Atomically Precise Bimetallic Au19Cu30 Nanocluster with an Icosidodecahedral Cu30 Shell and an Alkynyl-Cu Interface

Article abstract of DOI:10.1021/jacs.7b04622

Bimetallic nanoclusters Au₁₉Cu₃₀ with chemical composition of [Au₁₉Cu₃₀(C CR)₂₂(Ph₃P)₆Cl₂](NO₃)₃ (where RC C is from 3-ethynylthiophene (H₃C₄S-3 - C CH) or ethynylbenzene (PhC CH)) has been synthesized. Single X-ray structural analysis reveals that Au₁₉Cu₃₀ has a multishelled core structure of Au@Au₁₂@Cu₃₀@Au₆, comprising a centered icosahedral Au₁₃ (Au@Au₁₂) surrounded by an icosidodecahedral Cu₃₀ shell and an outmost shell of a chairlike hexagonal Au₆. The alkynyl carbon is bound to the hollow sites on the Au₁₉Cu₃₀ nanocluster surface, which is a novel interfacial binding mode in alkynyl-protected alloy nanoclusters. The Cu₃₀ icosidodecahedron is unprecedented and Au₁₉Cu₃₀ represents the first alkynyl-protected Au-Cu alloy nanocluster.

Full text of DOI:10.1021/jacs.7b04622

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Communication
An Atomically Precise Bimetallic Au19Cu30 Nanocluster with
an Icosidodecahedral Cu30 Shell and an Alkynyl-Cu Interface
Xian-Kai Wan, Xiao-Ling Cheng, Qing Tang, Ying-Zi Han, Guoxiang Hu, De-en Jiang, and Quan-Ming Wang
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.7b04622 • Publication Date (Web): 30 Jun 2017
Downloaded from http://pubs.acs.org on June 30, 2017
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An Atomically Precise Bimetallic Au19Cu30 Nanocluster with an Ico-
sidodecahedral Cu30 Shell and an Alkynyl-Cu Interface
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&
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†,‡
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‡
Xian-Kai Wan , Xiao-Ling Cheng , Qing Tang , Ying-Zi Han , Guoxiang Hu , De-en Jiang * and
†,‡.
Quan-Ming Wang *
†Department of Chemistry, Tsinghua University, Beijing, 10084, P. R. China
‡Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, P.
R. China.
&Department of Chemistry, University of California, Riverside, CA 92521, USA
Supporting Information Placeholder
Ph, 2). The 49-metal-atom kernel has a Russian doll struc-
ture Au@Au12@Cu30@Au6, in which the Cu30 shell has a
shape of icosidodecahedron. New bonding modes of al-
kynyls are found in Au19Cu30, suggesting the interfacial
structure between alkynyls and copper may be different
from alkynyl-gold. It is worth noting that Au19Cu30 has
twenty-two free electrons, which is a rare case in ligand-
protected gold nanoclusters.
ABSTRACT: Bimetallic nanoclusters Au19Cu30 with
chemical composition of
[Au19Cu30(CCR)22(Ph3P)6Cl2](NO3)3 (where RCC is
from 3-ethynylthiophene (H3C4S-3-CCH) or ethynylben-
zene (PhCCH)) has been synthesized. Single X-ray struc-
tural analysis reveals that Au19Cu30 has a multishelled core
structure of Au@Au12@Cu30@Au6, comprising a centered
icosahedral Au13 (Au@Au12) surrounded by an icosidodec-
ahedral Cu30 shell and an outmost shell of a chair-like hex-
agonal Au6. The alkynyl carbon is bound to the hollow sites
on the Au19Cu30 nanocluster surface, which is a novel inter-
facial binding mode in alkynyl-protected alloy nanoclusters.
The Cu30 icosidodecahedron is unprecedented and
Au19Cu30 represents the first alkynyl-protected Au-Cu al-
loy nanocluster.
The preparation of 1 involved the direct reduction of a
mixture containing H3C4S-3-CCAuPPh3, Cu(NO3)2 and
Ph3PAuCl by NaBH4 in dichloromethane. Cluster 2 was
prepared in a slightly modified method via the reduction of
PhCCAuPPh3, Cu(NO3)2 and CuCl by NaBH4 in di-
chloromethane. Details of synthesis are provided in the
supporting information. Transmission electron micro-
scopic (TEM) analyses revealed that the as-prepared
Au19Cu30 nanoclusters have roughly uniform size (Fig-
ure S1a).
