Same Magic Number but Different Arrangement: Alkynyl-Protected Au25 with D3 Symmetry

Article abstract of DOI:10.1002/anie.201811859

Two homoleptic alkynyl-protected gold clusters with compositions of Na[Au₂₅(C≡CAr)₁₈] and (Ph₄P)[Au₂₅(C≡CAr)₁₈] (Na?1 and Ph₄P?1, Ar=3,5-bis(trifluoromethyl)phenyl) were synthesized via a direct reduction method. 1 is a magic cluster analogous to [Au₂₅(SR)₁₈]^? in terms of electron counts and metal-to-ligand ratio. Single-crystal structure analysis reveals that 1 has an identical Au₁₃ kernel to [Au₂₅(SR)₁₈]^?, but adopts a distinctly different arrangement of the six peripheral dimer staple motifs. The steric hindrance of alkynyl ligands is responsible for the D₃ arrangement of Au₂₅. The introduction of alkynyl also significantly changes the optical absorption features of the nanocluster as supported by DFT calculations. This magic cluster confirms that there is a similar but quite different parallel alkynyl-protected metal cluster universe in comparison to the thiolated one.

Full text of DOI:10.1002/anie.201811859

A Journal of the Gesellschaft Deutscher Chemiker
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Accepted Article
Title: Same Magic Number but Different Arrangement: Alkynyl-
Protected Au25 with D3 Symmetry Jiao-Jiao Li, Zong-Jie Guan,
Zhen Lei, Feng Hu, and Quan-Ming Wang*
Authors: Jiao-Jiao Li, Zong-Jie Guan, Zhen Lei, Feng Hu, and Quan-
Ming Wang
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201811859
Angew. Chem. 10.1002/ange.201811859
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Same Magic Number but Different Arrangement: Alkynyl-
Protected Au25 with D3 Symmetry
Jiao-Jiao Li, Zong-Jie Guan, Zhen Lei, Feng Hu, and Quan-Ming Wang*
Abstract: We synthesize two homoleptic alkynyl-protected gold
[Au25(SR)18]- is not. To our surprise, 1 has better stability against
oxidation in comparison with [Au25(SR)18]- (R = CH2CH2Ph).
clusters
with
compositions
(Na1
of
Na[Au25(C≡CAr)18]
Ph4P1, Ar
and
3,5-
(Ph4P)[Au25(C≡CAr)18]
and
=
bis(trifluoromethyl)phenyl) via direct reduction method. 1 is a magic
cluster analogous to [Au25(SR)18]- in terms of electron counts and
metal-to-ligand ratio. Single crystal structure analysis reveals that 1
has identical Au13 kernel to [Au25(SR)18]-, but adopts distinctly
different arrangement of the six peripheral dimer staple motifs. The
steric hindrance of alkynyl ligands is responsible for the D3
arrangement of Au25. The introduction of alkynyl also significantly
changes the optical absorption features of the nanocluster as
supported by DFT calculations. This magic cluster confirms that
there is a similar but quite different parallel alkynyl-protected metal
cluster universe in comparison to the thiolated one.
Ligand-protected gold clusters have attracted intense interests
for their fascinating structures and potential applications in
luminescence, catalysis, sensing and bio-related applications.[1-6]
In the past decade, remarkable advances have been made with
Figure 1. ESI-MS of Na·1 in negative mode. Insert: the experimental isotropic
pattern (blue) and stimulated (red) data of 1. The asterisk (*) indicates
dianionic 1.
thiolate-protected gold nanoclusters.[7-17] Recently, attention has
been diverted to alkynyl-protected nanoclusters,[5,
which
18-27]
suggests a parallel universe vs thiolate-protected Aun(SR)m. Our
recent findings revealed that Au36(C≡CPh)24 and Au44(C≡CPh)28
are isostructural to their counterparts Au36(SR)24 and Au44(SR)28,
respectively.[19] We also managed to achieve total structure
determination of alkynyl-protected Au144, which gave important
information on the elusive structure of Au144(SR)60.[27] These
findings raises a question whether there exists Au25 protected by
alkynyl ligands as the counterpart of the most extensively
studied gold nanocluster [Au25(SR)18]-.[8, 9, 28]
a)
Our attempts to study the effects of ligands on the structures
of gold nanoclusters revealed that Na[Au25(C≡CAr)18] can be
isolated when 3,5-bis(trifluoromethyl)phenylacetylide (Ar = 3,5-
(CF3)2C6H3) was used as the protecting ligand. To our surprise,
its molecular structure is not isostructural to [Au25(SR)18]-, which
has a different arrangement of the staple motifs surrounding the
Au13 core. Herein, we report the synthesis, structure and optical
properties of Na[Au25(C≡CAr)18] (Na·1) and its derivative
(Ph4P)[Au25(C≡CAr)18] (Ph4P·1). It is noteworthy that the steric
hindrance of alkynyl ligands play a key role in dictating the
formation of the different arrangement of staples, leading to the
formation of a D3 symmetry, i.e. [Au25(C≡CAr)18]- is chiral while
d)
c)
b)
b)
b)
Figure 2. (a) Molecular structure of [Au25(C≡CAr)18]- (1) in Na·1. Color codes:
orange, Au; gray, C; bright green, F. (b) the centered icosahedral Au13 core.
