Anion-Templated Nanosized Silver Alkynyl Clusters: Cluster Engineering and Solution Behavior

Article abstract of DOI:10.1002/chem.201605440

Assembly of nanosized polynuclear metal clusters from simple building blocks usually involves complicated self-organization processes and thus is a long-standing challenge. Here, we demonstrate the controllable assembly, single-crystal structures and solution behaviors of four molecular assemblies based on nanosized silver alkynyl clusters, formulated as {[(CrO₄)₂Cl@Ag₄₂(PhC≡C)₃₄(CF₃COO)₂]?CF₃COO} (1), {(NH₄)[(CrO₄)₂Cl@Ag₄₂(PhC≡C)₃₄(CrO₄)(H₂O)₂]?2BF₄?CH₃OH}_n (2), [(CrO₄)@Ag₂₂(PhC≡C)₁₆(CF₃SO₃)₄]_n (3), and {[(CrO₄)₂@Ag₃₁(PhC≡C)₂₂(CF₃SO₃)₄]?CF₃SO₃?2CH₃OH?H₂O}_n (4). In the presence of concomitant CrO₄^2? and Cl^? templates, we could isolate a discrete cluster 1 and a polymeric chain-like compound 2 by using different silver salts. Both 1 and 2 have a similar 42-metallic cage, which traps two CrO₄^2? and one Cl^? as anion templates. Using sole CrO₄^2? template, 3 and 4 were simultaneously isolated in a one-pot reaction. Both of them are 1D chain structures based on single CrO₄^2? templated Ag₁₈ and double CrO₄^2? templated Ag₃₀ clusters, respectively. HR-ESI-MS was used to study the solution behaviors of 1–4. This work has the following purposes: i) it presents the cluster engineering concept used in the assembly of polynuclear silver alkynyl clusters; ii) it exemplifies template effects from hetero and homo anions; and iii) it provides a controllable way to achieve assembly of silver alkynyl clusters.

Full text of DOI:10.1002/chem.201605440

A Journal of
Accepted Article
Title: Anion-Templated Nanosized Silver Alkynyl Clusters: Cluster
Engineering and Solution Behavior
Authors: Shan-Shan Zhang, Haifeng Su, Zhi Wang, Chen-Ho Tung, Di
Sun, and Lan-Sun Zheng
This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
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to ensure accuracy of information. The authors are responsible for the
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To be cited as: Chem. Eur. J. 10.1002/chem.201605440
Link to VoR: http://dx.doi.org/10.1002/chem.201605440
Supported by