Ligand-protected gold nanoclusters have experienced
great advances in the past decade.1-24 To further tune their
structures and properties, alloy nanoclusters have been syn-
thesized from the mixing of the second or third metal ele-
ments.25-34 Ligand choice is important in dictating the com-
positions and properties of nanoclusters. Recently, alkynyl
ligands have been used in the preparation of gold21,35-38 and
gold-silver nanoclusters and aklynyl protected Au-Ag bi-
metallic nanocluster such as Au24Ag20, Au34Ag28 and
Au80Ag30 have been successfully crystallized and yielded to
structural determination.39-41 However, aklynyl-protected
Au-Cu bimetallic nanocluster has not been reported so far.
Although Au and Ag are of very similar atomic radii, the
atomic radius of Cu is significantly smaller than Au. This
Au-Cu size disparity may lead to new structures of metal
kernel and interface that are very different from the recent-
ly discovered aklynyl-protected Au-Ag nanoclusters.
Figure 1. Mass spectra of the Au19Cu30 clusters. Inset: The meas-
ured (black trace) and simulated (red trace) isotopic patterns. (a)
[Au19Cu30(CC-3-SC4H3)22(Ph3P)6Cl2]3+; (b) [Au19Cu30(CCPh)22
(Ph3P)6Cl2]3+.
Chemical compositions were determined by electro-
spray ionization time of flight mass spectrometry (ESI-
TOF-MS) in positive mode (Figure 1). The clean spectra
show tri-cation at m/z = 3216.84 (theory: 3216.87 for 1)
and 3172.51 (theory: 3172.53 for 2), corresponding to the
molecular ions [Au19Cu30(CC-3-SC4H3)22(Ph3P)6Cl2]3+
and [Au19Cu30(CCPh)22(Ph3P)6Cl2]3+, respectively. The
observed isotopic patterns of the tricationic clusters are in
good agreement with the simulation (Figure 1 inset). The
Herein, we report the synthesis and total structure deter-
mination of two isostructural Au19Cu30 bimetallic
nanoclusters
in
the
formula
of
[Au19Cu30(CCR)22(Ph3P)6Cl2](NO3)3 (R = H3C4S, 1; R =
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Au 4f7/2 and Cu 2p3/2 binding energies were determined
to be 84.3 and 932.9 eV, respectively (Figure S2). These
values are slightly higher than corresponding bulk met-
als (84.0 for Au and 932.4 eV for Cu), indicating the
metal atoms are mostly in reduced form.
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Structural determination revealed that 1 and 2 are
isostructural (Figure S3).42 The only difference between 1
and 2 is the R groups in the alkynyl ligands. For simplicity,
we focus discussion on 1. Figure 2 shows that the trication-
ic cluster [Au19Cu30(CC-3-SC4H3)22(Ph3P)6Cl2]3+ consists
of 19 gold atoms, 30 copper atoms, 22 H3C4S-3-CC- lig-
ands, 6 Ph3P and 2 chlorides. After removing the benzene
ring and alkynyls, the Au19Cu30 metal framework clearly
show C2h symmetry (Figure S4), and the 6 phosphines can
be classified into two types (highlighted in yellow and
pink). Accordingly, based on the number of P atoms of
each type, the 31P NMR should display two peaks at an
intensity ratio of 1 : 2. Experimentally, two peaks at 55.88
and 65.58 ppm with a peak area ratio of 1 : 2 were ob-
served for 1 (Figure S5).
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Figure 3. Anatomy of Au19Cu30 kernel structure in 1 or 2. (a)
Centered icosahedron Au@Au12. (b) Cu30 icosidodecahedron. (c)
Au@Au12@Cu30 multishelled structure. (d) Six outmost Au atoms
highlighted in green.
In the central Au13 core, the Au···Au distances from the
central Au atom to the peripheral Au12 shell give an aver-
age value of 2.783 Å. It is shorter than the 2.88 Å bond
length in bulk gold, indicating strong interactions between
central Au and peripheral Au. The Au···Au distances on
the Au12 icosahedron has an average value of 2.926 Å. The
average Cu···Cu distance in Cu30 shell is 2.917 Å, which is
much longer than that (2.56 Å) in bulk copper. The
Au···Cu bond lengths between Au12 and Cu30 shells can be
classified into two groups: shorter distances in the range of
2.651(2)-2.758(2) Å and longer distances in the range of
2.773(2)-3.019(2) Å, together giving an average distance of
2.774 Å, which is comparable to 2.72 Å (sum of the atomic
radii of Au and Cu). The six gold atoms (Figure S7, high-
lighted in orange) at the third shell cap six pentagonal Cu5
faces of the Cu30 shell, and form a hexametric ring of a
chair conformation (Figure S7, blue shadowed).