(c) Au13 with the exterior 12 Au atoms. (d) Au13 with six V-shaped “C≡C-Au-
C≡C-Au-C≡C” staples (staples highlighted in pink and green).
Bis(trifluoromethyl)phenyl groups omitted for clarity.
[*]
J.-J. Li, Z.-J. Guan,Dr. Z. Lei, F. Hu, Prof. Dr. Q.-M. Wang
Department of Chemistry, Tsinghua University
Beijing, 100084 (P. R. China)
E-mail: qmwang@tsinghua.edu.cn
Homepage: http://www.wangqmlab.org.cn
Z.-J. Guan, Prof. Dr. Q.-M. Wang
Department of Chemistry, College of Chemistry and Chemical
Engineering, Xiamen University
Xiamen, 361005 (P. R. China)
Cluster Na1 was synthesized by “direct reduction” method,
which involves the reduction of AuC≡CAr with NaBH4. This
method is convenient and effective for the synthesis of gold
nanoclusters protected by alkynyl ligands. Typically, a freshly
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prepared solution of NaBH4 was added dropwise to the
suspension of AuC≡CAr in mixed solvent of chloroform and
methanol under vigorous stirring, followed by the addition of
Et3N. The color immediately changed from yellow to black. This
reaction continued in the dark for 20 h at room temperature. The
mixture was rotary-evaporated to dryness to give a dark solid.
The crude product was extracted with CH3OH and the solution
was taken to dryness again. The solid was dissolved in mixed
solvent of CH2Cl2 and toluene (v:v = 1:1) and the resulted
solution was subjected to diffusion of n-hexane. Black block
crystals were obtained after ca. two weeks. To confirm that the
cluster is negatively charged, Ph4P·1 was synthesized via a
similar procedure. Black plate-like crystals were obtained after
ca. three weeks. The composition of Na1 nanocluster was
characterized by electrospray ionization mass spectrometry
(ESI-MS) in negative mode. As shwon in Figure 1, the main
peak appears at m/z ~ 9191.4 corresponding to 1, and its
isotropic distribution matches perfectly with the simulated.
triangles, respectively, in contrast to the case in [Au25(SR)18]-
where all capped triangles are evenly distributed. With the new
arrangement of the gold atoms, the Au25 core in 1 is intrinsically
chiral with a D3 symmetry, and the total structure of 1 also chiral.
However, both enantiomers are present in one single crystal so
the crystal is racemic (Figure S1).
Figure 4. Comparisons of staple arrangement of
[Au25(SR)18]- (R = CH2CH2Ph, right) [8]
1 in Na·1 (left) and
.
The structures of Na1 and Ph4P1 were determined by X-ray
single-crystal diffraction.[32] The only difference is the cation
being Na+ or Ph4P+. As shown in Figure 2, 1 contains 25 gold
atoms and 18 alkynyl ligands with D3 symmetry. It has eight
valence electrons and a centered icosahedral Au13 kernel
(Figure 2b). The average Au-Au distance in 1 from the central
gold atom to the vertexes of Au12 icosahedron is 2.776 Å, and
the average Au-Au distance of gold atoms on the Au12 shell is
2.919 Å. The Au-Au distances of the Au13 kernel are the same
To spot the reason that the metal core of 1 cannot be
arranged as that of thiolate-protected Au25, we simulated the
structure of [Au25(C≡CPh)18]- (-CF3 groups were omitted for
clarity) adopting the same arrangement of [Au25(SR)18]- by
Material Studio program (Figure S2). It turns out that
unreasonable contacts between phenyl groups occur, indicating
that it is impossible for [Au25(C≡CPh)18]- to be isostructural to
[Au25(SR)18]-. This is because of the steric hindrance coming
from the rigid nature of alkynyl, while the -C-S-Au binding in
thiolate-protected Au25 is flexible (Figure 4).
as those of [Au25(SR)18]- (R
= CH2CH2Ph). The core is
surrounded by six V-shaped ArC≡C-Au-C≡C(Ar)-Au-C≡CAr
staple motifs, as shown in Figures 2c and 2d. Each staple is
connected to two neighboring faces of the icosahedron, resulting
in twelve occupied faces and eight vacant triangles.