Chemistry - A European Journal
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Anion-Templated Nanosized Silver Alkynyl Clusters: Cluster
Engineering and Solution Behavior
†
[
a],
[b]
[a]
[c]
[a]
[a]
Shan-Shan Zhang, Hai-Feng Su, Zhi Wang, Lina Wang, Quan-Qin Zhao, Chen-Ho Tung, Di
[
a]
[b]
Sun*, Lan-Sun Zheng,
Dedication ((optional))
Abstract: Assembly of nanosized polynuclear metal clusters from
simple building blocks usually involves complicated self-
organization processes and thus is a long-standing challenge.
Herein we demonstrate the controllable assembly, single crystal
structures and solution behaviors of four molecular assemblies
based on nanosized silver alkynyl clusters, formulated as
soluble silver salt was used to the decompose polymeric silver
alkynyls to soluble oligomers.[2] Based on these oligmeric silver-
alkynyl supramolecular synthons, series of 1D, 2D, and 3D
networks were obtained by Mak group.[3] Further advances in
silver-alkynyl complexes were achieved by introducing various
-
-, CO
2-, SO
2-,
anions as templates including inorganic Cl , NO
3
3
4
{
{
(
{
[(CrO
4
)
2
Cl@Ag42(PhCC)34(CF
)[(CrO Cl@Ag42(PhCC)34(CrO
[(CrO )@Ag22(PhCC)16(CF
@Ag31(PhCC)22(CF SO ]·CF
3
COO)
2
]·CF
3
COO}
]·2BF
(3),
OH·H
and Cl templates, we could
isolate a discrete cluster 1 and a polymeric chain-like compound
(1),
CrO
4
2-, and larger polyoxometalate and even organic squarate to
(NH
4
)
4 2
4
)(H O)
2
2
4
·CH
3
OH}
n
achieve high-nuclear clusters.[4] Although many large silver
alkynyl clusters have been synthesized by Mak, Wang groups and
so on,[5] the assembly of silver and alkynyl into highly ordered
high-nuclear clusters is still a matter of chance. On the other hand,
different anions as templates caged in one silver alkynyls clusters
have rarely been observed in this field. Different anions have
different dimension, geometry and charge state which can
aggregate silver atoms around themselves in a respective fashion
on the basis of electrostatic interactions, then creating more
complex and amazing silver-alkynyl clusters finally.[6] To the best
of our knowledge, only one example is an anionic Ag36 cluster
2),
4
3
SO
)
3 4
]
n
and
O} (4).
2 n
[(CrO
4
)
2
3
3
)
4
2
3
SO
3
·2CH
3
-
-
In the presence of concomitant CrO
4
2
by using different silver salts. Both 1 and 2 have a similar 42-
2-
and one Cl- as anion
and were
simultaneously isolated in one-pot reaction. Both of them are 1D
metallic cage which traps two CrO
4
2-
templates. Using sole CrO
4
template,
3
4
2-
chain structures based on single CrO
double CrO 2
4
templated Ag18 and
-
4
templated Ag30 clusters, respectively. High-
resolution electrospray mass spectrometry (HR-ESI-MS) was
used to study the solution behaviors of 1-4. This work i) presents
the cluster engineering concept used in the assembly of
polynuclear silver alkynyl clusters; ii) exemplifies template effects
from hetero and homo anions; and iii) provides a controllable way
to achieve assembly of silver alkynyl clusters.
-
]4-. In this case, smaller Cl-
template by one Cl and two [(O) V O
2 2 6
]4-
2 2 6
shaped a smaller Ag13 cage, whereas the larger [(O) V O
logically gave a larger Ag30 cage. Two cages fused together by a
vertex-sharing mode to form the final Ag36 cluster. [7]
Introduction
As one of the oldest organometallics known, silver alkynyls
have been considerably focused due to their potential
applications in many fields such as catalysis, organic
optoelectronics, and luminescent materials and so on.[1] Due to
their strong coordination ability to silver ions, silver alkynyls are
usually considered to be very difficult to dissolve in common
solvents, which was not resolved until high concentrations of
Scheme 1. Top: Schematic presentation of bottom-up assembly of 1-4.
Bottom: Photographs for crystals of 1-4 taken under the microscope (TMAH =
‡
[
[
[
a]
b]
c]
S.-S Zhang, Z. Wang, Dr. Q. Q. Zhao, Prof. C-H Tung, Dr. D. Sun
