Two-Way Alloying and Dealloying of Cadmium in Metalloid Gold Clusters

Article abstract of DOI:10.1021/acs.inorgchem.9b00125

The alloying of monometal nanoparticles with a transition element has recently attracted extensive interest; however, the dealloying of alloy nanoparticles has rarely been reported. Two-way alloying and dealloying in metal nanoparticles is not known so far to the best of our knowledge. In this work, for the first time, we successfully achieved two-way alloying and dealloying of cadmium in metalloid gold clusters via an antigalvanic reaction in combination with a quasi-antigalvanic reaction and demonstrated reactant-ion-dependent dealloying as well.

Full text of DOI:10.1021/acs.inorgchem.9b00125

Communication
pubs.acs.org/IC
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
Two-Way Alloying and Dealloying of Cadmium in Metalloid Gold
Clusters
†
,‡,§,⊥
†,§,⊥
Lingwen Liao,†,§ Hongwei Dong,†,‡,§ Nan Xia,†,§ Jin Li,∥
Wenhao Zhang,
Shengli Zhuang,
Haiteng Deng,¶ and Zhikun Wu*
,†,§
†Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in
Nanoscience, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei, Anhui 230031, P. R. China
‡
University of Science and Technology of China, Hefei, Anhui 230026, P. R. China
§
Institute of Physical Science and Information Technology, Anhui University, Hefei, Anhui 230026, P. R. China
∥
¶
Tsinghua University-Peking University Joint Center for Life Sciences, School of Life Sciences, and MOE Key Laboratory of
Bioinformatics, School of Life Sciences, Tsinghua University, Beijing 100084, P. R. China
*
S Supporting Information
are any other alloying modes and whether the Cd atom(s) can
be removed (dealloyed) with the structure changed or not,
especially whether the two-way alloying and dealloying of
ABSTRACT: The alloying of monometal nanoparticles
with a transition element has recently attracted extensive
interest; however, the dealloying of alloy nanoparticles has
rarely been reported. Two-way alloying and dealloying in
metal nanoparticles is not known so far to the best of our
knowledge. In this work, for the first time, we successfully
achieved two-way alloying and dealloying of cadmium in
metalloid gold clusters via an antigalvanic reaction in
combination with a quasi-antigalvanic reaction and
demonstrated reactant-ion-dependent dealloying as well.
8e,9a,c,d,10
metalloid gold clusters can be achieved. Antigalvanic
9d,10a,11
and quasi-antigalvanic
reactions were recently intro-
duced into nanochemistry for the synthesis of alloy or
monometal clusters. Interestingly, we fullfilled the two-way
alloying and dealloying of cadmium in metalloid gold clusters by
successively employing the antigalvanic and quasi-antigalvanic
methods.
12
Au (CHT)
was chosen as the precursor cluster because
3
4
22
of its facile access to us. The Cd alloying of Au (CHT) via an
3
4
22
antigalvanic reaction is very facile. For reaction details, see the
Supporting Information, and for UV−vis/near-IR (NIR)
spectroscopy monitoring, see Figure S1. The formula of the
as-prepared material was determined by electrospray ionization
mass spectrometry (ESI-MS) in positive mode, assisted by
cesium acetate (CsOAC). Note that no rational signals were
obtained from both positive and negative ionization modes
without the addition of CsOAC, which implies charge neutrality
of the as-obtained clusters (Figure S2). Additional experimental
results provide support for this (Figures S3 and S4). Figure 1
shows one dominant peak centered at m/z 4187.08 correspond-
he alloying of metal nanoparticles is of great significance
T
not only for fundamental scientific research but also for
practical applications because alloying can effectively tune the
1
structural and electronic properties of metal nanoparticles.
However, for relatively larger metal nanoparticles, conventional
characterization techniques, such as electron microscopy,
cannot always map an atomically precise structure, especially
the surface structure, to the extent that the alloying effects and
2
resultant properties can be understood in-depth. The
2
−7
emergences of metalloid clusters
with well-defined compo-
2
+
sitions and structures provide excellent platforms for solving
ing to the [Au Cd (CHT) + 2Cs] species (calcd, m/z
2
6
4
22
8e,9a,b
these challenging issues.
The majority of previous research
4186.93; deviation, m/z 0.15), and the calculated isotopic
pattern is in agreement with the experimental isotopic pattern
on metalloid cluster alloying focused on silver, copper, and gold
8
metals. Recently, metalloid gold clusters alloyed with IIB group
9
metals, such as cadmium (Cd) and mercury, are highly
regarded not only because Cd is an active metal compared to the
previously mentioned elements but also because Cd alloying
leads to rich structures and properties of metalloid gold clusters.