Figure 2. Molecular structure of [Au19Cu30(CC-3-
SC4H3)22(Ph3P)6Cl2]3+.
In the Au55 Mackay icosahedron (Au55-MI)3 and icosa-
hedral-based Au144 nanoclutser,43,44 there is a icosahedral
Au42 shell around the central Au13. This Au42 icosahedron
can be taken as Au30@Au12, i.e. 12 gold atoms capping an
icosidodecahedral Au30. Au19Cu30 can be derived from
icosahedral Au55 by replacing the Au30 by Cu30 and remov-
ing 6 Au atoms of the outmost Au12. This structural similar-
ity implies that the Au30 shell in Au55 or Au144 may be the
substitution positions when these clusters are doped by
copper. Previous prediction is that the preferable doping
sites are inner metal core and the maximum numbers of Cu
atom were 30 and 23 respectively.27,45 Calculation by Zeng
et al.29 suggests that in gas phase copper-doped multishell
structured Au55 prefer to form alloy cluster Au43Cu12, and
the preferable doping sites are the inner Au12 shell. The
present work offers new possibilities for the doping sites in
gold nanoclusters.
Anatomy of the Au19Cu30 kernel is illustrated in Figure 3.
It has a Russian doll structure Au@Au12@Cu30@Au6. The
central part of the kernel is a conventional Au13 (Au@Au12)
(Figure 3a), which is enclosed in a second shell of Cu30
icosidodecahedron (Figures 3b and 3c). The third shell con-
sists of 6 Au atoms (Figure 3d) forming a chair-like hexa-
gon (Figure S7). The icosidodecahedral structure of the
Cu30 (Figure 3b) is of special interest, which has not been
observed in gold alloy nanoclusters before. An icosidodec-
ahedron is one of the Archimedean solids, consisting of
twenty triangular faces and twelve pentagonal faces. Two
triangles and two pentagons meet at each vertex. There are
60 identical edges, each separating a triangle from a penta-
gon. An icosidodecahedron has icosahedral symmetry, and
it can be generated with the 30 vertices located at the mid-
points of the edges of an icosahedron. For comparison, the
30 Cu atoms are arranged quite differently in
[Au12Cu32(SPhCF3)30]4- as a pentagonal dodecahedral Cu20
attached by 6 Cu2(SR)5 units.34
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Figure 4. The coordination models of 22 H3C4S-3-CC- ligands
on surface of the Au19Cu30: (a) μ3-η1(Cu),η1(Cu),η1(Cu), two; (b)
9
μ3-η1(Cu), η1Cu),η2(Cu), two; (c) μ3-η1(Cu),η2(Cu),η2(Cu), 14; (d)
μ3-η1(Au),η2(Cu),η2(Cu), four. Color legend: orange = Au; tur-
quoise = Cu; yellow = S; gray = C.
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Figure 5. Comparison of the optical absorption spectrum of the
[Au19Cu30(C≡C-SC4H3)22(PH3)6Cl2 ]3+ cluster between experi-
ment and simulation (TD-DFT).
There are 22 H3C4S-3-CC- ligands, 6 Ph3P and 2 chlo-
rides in 1. Each of the six Au atoms in the outmost shell is
ligated terminally by one Ph3P ligand, and each chloride
bridges two Cu atoms (Figure 2). Although staple motifs
such as PhCC-Au-C2(Ph)-Au-CCPh and PhCC-Au-
CCPh were found in alkynyl-protected Au or Au-Ag
nanoclusters,21,39,41 there is no such staple motifs in 1
whose surface is dominated by Cu atoms. Formation of
staple motifs on the gold surface is facilitated by two fac-
tors: gold’s preference for a linear twofold coordination;
ease of creation of a gold adatom on the surface (energy
penalty is about 0.6 eV from DFT; see Table S1 in SI). In
contrast, it is harder to create an adatom on the Cu surface
(energy penalty is about 1.0 eV), so the PhC≡C groups pre-
fer to bind to the Cu surface individually at the tight Cu3
triangles (due to the smaller atomic radius of Cu). We
found that all the 22 alkynyls in 1 function as μ3-bridges on
M3 triangles. The RCC group can be an exclusively σ
donor to bind triangular Cu3 (Figure 4a) or both σ and π
donors to bind Cu3 (Figure 4b and 4c). Interestingly, the Au
atom in Figure 4d is from the inner Au12 shell, while the Cu
atoms are from the Cu30 shell. These interfacial binding
structures account for the distinct arrangement of alloy
metal atoms in the Au19Cu30 cluster.