Key Lab of Colloid and Interface Chemistry, Ministry of Education,
School of Chemistry and Chemical Engineering, Shandong
University, Jinan, 250100, P. R. China. E-mail: dsun@sdu.edu.cn.
tetramethylammonium hydroxide and TMEDA
ethylenediamine)
= N,N,N’,N’-tetramethyl-
With aforementioned in mind, herein we systematically
modulate the silver salts and the templates in the [PhCCAg]
‡
H.-F Su, Prof. L-S Zheng
n
State Key Laboratory for Physical Chemistry of Solid Surfaces and
Department of Chemistry, College of Chemistry and Chemical
Engineering, Xiamen University, Xiamen, 361005, P. R. China.
Dr. L. Wang
College of Environment and Safety Engineering, Qingdao University
of Science and Technology, Qingdao, 266042, China.
These authors have equally contributed to this work.
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201xxxxxx.
assembly system and isolated four novel silver alkynyls with
different cluster units template by one or two kinds of anions.
Different anions play respective roles in the construction of silver
alkynyls and synergistically stabilize the final products. High-
resolution electrospray mass spectrometry (HR-ESI-MS) was
also used to study the solution behaviors of them and provided
some possible clues relating to their assembly process in
solution.
‡
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Chemistry - A European Journal
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FULL PAPER
-
highlighted by blue polyhedra and Cl by bigger yellow ball. (c) [(CrO
cage. (d) [Cl@Ag10] cage.
4
)@Ag21]
Results and Discussion
Synthesis Discussions
X-Ray
Crystal
Structures
COO} (1),
O) ]·2BF ·CH
(3), and
·2CH OH·H
{
[(CrO
(NH
4
)
2
Cl@Ag42(PhCC)34(CF
3
COO)
2
]·CF
)(H
)@Ag22(PhCC)16(CF SO
@Ag31(PhCC)22(CF SO ]·CF SO
3
The synthetic details are shown in the Supporting Information
{
4
)[(CrO
(2), [(CrO
[(CrO
(4)
4
)
2
Cl@Ag42(PhCC)34(CrO
4
2
2
4
3
O
n
(SI). Directly mixing [PhCCAg] precursors with silver salts, then
H}
n
4
3
3
)
4
]
n
stirring or ultrasound treating them only gave turbid solutions. In
{
}
4
)
2
3
3
)
4
3
3
3
2
O
a typical synthesis, solvothermal reaction of above turbid mixtures
n
o
at low temperature (~70 C) could make the solution much more
clear. The filtrates evaporated at room temperature could produce
tiny crystals with yields of 20-30% for 1 and 2. The 3 and 4 were
formed as mixture and isolation of them was finished by hand
picking one by one on the basis of their different morphologies
As portrayed in Figure 1a, the structure of 1 was determined by
-
X-ray crystallography with totally 42 Ag atoms, 34 PhCC ligands
-
2-
and 2 coordinated CF
3
COO anions as well as two CrO
4
and one
-
Cl in the interior. Cluster 1 crystallized in the monoclinic C2/c
(Scheme 1). Two kinds of bases were used in this system and the
space group and the asymmetric unit contains only a half of
usage of them is specific to the synthesis of each compound.
During synthesis of 1 and 2, we also explored the influence of
amount of NaCl on the yields of them. When the amount of NaCl
varied from 0.5 to 10 mg with an increment of 0.5 mg, the best
yield of 30 % was obtained when 1 mg NaCl added. We also tried
-
cluster with Cl sitting on an inversion center. The length of 1 is
1
.68 nm without considering the organic shell, whereas both ends
and the waist diameter is 0.88 and 0.49 nm, respectively, giving 1
a dumbbell like geometry. The structure of all-silver skeleton of 1
4
could be seen as arising from two [(CrO )@Ag21] cluster at two
-
-
to introduce Br and I into 1 and 2, and the results showed the
ends sandwiched one [Cl@Ag10] cluster at waist through face-
synthesis was highly specific to the chloride ion as a template,
2-
shared pentagons (Figure 1b). Tetrahedral CrO
4
resides in the
-
-
which may be caused by the unsuitable radius of Br and I or/and
bigger cage (Figure 1c) and interacts with Ag atoms by a 10
-
much smaller Ksp of AgBr and AgI.
2
2
3
3