For example, three Cd alloying modes have been observed to
date. The first case is that the Cd atom replaces a kernel atom in
the metalloid gold cluster 1:1 without altering the staple
9c
structure, such as in Au Cd(CH CH Ph) . The second case
24
2
2
18
is that the Cd atoms occupy both the kernel and staple positions
of the metalloid gold clusters, changing the original structure,
9d
Figure 1. ESI-MS spectra of the as-prepared Au Cd (CHT) .
2
6
4
22
such as in Au Cd (SH)(CHT) (CHT = S-c-C H ). Last,
2
0
4
19
6
11
the third case is that the Cd atoms substitute the staple Au atoms
:2 without essentially changing the kernel structure, as in
1
Received: January 14, 2019
9b
[
Au Cd (CHT) ]. However, it is unknown whether there
19 2 16
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.9b00125
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
see the inset of Figure 1). Thereby the formula of the as-
Communication
(
ranging from 2.78 to 3.01 Å indicates that the Cd atoms in the
staple have strong interaction with the Au atoms in the kernel.
Additionally, the compacting of the staple motif and the
shortening of the intraparticle H−H distances after the
replacement of two Au atoms by one Cd atom were also
prepared cluster is concluded to be Au Cd (CHT) , which
26
4
22
was further supported by X-ray photoelectron spectroscopy
XPS) and thermogravimetric analysis (TGA): XPS reveals a
(
Au/Cd/S atomic ratio of 26/4.07/21.96, very close to the
expected ratio of 26/4/22 for Au Cd (CHT) ; TGA shows a
−
observed (Figure S7). For the case of [Au Cd (CHT) ] , four
26
4
22
19
2
16
−
weight loss of 31.08 wt %, in well agreement with the theoretical
value (31.24 wt %; Figure S5) of Au Cd (CHT) .
surface Au atoms of [Au (CHT) ] were replaced by two Cd
23 16
9b
atoms, with the kernel being unchanged. In Au Cd (CHT) ,
26
4
22
26
4
22
The complete structure of the Au Cd (CHT) cluster was
a distinct kernel change was observed compared with
Au (CHT) and is probably due to the relatively heavy
26
4
22
revealed by X-ray crystallography (XRC), as shown in Figure S6.
The absence of a counterion also provides evidence for
neutrality of the as-obtained clusters. Parts a−c of Figure 2
3
4
22
substitution of Cd in Au Cd (CHT) compared with the
2
6
4
22
−
substitution in [Au Cd (CHT) ] . As shown in Figure 2h, it is
1
9
2
16
suggested that two Au atoms (orange) in the Au (CHT)
3
4
22
cluster were shifted along the arrow direction. Because certain
Au−Au bonds in the kernel were stretched to fracture, a
distorted fcc Au kernel structure was created. It is found that
1
6
the average Aukernel−Au
bond length of Au Cd (CHT)
kernel
26 4
22
(
2.84 Å) is a little shorter than the average Aukernel−Au
bond
kernel
length of Au (CHT) (2.90 Å). Therefore, the Cd atoms not
3
4
22
only replaced the surface Au atoms by a 1:2 Cd/Au ratio but also
led to structural changes in the kernel. Such an alloying mode
was not previously reported and can be listed as the fourth
alloying mode of Cd in metalloid gold clusters.
Interestingly, Cd alloying not only tailors the interior
structure but also changes the exterior crystallographic arrange-
ment from the 2H to 4H phase array (Figure 3). It was known
Figure 2. Structure of Au Cd (CHT) : kernel (a), surface motif (b),
2
6
4
22
and the complete structure from different perspectives (c). Structure of
Au (CHT) : kernel (d), surface motif (e), and the complete structure
34
22
of from different perspectives (f). Comparison of the surface motifs
Au (CHT) (upper) and Au Cd (CHT) (lower), in which one Cd
34
22
26
4
22
atom replaces two nearby surface Au atoms (g). Comparison of the
kernel structures Au (CHT) (upper) and Au Cd (CHT) (lower)
3
4
22
26
4
22
(h). Color labels: yellow, S; red, Cd; others, Au. C and H atoms were
omitted.
Figure 3. Crystallographic arrangement of the Au (CHT) (a) and
3
4
22
depict structural details of Au Cd (CHT) , which contains a
distorted face-centered-cubic (fcc) Au16 kernel capped by two
Au Cd (CHT) (b) clusters in the single crystals. To highlight the
26
4
22
26 4 22
arrangement, the Au and Cd atoms of the clusters in each close-packed
plane are labeled in different colors.