We measured the optical absorption spectrum of 1 (Fig-
ure 5) which shows three main broad bands at 1.36 eV (α),
1.83 eV (β), and 2.34 eV (γ). They are well reproduced in
the simulated spectrum from time-dependent DFT, despite
the underestimate of the excitation energies. We found that
the α peak mainly comes from the HOMO-4 to LUMO+1
transition, while the β and γ peaks all have multiple contri-
butions of similar oscillator strength.
In summary, two novel alkynyl-protected multishell
structured Au19Cu30 nanoclusters have been synthesized
and structurally determined. The novel shell-by-shell struc-
ture Au@Au12@Cu30@Au6 offers new mode for under-
standing the preferable doping sites when Au nanoclusters
are doped with copper. The interfacial structures of alkynyl
ligands on the Cu30 shell via μ3-bridges are distinctly dif-
ferent from those of alkynyls on Au or Au-Ag nanoclusters.
The 22 electron count of the two clusters is also unusual.
The new geometry, interface, and electronic structure of the
Au19Cu30 nanoclusters offer exciting opportunities to ex-
plore their functions in the new future.
ASSOCIATED CONTENT
This material is available free of charge via the Internet at
http://pubs.acs.org.
We next discuss the electronic structure of cluster 1
which has 22 valence electrons according to the superatom
complex model: N* = NAu+Cu - Nalkynyl - Nchloride - Q = 49 -
22 - 2 - 3 = 22.46 Because 20 is a magic number corre-
sponding to a spherical shell closing, 22 is hence an unusu-
al number of free electron count in gold nanoclusters, and
the previous example is the diphosphine-protected Au22
cluster having a rod-like shape.10 The jellium model, which
the superatom complex model is based on, predicts that the
22-electron system has the shape of a sphere with two
elongated poles,47 quite different from the roughly spheri-
cal shape of 1. Hence the Au19Cu30 cluster with its 22 elec-
tron count could be another example whose complexity is
beyond the superatom model. On the other hand, our analy-
sis of the HOMO and LUMO orbitals from density func-
tional theory (DFT) does show that they are delocalized
around the whole cluster (Figure S8). The HOMO looks
like two D-type orbitals with an inversion symmetry, while
the LUMO looks like one D-type orbital. In contrast, the
superatom model would predict F-type orbitals for the fron-
tier orbitals of a 22-electron system. This again shows that
our 22-electron Au19Cu30 cannot be described by the super-
atom model.48
AUTHOR INFORMATION
Corresponding Author
qmwang@tsinghua.edu.cn; djiang@ucr.edu
Notes
The authors declare no competing financial interest
ACKNOWLEDGMENT
This work was supported by the National Natural Science Foun-
dation of China (21473139, 21521091 and 21631007), and the
973 program (2014CB845603). The DFT computation was sup-
ported by University of California, Riverside.
REFERENCES
(1) Jin, R.; Zeng, C.; Zhou, M.; Chen, Y. Chem. Rev. 2016, 116,
10346.
(2) Parker, J. F.; Fields-Zinna, C. A.; Murray, R. W. Acc. Chem. Res.
2010, 43, 1289.
(3) Schmid, G. Chem. Soc. Rev. 2008, 37, 1909。
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 4 of 5
(4) Lei, Z.; Wan, X.-K.; Yuan, S.-F.; Wang, J.-Q.; Wang, Q.-M. Dal-
(41) Zeng, J.-L.; Guan, Z.-J.; Du, Y.; Nan, Z.-A.; Lin, Y.-M.; Wang,
ton. Trans. 2017, 46, 3427.
(5) Yamazoe, S.; Koyasu, K.; Tsukuda, T. Acc. Chem. Res. 2014, 47,
816.
(6) Li, G.; Jin, R. Acc. Chem. Res. 2013, 46, 1749.