: : : mode with Ag-O distances of 2.42-2.77 Å, whereas
-
spherical Cl resides in the smaller pentagonal anti-prism cage
(Figure 1d) and is fixed by surrounding ten Ag atoms with Ag-Cl
distances of 2.85-3.11 Å. Excluding the supporting effects from
inner anions, the overall silver skeleton is also reinforced by
Ag···Ag interactions[8] ranging from 2.79 to 3.43 Å and exteriorly
protected by PhCC- ligands and CF COO- anions. The
3
argentophilic interactions were also evidenced by the low-
frequency solid-state Raman spectrum (Figure S1). The
moderate sharp peak located at 64.2 cm-1 was observed with
laser excitation at ex = 632.8 nm, which corresponded to the
stretching vibrations of the Ag···Ag bonds.[ The 34 PhCC-
ligands show diverse coordination fashions with mixed - and -
9]
1
1
2
1
2
2
type bonding modes, 6 in 
3
-
1:

:
1

:

; 2 in 
3
-

:

:

; 6 in
1
1
1
1:
1: 
1:
1


3
-

1:
:

:
2

; 12 in 
3
-



; 6 in 
3
-



; 2 in  -
3
1


:

. The Ag-C distances range from 2.06 to 2.49 Å and the
is ca. 0.2~0.4 Å longer than that of Ag-C
which are comparable to those reported silver alkynyl
bond lengths of Ag-C