The average distance from the staple Au atoms to the vertex
of Au13 is 3.087 Å, which is slightly shorter than that in thiolate-
protected Au25 (3.163 Å). The bond length differences are
caused by the binding preferences of alkynyl and thiolate ligands
as shown in Figure 4. The angle between terminal -C≡C- and Au
atom is nearly 180º ， whereas the C-S-Au angle is 97.75-
105.78º. The flexibility of C-S-Au binding can avoid the collision
of the R groups in SR ligands.
b)
b)
a)
b)
In addition to ESI-MS, nuclear magnetic resonance (NMR)
analysis also confirms the structure of Na∙1 remains intact in
solution (Figures S3 and S4). In 19F NMR, the chemical shift
values around -62.91, -63.56 and -63.73 ppm indicate that there
are three types of F, which correspond the three alkynyl-groups
in V-shaped staples. Six peaks are found in 1H NMR and their
integration ratios (2:2:2:1:1:1) are consistent with the numbers of
phenyl H atoms in different chemical environments.
Figure 3. The different arrangements of three V-shaped staples: a) cluster 1.
b) [Au25(SR)18]- (R = CH2CH2Ph)[8]
.
The optical absorption spectrum of Na·1 in CH2Cl2 solution is
shown in Figure 5. Apart from three main absorption bands at
~430, 520, and 700 nm, there are additional fine spectral
features containing two small shoulders at ∼590 and 820 nm.
The optical features of cluster 1 bears a resemblance to
[Au25(SR)18]-. For instance, 1 and [Au25(SR)18]- have very similar
broad absorption around 700 nm. The other peaks are quite
different between 1 and [Au25(SR)18]-. These facts strongly
suggest that their electronic structures are different, which might
result from the arrangement of staples including protecting
alkynyl and thiolate ligands.
The six V-shaped [Au2(C≡CAr)3] staples in 1 are similar to
the [Au2(SR)3] dimer staples in [Au25(SR)18]-, but are different in
connection to Au13 kernel. As shown in Figure 3, when the
cluster is viewed down a 3-fold axis, three of the twelve staple
gold atoms in 1 (three blue atoms in Figure 3a) are twisted about
60 referring to those in [Au25(SR)18]- (three green atoms in
Figure 3b) while the remaining 9 staple gold atoms stay still.
This new arrangement of staple gold atoms leads to the
formation of a pattern that two gold atoms cap two neighbouring
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a)
Figure 5. Absorption spectra of 1 (red) and [Au25(SR)18]- (black).
We monitored the stability of Na·1 with UV-vis spectroscopy
in the presence of oxidants such as O2 in air and H2O2 (Figure
S5 and S6). No decomposition was observed after stored under
ambient conditions for at least 12 days. Moreover, the cluster
showed no change for 3 h even under strong oxidation condition
(H2O2). It is noted that [Au25(SR)18]- was oxidized to [Au25(SR)18]0
in air in several hours, and in the presence of H2O2, the
conversion was much faster.[29-31]
To understand the relationship between electronic structure
and optical absorption properties of 1, we carried out density
functional theory (DFT) calculations using Amsterdam Density
Functional (ADF 2017) software packages. We adopted the
molecular structure from X-ray structural determination as the
TDDFT calculation model without structural optimization. As
shown in Figure 6a, there are three distinct features at 1.76 (β),
2.41 (γ), and 2.82 eV (δ) in the experimental spectrum, which is
well reproduced in the calculated spectrum except for a red-shift.
We also found that a weak shoulder peak at 1.38 eV (α) in the
simulated spectrum is in good agreement with the experimental
(1.50 eV), which corresponds to a HOMO to LUMO transition. It
is worth noting that a similar absorption peak at 1.59 eV in the
experimental spectra of [Au25(SR)18]- is also observed,[8] but this
peak was missing in the simulation. The band at 1.8 eV of
thiolate-protected Au25 was assigned to the HOMO-LUMO
transition, whereas β peak at 1.62 eV in title cluster arises
primarily from the HOMO-1 to LUMO transition. In addition, the γ
peak comprises HOMO-1 to LUMO+1 and HOMO to LUMO+2
transitions and the δ peak is mostly contributed by the HOMO-5
to LUMO and HOMO to LUMO+7 transitions. The detailed
transitions corresponding to the significant peaks of
[Au25(C≡CAr)18]- are listed in Table S1. Figure 6b illustrates the
frontier orbitals of 1, and one can see that the HOMO-1, LUMO
and LUMO+1 are doubly degenerated, which is different from
that of [Au25(SR)18]-.
b)
Figure 6. a) Experimental absorption spectrum of 1 and simulated spectrum of
[Au25(C≡CAr)18]-. b) Frontier orbitals including HOMO-1, HOMO, LUMO and
LUMO+1 of [Au25(C≡CAr)18]-.