(7) Pensa, E.; Cortés, E.; Corthey, G.; Carro, P.; Vericat, C.; Fonticelli,
M. H.; Benítez, G.; Rubert, A. A.; Salvarezza, R. C. Acc. Chem. Res.
2012, 45, 1183.
(8) Zeng, C.; Chen, Y.; Kirschbaum, K.; Lambright, K. J.; Jin, R.
Science 2016, 354, 1580.
(9) Teo, B. K.; Shi, X.; Zhang, H. J. Am. Chem. Soc. 1992, 114, 2743.
(10) Chen, J.; Zhang, Q.-F.; Bonaccorso, T. A.; Williard, P. G.; Wang,
L.-S. J. Am. Chem. Soc. 2014, 136, 92.
(11) Wan, X.-K.; Lin, Z.-W.; Wang, Q.-M. J. Am. Chem. Soc. 2012,
134, 14750.
(12) Wan, X.-K.; Yuan, S.-F.; Lin, Z.-W.; Wang, Q.-M. Angew. Chem.
Int. Ed. 2014, 53, 2923.
(13) Jadzinsky, P. D.; Calero, G.; Ackerson, C. J.; Bushnell, D. A.;
Kornberg, R. D. Science 2007, 318, 430.
(14) Jin, R. Nanoscale 2015, 7, 1549.
(15) Zeng, C.; Chen, Y.; Liu, C.; Nobusada, K.; Rosi, N. L.; Jin, R.
Sci. Adv. 2015, 1, e1500425.
(16) Zeng, C.; Chen, Y.; Kirschbaum, K.; Appavoo, K.; Sfeir, M. Y.;
Jin, R. Sci. Adv. 2015, 1, e1500045.
(17) Zhu, M.; Aikens, C. M.; Hollander, F. J.; Schatz, G. C.; Jin, R. J.
Am. Chem. Soc. 2008, 130, 5883.
(18) Crasto, D.; Malola, S.; Brosofsky, G.; Dass, A.; Häkkinen, H. J.
Am. Chem. Soc. 2014, 136, 5000.
(19) Heaven, M. W.; Dass, A.; White, P. S.; Holt, K. M.; Murray, R.
W. J. Am. Chem. Soc. 2008, 130, 3754.
(20) Song, Y.; Wang, S.; Zhang, J.; Kang, X.; Chen, S.; Li, P.; Sheng,
H.; Zhu, M. J. Am. Chem. Soc. 2014, 136, 2963.
(21) Wan, X.-K.; Tang, Q.; Yuan, S.-F.; Jiang, D.-e.; Wang, Q.-M. J.
Am. Chem. Soc. 2015, 137, 652.
(22) Wan, X.-K.; Yuan, S.-F.; Tang, Q.; Jiang, D.-e.; Wang, Q.-M.
Angew. Chem. Int. Ed. 2015, 54, 5977.
(23) Wan, X.-K.; Xu, W. W.; Yuan, S.-F.; Gao, Y.; Zeng, X.-C.;
Wang, Q.-M. Angew. Chem. Int. Ed. 2015, 54, 9683.
(24) Yang, S.; Chai, J.; Song, Y.; Kang, X.; Sheng, H.; Chong, H.;
Zhu, M. J. Am. Chem. Soc. 2015, 137, 10033.
(25) Negishi, Y.; Iwai, T.; Ide, M. Chem. Commun. 2010, 46, 4713.
(26) Negishi, Y.; Igarashi, K.; Munakata, K.; Ohgake, W.; Nobusada,
K. Chem. Commun. 2012, 48, 660.
(27) Dharmaratne, A. C.; Dass, A. Chem. Commun. 2014, 50, 1722.
(28) Wang, S.; Meng, X.; Das, A.; Li, T.; Song, Y.; Cao, T.; Zhu, X.;
Zhu, M.; Jin, R. Angew. Chem. Int. Ed. 2014, 53, 2376.
(29) Gao, Y.; Shao, N.; Pei, Y.; Zeng, X. C. Nano Lett. 2010, 10,
1055.
(30) Yang, H.; Wang, Y.; Huang, H.; Gell, L.; Lehtovaara, L.; Malola,
S.; Häkkinen, H.; Zheng, N. Nat. Commun 2013, 4, 2422.