,
compounds.[10] The CF
with Ag-O distances of 2.34 and 2.39 Å.
When changing silver salt and base from CF
COO is in a  - : coordination mode
-
1
1
3
2
3
COOAg and
TMAH to AgBF
4
and TMEDA, we isolated compound 2 as a 1D
)Cl@Ag42] with two CrO 2
-
and
infinite chain consisting of [(CrO
4
4
-
one Cl in the interior. X-ray crystallography revealed that 2
crystallized in monoclinic P2
1
/n space group and the asymmetric
unit contains one [(CrO
4
)Cl@Ag42] cluster (Figure 2a) protected
-
by 34 PhCC and two aqua ligands. The overall silver skeleton
of 2 looks extremely like that of 1. Differently, the [(CrO
4
)@Ag21]
Figure 1. (a) X-ray structure of the 1 with H atoms and guest anion omitted for
clusters at two ends are opened at Ag2 site (Figure 2b) which may
clarity. (Magenta: Ag; atrovirens: Cr; green: Cl; greenyellow: F; black: C) (b)
2
-
2
-
be caused by the tension force from the outer CrO
4
bridges. Due
COO-,
Ball-and-stick view of overall silver skeleton of 1 with tetrahedral CrO
4
to the weak coordination ability of BF -
compared to CF
4
3
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CrO 2
-
here not only acts as anion template within the cage but
4
also takes the role of bridging anion to link the [(CrO
4
)Cl@Ag42]
clusters to the 1D zig-zag chain (Figure 2c).
Figure 3. (a) X-ray structure of the 1D zig-zag chain of 3 with H atoms and guest
anion omitted for clarity. (Magenta: Ag; atrovirens: Cr; green: Cl; greenyellow:
F; gray: C) (b) Ball-and-stick view of [(CrO
4
)@Ag18] cluster of 3 with tetrahedral
highlighted by space-filling mode. (c) The [Ag (PhCC) ] square unit. (d)
Ag12 quadrangular prism.
2
-
CrO
4
4
4
Shuttle-like yellow crystals of 4 were grown along with 3. Single-
crystal X-ray diffraction revealed that compound 4 contains two
Figure 2. (a) X-ray structure of the 2 with H atoms and guest anion and cation
omitted for clarity. (Magenta: Ag; atrovirens: Cr; green: Cl; black: C) (b) Ball-
2
-
and-stick view of overall silver skeleton of 2 with tetrahedral CrO
4
highlighted
4 2
halves of [(CrO ) @Ag30] clusters with another Ag (Ag16) atom
-
by blue polyhedra and Cl by bigger yellow ball. (c) The 1D structure based on
sandwiched by them at the vertex in the asymmetric unit. As
2
-
[
(CrO
4
)Cl@Ag42] units and CrO
4
bridges.
depicted in Figure 4a, the basic building block in 4 is a double
-
anions templated cluster with totally 30 Ag atoms, 22 PhCC and
-
2-
-
4 CF
3
SO
3
anions. The inversion center related to two CrO
4
(10-
In absence of Cl , we simultaneously obtained 3 and 4 in one-
2
2
3
3
pot reaction with solely CrO 2-
 : : : ) templates resides in the Ag
30 cluster (Figure 4b). Of
4
as template. X-ray single crystal
-
1
1; 8 in 
1
1: 1
the 22 PhCC ligands, 1 in 
2
-

1
:

3
-

:


4
;4 in  -
. Three of four
diffraction demonstrated that 3 crystallized into the monoclinic
C2/c space group and the asymmetric unit contains only a half of
1
1
1
1
1
1:
1:
1:
2


: 

:

:

; 6 in 
3
-

:


1
; 3 in 
3
-



1
CF
3
SO -
3
anions adopt the 
remaining 
2
- : coordination fashion and the
- . On the surface of Ag30 cluster, short Ag···Ag
[
(CrO
Compound 3 is a neutral 1D zig-zag chain (Figure 3a) comprised
of alternating [(CrO )@Ag18 clusters (Figure 3b) and
Ag (PhCC) ] squares (Figure 3c), and the latter are sandwiched
by a pair of formers purely through Ag···Ag interactions (3.22-3.39
Å). The [(CrO
4
)@Ag18] cluster and a half of [Ag
4
4
(PhCC) ] square.
1
1
contacts are in the range of 2.86-3.42 Å. Furthermore, Ag30
clusters were extended by Ag16 atom to form the 1D linear chain
structure (Figure 4c), in which each Ag16 atom is bound to two
quadrangular pedestals of two different Ag30 clusters through
eight-fold Ag···Ag interactions (2.98-3.32 Å) and further jointed
with Ag30 cluster through two -type Ag-C coordination bonds
(Ag3-C72 and Ag3-C96; Figure 4d).
4
]
[
4
4
4
9
)@Ag18] cluster is interiorly supported by a  -
2
(
2
2
3
2-
-
: : : CrO
4
and peripherally protected by 12 PhCC ligands
1
1: 1
1
1
1
1
1
2
4 in 
3
-