According to the Kohn-Sham molecular orbital (MO) energy
levels diagram and the analysis of atomic orbital (AO) character
in the composition of MOs of [Au25(C≡CAr)18]- (Figure 7). The
HOMO-1, HOMO, and LUMO are mainly constituted by the Au
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(d and sp) atomic orbitals, while the LUMO+1 and LUMO+2 are
constituted by the Au(sp) and C(p) atomic orbitals (Figure S7).
Therefore, the α absorption band at 1.38 eV and β band (Figure
6a) primarily attribute to the charge transfer within metal kernel,
and the γ peak essentially arises from the mixing of MMCT and
the MLCT processes. Notably, because the HOMO-5 and
LUMO+7 has large portion of C(p) character of alkyne ligands
(Figure S7), the δ peak around 2.4 eV is distinctly different from
that in [Au25(SCH2CH2Ph)18]- (3.1 eV).[8] The electronic structure
is influenced significantly by protecting alkynyl ligands in 1,
which gives the absorption spectrum with different profile in
comparison that of [Au25(SCH2CH2Ph)18]-.
evaporated to dryness to give a dark solid. The crude product was
extracted by 3 mL CH3OH and the supernatant was collected by
centrifugation (9000 r/min, 2 min). After evaporation, the resulted solid
was dissolved in a mixed solvent of CH2Cl2 and toluene (v:v = 1:1) and
the resulted solution was subjected to diffusion of n-hexane to afford
black block crystals after two weeks (3.0 mg, yield 8%, based on Au). 1H
NMR (400.0 MHz, CD3OD, ppm): δ 8.15 (s, 12H, Ph), 7.96 (s, 12H, Ph),
7.82 (s, 6H, Ph), 7.41 (s, 6H, Ph), 7.37 (s, 12H, Ph), 7.35 (s, 6H, Ph). 19F
NMR (564.6 MHz, CDCl3, ppm): -62.91 (s), -63.56 (s), -63.73 (s).
(Ph4P)[Au25(C≡CC6H3-3,5-(CF3)2)18] (Ph4P·1): The synthetic procedure
is similar to that of Na·1. Ph4PCl (20 mg) was added before the addition
of reducing agent. Black plate-like crystals were obtained by slow
diffusion of hexane into a solution of Ph4P·1 in CH2Cl2/toluene. (3.6 mg,
yield: 9%, based on Au).
Acknowledgements
This work was supported by the National Natural Science
Founda-tion of China (21473139, 21521091 and 21631007).
Conflict of interest
The authors declare no competing financial interest.
Figure 7. Kohn-Sham molecular orbital energy levels diagram and the
associated populations of atomic orbitals in each KS molecular orbital for a
model compound [Au25(C≡CAr)18]-.
Keywords: alkynyl ligands • cluster compounds • gold • optical
properties • structure determination
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[32] (a) Crystal data for Na∙1: C180H54F108NaAu25, a = b = 20.0438(4), c =
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31.2582(3) Å, V = 11431.9(2) Å3, trigonal space group P31c, Z = 2, T =
100.00(11) K, 164676 reflections measured, 13437 unique (Rint = 0.0988),
final R1 = 0.0430, wR2 = 0.1106 for 12926 observed reflections [I > 2σ(I)].
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Entry for the Table of Contents (Please choose one layout)
Layout 1:
COMMUNICATION
Magic clusters Na[Au25(C≡CAr)18] and
Jiao-Jiao Li, Zong-Jie Guan, Zhen Lei,
Feng Hu, and Quan-Ming Wang*
(Ph4P)[Au25(C≡CAr)18] (Ar
=
3,5-
bis(trifluoromethyl)phenyl)
exhibit
Page No. – Page No.
novel connection between staples and
Au13 core. Steric hindrance caused by
rigid ligand coordination preference
accounts for the different geometric
and electronic structures.
Same Magic Number but Different
Arrangement: Alkynyl-Protected Au25
with D3 Symmetry
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