ag12a into 2mL
CH3OH and DMF mixed solvent and recrystallize it through the
diffusion process, about 5 mg block crystals of Ag12b can be
obtained. The structure of the crystals can be confirmed by
single-crystal X-ray analysis. We successfully realized the
isomerization between Ag12a and Ag12b. If we dissolved the
crystals of Ag12a into DMF, CH3CN, water and recrystallized it
through the similar diffusion process, the crystals of Ag12c
were isolated and thus isomerization between Ag12a and
Ag12c can also be realized. The following experiments
indicated that the three Ag12 isomers can be readily
transformed into each other in the related solvent systems.
The powder X-ray diffraction analysis was also employed to
confirm the reversible configuration transformation between
Ag12a, Ag12b and Ag12c. The experimental PXRD patterns of
Ag12a can match its calculated patterns very well (Fig. S4,
ESI†), which demonstrated the high purity of its bulk sample.
After dissolving crystals of Ag12a into DMF and recrystallizing
it through the diffusion process, the new PXRD patterns
presented a structural change from Ag12a to Ag12b, which
can meet those derived from the single crystal data (Fig. S5b†).
in CH3CN) had
a major fragment at m/z = 662.96
corresponding to [Ag4(Tab)4(TFA)2]2+ (Fig. S7†). However, the
Ag12b solution (obtained from dissolving Ag12a in DMF)
showed more characteristic fragments like [Ag4(Tab)3(TFA)2]2+,
[Ag4(Tab)3(TFA)2(DMF)2]2+,
(Ag5(Tab)4(TFA)3)2+,
and
(Ag6(Tab)4(TFA)4)2+ (Fig. S8†). The much heavier fragments
[Ag7(Tab)4(TFA)5]2+ and [Ag8(Tab)4(TFA)6]2+ were observed in
the Ag12a solution in H2O/CH3CN/DMF (Fig. S9†) compared to
the previous two isomers.9a A meaningful result was the
pronounced
DMF-containing
fragment
signal
of
[Ag4(Tab)3(TFA)2(DMF)2]2+ (m/z = 652.46) (Fig. S8-S9†) or
[Ag6(Tab)4(TFA)3(DMF)2]2+ (m/z = 873.35) (Fig. S10†) which
indicated that the DMF molecules might coordinate with silver
atoms in Ag12a, Ag12b and Ag12c during the assembly
process but were substituted by TFA anions ultimately. The
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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Wang, C. H. Tung, D. Sun and L. S. Zheng, J. Am. Chem. Soc.,
isomerism between Ag12b and Ag12c was also monitored by
ESI-MS (Fig. S10-S11†), thus confirming the solvent effects.
In conclusion, a novel Ag12 cluster, Ag12a, was synthesized
to explore the isomerization process of Ag12 cluster isomers.
Through adjusting the solvent systems in the synthetic
reactions, another two Ag12 isomers, Ag12b and Ag12c were
successfully obtained. In particular, these three Ag12 isomers
can be converted into each other by changing the solvent
systems. The isomerization of the Ag12 isomers can be also
confirmed by PXRD. Furthermore, the mechanism of the
isomerization processes of Ag12 cluster isomers can be
illustrated through the detailed structural analysis. This work
offers not only new insight into the isomerization of the metal
thiolate nanoclusters but also a new entry to synthesize novel
metal thiolate nanoclusters. In addition, this work also extends
the multi-dimensional Ag cluster-based frameworks through
enriching the Ag cluster second building units with different
symmetries.
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9
This work was financially supported by the National Natural
Science Foundation of China (Grant Nos. 21531006 and
21773163), the State Key Laboratory of Organometallic
Chemistry of Shanghai Institute of Organic Chemistry (2018kf-
05) and the Project of Scientific and Technologic Infrastructure
of Suzhou (SZS201905). We are grateful to the useful
comments of the editor and the reviewers.
Conflicts of interest
There are no conflicts to declare.
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DOI: 10.1039/D0CC01195A
Graphic Contents Entry
The solvent-induced isomerizations of Ag12 clusters with symmetry transformations were realized
by changing the coordinated solvent molecules at room temperature.
Figure for Graphic Contents Entry