:


; 4 in 
3
-

:

:

; 4 in 
3
-
  
: : ) and 4
-
1
1
1
1
CF
3
SO
3
anions (2 in 
1
- and 2 in 
3
- : : ). The Ag-C and
Until now, only three chromate templated silver-alkynyl clusters
Ag-O distances fall in the range of 2.08-2.27 Å and 2.27-2.76 Å,
t
have
been
@Ag35(PhCC)28(TMEDA)
@Ag18(iPrCC)12]·4ClO }.[12] No hetero anions template
reported,
{[(CrO
4
)@Ag22(Bu CC)18]·2BF
4
},
respectively. The [Ag
4
4
(PhCC) ] square is only coordinated by
},[11]
and
-
{[(CrO
4
)
2
4
]·3BF
4
four PhCC ligands at its four edges with a -type interaction (
2
-
1
1
{[CrO
4
4


:
and [Ag
.85-2.87 Å, respectively. Alternatively, the 1D chain of 3 could
also be understood as alternating [(CrO )@Ag18] cluster and Ag12
quadrangular prism fused together by face sharing (Figure 3d).

). The Ag···Ag interactions within [(CrO
4
)@Ag18] cluster
members in this family have been reported. The successful
isolation of 1-4 demonstrate that i) hetero anion templates indeed
play an important role in shaping the final cluster, ii) anions from
silver salts with different coordination abilities also have strong
impacts on the final silver-alkynyl assemblies.
4
(PhCC) ] square are in the range of 2.91-3.36 Å and
4
2
4
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-
calcd m/z = 2163.274), all of which don’t contain Cl template and
correspond to a half of the parent cluster bisected at the waist
2
section plus one [Ag(PhCC)], [Ag(OH)] or [Ag(PhCC)(H O)]
unit. The doubly charged envelop around m/z = 4200 also
contains overlapped 1c, 1c’ and 1c’’ with assigned formulae of
3 3 3 2
COO] , [1-3CF COO+2CH OH+2H
O+OH]2+ and [1-
2
+
[
1-2CF
2+
CF COO-PhCC] , respectively. The detailed formulae assigned
3
for 1c, 1c’ and 1c’’ are listed in Table 1. All these results could
match well with the crystallographic observation of hetero anion
templates in 1.
4 2
Figure 4. (a) X-ray structure of the [(CrO ) @Ag30] cluster of 4 with H atoms and
guest anion omitted for clarity. (Magenta: Ag; blue: Cr; green: F; gray: C) (b)
Ball-and-stick view of the skeleton of [(CrO @Ag30] cluster of 4 with tetrahedral
highlighted by polyhderal mode. (c) Space-filling mode of 1D linear chain
4 2
)
2
-
CrO
4
4 2
of 4. (d) Two [(CrO ) @Ag30] clusters linked by a single Ag atom (shown as
green ball)
Electrospray Ionization Mass Spectrometry (ESI-MS)
Studies
Recently, we and other groups used ESI-MS technique to
investigate the assembly of complicated polynuclear metal
clusters, which unveiled much information regarding the structural
integrity in solution and intermediate species during assembly.[13]
Single crystals of 1 and 2 were dissolved in CH
2 2
Cl , diluted by
CH OH, and then transferred to the gas phase by electrospray
3
ionization (ESI). For 1, there are three predominated envelops in
m/z range of 1000-5000 at a first glance. Surprisingly, the shapes
of all of them deviate from gauss-distribution when expanding
each envelop, indicating there are subpopulations in each
envelops, which makes the analysis of ESI-MS much more
challenge. After carefully matching experimental mass spectra
with calculated isotope distributions, we can split each envelop to
two or three species. The highest intensity envelope comprises
two overlapping triply charged species, 1b and 1b’, which can be
2 2
Figure 5. Positive ion mass spectra of 1 (a) in CH Cl and 3 (b) in DMA
(dimethylacetamide) solution showing three and one predominated envelops,
respectively. Black line: experimental data, red/blue/green lines: profile lines of
the simulated isotope patterns. The inserted is a proposed assembly subunit in
formation of chain-like 3.
The ESI-MS of 2 is extremely analogous to that of 1 and
contains the same species (2a and 2b) to 1a and 1b (Figure S3).
A doubly charged envelope (2c) at m/z = 4174.567 is different
2 3
O)
(OH)]3+
formulated as [(CrO
at m/z 2746.055 (calcd m/z
(CrO Cl@Ag42(PhCC)33(CF
COO)]3+ at m/z = 2749.391 (calcd
m/z = 2749.367), respectively. Another doubly charged envelope
contains three overlapped species assigned to
(CrO
)@Ag22(PhCC)18]2+ (1a, exptl m/z = 2154.271; calcd m/z =
154.268), [(CrO
exptl m/z 2155.272; calcd m/z
(CrO )@Ag22(PhCC)18(H
4 2
) Cl@Ag42(PhCC)33(CH
3
OH)(H
=
= 2746.058) and
[
)
4 2
3
with
1c
and
)(CH
assigned
(calcd
to
=
[(CrO
)
4 2
@Ag42(PhCC)34(CrO
4
3
OH)]2+
m/z
4174.567). The detailed assignment of main envelopes of 2 was
listed in Table S3. Based on above result, we can see that the