(31) Wang, S.; Jin, S.; Yang, S.; Chen, S.; Song, Y.; Zhang, J.; Zhu,
M. Sci. Adv. 2015, 1, e1500441.
(32) Teo, B. K.; Zhang, H.; Shi, X. J. Am. Chem. Soc. 1993, 115,
8489.
(33) Yao, C.; Lin, Y.-j.; Yuan, J.; Liao, L.; Zhu, M.; Weng, L.-h.;
Yang, J.; Wu, Z. J. Am. Chem. Soc. 2015, 137, 15350.
(34) Yang, H.; Wang, Y.; Yan, J.; Chen, X.; Zhang, X.; Häkkinen, H.;
Zheng, N. J. Am. Chem. Soc. 2014, 136, 7197.
(35) Maity, P.; Tsunoyama, H.; Yamauchi, M.; Xie, S.; Tsukuda, T. J.
Am. Chem. Soc. 2011, 133, 20123.
(36) Maity, P.; Wakabayashi, T.; Ichikuni, N.; Tsunoyama, H.; Xie, S.;
Yamauchi, M.; Tsukuda, T. Chem. Commun. 2012, 48, 6085.
(37) Maity, P.; Takano, S.; Yamazoe, S.; Wakabayashi, T.; Tsukuda,
T. J. Am. Chem. Soc. 2013, 135, 9450.
(38) Kobayashi, N.; Kamei, Y.; Shichibu, Y.; Konishi, K. J. Am.
Chem. Soc. 2013, 135, 16078.
(39) Wang, Y.; Su, H.; Xu, C.; Li, G.; Gell, L.; Lin, S.; Tang, Z.;
Häkkinen, H.; Zheng, N. J. Am. Chem. Soc. 2015, 137, 4324.
(40) Wang, Y.; Wan, X.-K.; Ren, L.; Su, H.; Li, G.; Malola, S.; Lin,
S.; Tang, Z.; Häkkinen, H.; Teo, B. K.; Wang, Q.-M.; Zheng, N. J.
Am. Chem. Soc. 2016, 138, 3278.
Q.-M. J. Am. Chem. Soc. 2016, 138, 7848.
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(42) (a) Crystal data for 1·8H2O, C240H156N3O9P6S22Cl2Cu30Au19
·8H2O a = 20.9011(3), b = 30.0147(5), c = 21.3713(4)Å,  = 90.00(0),
 = 91.906(2),  = 90.00(0), V = 13399.7(4) Å3, space group P21/n, Z
= 2, T = 100K, 104125 reflections measured, 22965 unique (Rint =
0.0649), final R1 = 0.0580, wR2 = 0.1486 for 17439 observed reflec-
tions [I
C284H194N3O9P6Cl2Cu30Au19·2CH3OH·2H2O a =
30.5259(3) Å, c = 21.5548(3) Å, β =
>
2(I)]; (b) Crystal data for 2·2CH3OH·2H2O
21.4943(2) Å, b =
90.8620(10)°, V =
14141.2(3) Å3, space group P21/n, Z = 2, T = 149.4(9) K, 96930 re-
flections measured, 24928 unique (Rint = 0.0463), final R1 = 0.0507,
wR2 = 0.1540 for 20940 observed reflections [I > 2].
(43) Weissker, H. C.; Escobar, H. B.; Thanthirige, V. D.; Kwak, K.;
Lee, D.; Ramakrishna, G.; Whetten, R. L.; López-Lozano, X. Nat.
Commun 2014, 5, 4785.
9
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13
14
15
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26
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47
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49
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51
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53
54
55
56
57
58
59
60
(44) Yamazoe, S.; Takano, S.; Kurashige, W.; Yokoyama, T.; Nitta,
K.; Negishi, Y.; Tsukuda, T. Nat. Commun 2016, 7, 10414.
(45) Malol, S.; Hartmann, M. J.; Häkkinen, H. J. Phys. Chem. Lett
2015, 6, 515.
(46) Walter, M.; Akola, J.; Lopez-Acevedo, O.; Jadzinsky, P. D.;
Calero, G.; Ackerson, C. J.; Whetten, R. L.; Grönbeck, H.; Häkkinen,
H. Pro. Natl. Acad. Sci 2008, 105, 9157.
(47) Koskinen, M.; Lipas, P. O.; Manninen, M. Z. Phys. D 1995, 35,
285.
(48) Xu, W. W.; Zhu, B.; Zeng, X. C.; Gao, Y. Nat. Commun. 2016, 7,
13574.
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