intact clusters of 1 and the basic cluster building blocks of 2 were
clearly observed as predominate species in positive-mode ESI-
MS.
[
4
2
4
)@Ag22(PhCC)17(CH
3
OH)(H
2
O)
(OH)]2+ (1a’,
3
=
=
2155.279), and
[
4
O)]2+ (1a’’, exptl m/z = 2163.278;
2
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FULL PAPER
2 2
Table 1. Assignment of the Key Species of 1 in CH Cl and 3 in DMA Solution
Identified by ESI-MS.
absence of the secondary anion template. ESI-MS identified the
stable species in solution of 1-4 and, more importantly, help us to
propose potential assembly route. This work shed light on i) how
to use the cluster engineering concept in the assembly of
polynuclear silver alkynyl clusters; ii) what is the differences of
template effects from hetero and homo anions.
a,b,c,d
Species
Assignment
[Δ(PhCC)18]2+
[Δ(PhCC)17(CH OH)(H
[Δ(PhCC)18(H
[Ɵ(PhCC)33(CH
[Ɵ(PhCC)33(CF
[Ɵ(PhCC)34(CF
Exp.
Sim.
1
1
1
1
1
1
1
1
3
a
2154.271
2155.272
2163.278
2746.055
2749.391
4174.568
4176.568
4180.570
2737.357
2154.268
2155.279
2163.274
2746.058
2749.367
4174.570
4176.616
4180.543
2737.361
O)(OH)]2+
a’
a’’
b
b’
c
c’
c’’
a
3 2
O)]2+
2
3
OH)(H
2
+
O)
3
(OH)]3+
3
3
COO)]
2
+
3
COO)]
OH)
COO)
[Ɵ(PhCC)34(CH
[Ɵ(PhCC)33(CF
[Ƞ(PhCC)29(CF
3
2
(H
2
]2+
O)
(OH)]2+
2
Experimental Section
3
2
3
SO
3
)
4
(CH
3
OH)
OH)
2
(H
2
3
+
O)
4
]
Materials and methods. The precursor [PhCCAg]
n
was synthesized by
3
a’
[Ƞ(PhCC)28(CF
3
SO
3
)
5
(CH
3
3
(H
2
2745.693
2745.907
mixing equivalent amounts of Ag O in ammonia solution and PhCCH in
2
3
+
O)]
)@Ag22; bƟ = (CrO
Both calculated and observed m/z values refer to the most intense, peaks in
ethanol. Other reagents employed were commercially available and used
as received without further purification. The Raman spectra of compounds
in solid state were recorded on a LabRAM HR800 (HORIBA Jobin Yvan)
a
4 2 4 2
) ) @Ag40
Cl@Ag42; cȠ = (CrO
Δ= (CrO
4
d
the isotopic envelope.
-
1
in the frequency range of 50-2500 cm . IR spectra were recorded on a
-
1
PerkinElmer Spectrum Two in the frequency range of 4000-400 cm . C,
N, and H analyses were performed on an EA1110 CHNS-0 CE 65
elemental analyzer. Mass spectra were recorded on an Agilent 6224 (USA)
spectrometer.
2 2
Crystals of 3 and 4 didn’t dissolve in CH Cl , but slightly
dissolved in DMA (dimethylacetamide) solution. For 3, as shown
in Figure 5b, only one clear peak was presented in the mass-to-
charge ratio range of 1000-5000. Expanding the envelop
maximum at ca. m/z = 2745.693 gave two peaks with small
fraction overlap. By matching with the theoretical isotope
Synthesis of {[(CrO
PhCCAg] (0.1 mmol, 21 mg) and CF
dissolved in distilled MeOH (5 mL). Then K
4
)
2
Cl@Ag42(PhCC)34(CF
COOAg (0.1 mmol, 22 mg) were
Cr (3 mg) and NaCl (1 mg)
3 2 3
COO) ]·CF COO} (1).
[
n
3
2
2 7
O
distributions,
we
@Ag40(PhCC)29(CF
2737.357; calcd
@Ag40(PhCC)28(CF SO
assigned
3a
and
(H O)
2737.361)
(H
O)]3+ (3a’, exptl
3a’
]3+ (3a, exptl
and
to
were added under stirring. After adding TMAH (10 μL), the resulting
solution was further stirred for 12 h at room temperature to give a turbid
solution which was sealed in a 25 mL Teflon-lined stainless steel autoclave
and kept at 70 oC for 2000 minutes and then slowly cooled to room
temperature. The yellow filtrate was left to stand in the dark at room
temperature. After 10 days, bright yellow crystals were deposited with a
[
(CrO
m/z
(CrO
)
4 2
3 3
SO )
4
(CH
m/z
(CH
3
OH)
2
2
4
=
=
[
)
4 2
3
3
)
5
3
OH)
3
2
m/z = 2745.693; calcd m/z = 2745.907), respectively. Based on
the structural analysis on the repeated unit in the 1D chain of 3,
the backbone of 3a and 3a’ should correspond to two
2 6
yield of 30 %. Anal. Calcd for C276H170Ag42ClCr F O12 (1) calcd (found): C,
3
(
9.17 (39.10); H, 2.02 (1.93) %. IR: 3053 (w), 2021 (w), 1659 (m), 1478
4
[(CrO )@Ag18] cluster plus one Ag
4
square, totally forty silver
m), 1442 (w), 1197 (m), 826 (s), 753 (s), 681 (s), 527 (s) cm-1
atoms. Such species fused together to give the solid state
structure of 3. In ESI-MS of 4 (Figure S4), we observed three
envelopes at m/z = 1788.851, 2745.691 and 2831.307, which are
assigned to species 4a, 4b and 4c, respectively. They were
assigned to double-chromates included species with formulae of
Synthesis
(NH )[(CrO
of
{
4
4
)
2
Cl@Ag42(PhCC)34(CrO
4
)(H
2
O)
2
]·2BF
4
·CH
3
OH}
n
(2). Pale
yellow crystals of 2 was synthesized using a procedure similar to that used
for 1, except that AgBF (0.1 mmol, 19.4 mg) and TMEDA (10 μL) were
used. Yield: 25 %. Anal. Calcd for C273 ClCr 15 (2), calcd
found): C, 38.18 (38.26); H, 2.03 (2.15) %. IR: 3053 (w), 2021 (w), 1478
4
H
173Ag42
B
2
3 8
F O
[
[
[
(CrO
(CrO
(CrO
)
4 2
)
4 2
)
4 2
@Ag37(PhCC)29]4+
@Ag40(PhCC)28(CF
@Ag42(PhCC)31(CF
(4a),
O)]3+ (4b) and
]3+ (4c). It is noted that 4b has
(
-1
3
SO
3
)
5
(CH
3
OH)
(H
3 2
(m), 1052 (m), 826 (s), 753 (s), 681 (s), 527 (s) cm
3
SO
3
)
4
Synthesis
of
4
[(CrO )@Ag22(PhCC)16(CF
3
SO
3
)
4
]
n
(3),
and
(4).
the same formula to 3a’, which indicates the dissolution of 3 and
with different structural features could give the same species,
{
[(CrO @Ag31(PhCC)22(CF
4
)
2
3
SO ]·CF SO ·2CH
3
)
4
3
3
3
OH·H O}
2 n
4
Applying an identical solvothermal procedure detailed in the synthesis of 1
but using CF SO Ag as silver salt and in the absence of NaCl led to growth
of single crystals of 3 and 4 in one batch. They are manually separated
under the microscopy one by one. Anal. Calcd for C132
vice versa, and the formation of 4 may experience the same
intermediate to that of 3. This case is not surprising in one-pot
synthesis of two different cluster-based 1D chain structures.
3
3
H
16 4
79Ag22CrF12O S
(
(
(
(
(
3), calcd (found): C, 33.72 (33.79); H, 1.69 (1.76) %. IR: 2982 (w), 2012
w), 1477 (m), 1215 (s), 1152 (m), 1016 (s), 826 (s), 745 (s), 690 (s), 636
-
1
2 15 26 5
s), 509 (s) cm ; Anal. Calcd for C183H118Ag31Cr F O S (4), calcd
Conclusions
found): C, 33.17 (33.26); H, 1.80 (1.69) %. IR: 2987 (w), 2012 (w), 1216
-
1
s), 1163 (m), 844 (m), 745 (s), 684 (s), 634 (s), 503 (s) cm .
In summary, we demonstrated the controllable assembly,
single crystal structures and solution behaviors of four molecular
assemblies based on nanosized silver alkynyl clusters. In the
X-ray Crystallography Single crystals of 1-4 with appropriate dimensions
were chosen under an optical microscope and quickly coated with high
vacuum grease (Dow Corning Corporation) to prevent decomposition and
one was mounted on a glass fiber for data collection on a Bruker Apex II
CCD diffractometer equipped with graphite-monochromated Mo K
radiation ( = 0.71073 Å) at 173 K. The cell parameters were retrieved
using SMART software and refined with SAINT on all observed
presence of CrO 2
-
-
4
and Cl templates, we successfully isolated
two hetero anion-templated assemblies based on silver alkynyl
clusters by tuning anion coordination abilities. For comparison,
2-
we also isolated two 1D assemblies based on single CrO
templated Ag18 and double CrO 2-
templated Ag30 clusters in the
4
[14]
reflections. Data reduction was performed with the SAINT software and
4
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Chemistry - A European Journal
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corrected for Lorentz and polarization effects. Absorption corrections were
applied with the program SADABS.[14] All structures were solved by direct
methods using SHELXS-97 and refined on F by full-matrix least-squares
procedures with SHELXL-97.[15] Atoms were located from iterative
examination of difference F-maps following least squares refinements of
the earlier models. Hydrogen atoms were placed in calculated positions
and included as riding atoms with isotropic displacement parameters 1.2-
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This work was supported by the NSFC (Grant No. 21571115), the
Natural Science Foundation of Shandong Province (No.
ZR2014BM027), Young Scholars Program of Shandong
University (2015WLJH24), and the Fundamental Research Funds
of Shandong University (104.205.2.5 and 2015JC045). M.K. is
funded by the CNRS-France.
Keywords: Silver Alkynyl Clusters • anion template • Cluster
Engineering • Solution Behavior
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Entry for the Table of Contents (Please choose one layout)
Layout 1:
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Cluster engineering of
Shan-Shan Zhang, Hai-Feng Su,[b] Zhi Wang, Lina
Wang, Quan-Qin Zhao, Chen-Ho Tung, Di Sun*,
Lan-Sun Zheng
nanosized silver alkynyl
clusters were achieved by
adjusting anion templates.
Page No. – Page No.
Title
Anion-Templated Nanosized Silver Alkynyl
Clusters: Cluster Engineering and Solution
Behavior†
‡
[
a]
This article is protected by copyright. All rights
School of Chemistry and Chemical Engineering, Shandong
S.-S Zhang, Z. Wang, C-H Tung Dr. D. Sun
re ed.
Ke ys eL ar vb of Colloid and Interface Chemistry, Ministry of Education,