“
paw-like” Cd(S−Au−S) motifs, one pentameric Au Cd (SR)
3
3
2
8
motif and one monomer Au(SR) motif. The Au Cd (SR)
2
3
2
8
−
8f
motif was not previously reported in metalloid clusters. It was
revealed that the structural framework of Au Cd (CHT)
that [Au Ag (CHT) ] (x ∼ 19) and Au Cd (SH)-
5−x
9d
2
x
18
20
4
(CHT)19 clusters also have different crystallographic arrange-
2
6
4
22
12
−
resembled that of Au (CHT)
(Figure 2d−f), and it can
be concluded that the “paw-like” Cd(S−Au−S) motif might
ments compared with the parent [Au (CHT) ] clusters
34
22
23
16
(Figure S8), which implies that alloying is also an effective way
3
14
have originated from one monomeric −S−Au−S− motif and
one trimeric −S−Au−S−Au−S−Au−S− motif, with one Cd
atom replacing two neighboring surface Au atoms (Figure 2g).
Cd substitution also induces the original staple motifs (two
monomeric −S−Au−S− motifs and one trimeric −S−Au−S−
Au−S−Au−S− motif) to transform into a newly found
pentameric Au Cd (SR) motif (Figure 2g), in which the
to influence the assembly of metalloid clusters.
Although the kernel of Au Cd (CHT) is distorted,
2
6
4
22
Au Cd (CHT) shows higher thermostability than
2
6
4
22
Au (CHT) based on UV−vis/NIR (Figure S9) probably
3
4
22
because of the formation of Cd(SR) motifs. Note that some
3
other influencing factors such as the protecting ligand and
charge can be excluded and so can the nominal shell-closing
electron count (N*) because the two clusters have the same N*
3
2
8
average S−Cd−S bond angle is slightly larger than that in the
Cd(S−Au−S) motif (∼109° vs ∼104°, respectively). Notably,
(N*Au34 = NvA − M − z = 34 × 1 − 22 − 0 = 12; N*
= 26
3
Au26Cd4
in the Cd(S−Au−S) and Au Cd (SR) motifs, the Cd−S bond
× 1 + 4 × 2 − 22 − 0 = 12). Alloying not only strengthens the
thermostability of the parent cluster but also effectively tunes the
optical properties of the parent cluster, as supported by the
maximum absorption shifts from 610 to 590 nm and from 465 to
479 nm, respectively (Figure S9). Besides, the maximum
emission blue shifts from 807 to 763 nm, and the fluorescence
3
3
2
8
length (varying from 2.55 to 2.61 Å) shows an obvious
difference from the Au−S bond length (from 2.17 to 2.46 Å),
indicating that the covalent radius of Cd is larger, as found in
many tables (for an example, see the previous work conducted
13
by Pyykko and Atsumi ). The close Aukernel−Cdstaple distance
B
DOI: 10.1021/acs.inorgchem.9b00125
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
intensity decreases by approximately 48% (Figure S10). The
emission blueshift may relate to the blueshift of the maximum
absorption of the Au (CHT) cluster in the NIR region, and
work provides novel insight into the structure of Cd-alloyed
metalloid gold clusters, has important implications toward the
structure−property correlation, reveals novel chemistry of
alloying and dealloying, and indicates a novel application of
AGR. Therefore, it is expected that this work will open new
avenues for engineering nanoparticles with atomic precision and
stimulating more research on metal nanoparticle alloying and
dealloying, as well as the structure−property correlation.
34
22
the fluorescence intensity decrease may be attributed to the fact
that the Cd atom has a weaker electron affinity than Au, thus
inhibiting charge transfer from the ligand to the metal core
1
5
through the metal−S bond.
Reversible dealloying of Cd in Au Cd (CHT) by a quasi-
26
4
22
9
d,10a,11
antigalvanic reaction
between Au Cd (CHT) and the
26 4 22
Au-CHT complex was observed (see Figures 4 and S11a and the
ASSOCIATED CONTENT
Supporting Information
■
*
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.9b00125.
Detailed synthesis method, characterization, crystal
structure refinements, Figures S1−S15, and Table S1
(PDF)
Accession Codes
CCDC 1871814 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge via
www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_
request@ccdc.cam.ac.uk, or by contacting The Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
Corresponding Author
E-mail: zkwu@issp.ac.cn.
■
Figure 4. Au-CHT complex that induced the transformation of
*
Au Cd (CHT) to Au (CHT) and Pt(CHT)2 complex that
2
6
4
22
34
22
induced the transformation of Au Cd (CHT) to Au (CHT) .
Color labels: yellow, S; red, Cd; others, Au; green, Pt; gray, C. H atoms
ORCID
2
6
4
22
18
14
Haiteng Deng: 0000-0003-2753-4590
Zhikun Wu: 0000-0002-2711-3860
Author Contributions
W.Z. and S.Z. contributed equally.
Notes
were omitted.
Experimental Section). Mass spectrometry identified the
⊥
product as Au (CHT) (Figure S11b). Note that the reduction
3
4
22
I
of Au is evidenced by the XPS results (Figure S12) and so is the
II
II
The authors declare no competing financial interest.
reduction of Cd in the reaction between Au (CHT) and Cd
34
22
(
Figure S13). Because the major metal in Au Cd (CHT) is
26 4 22
ACKNOWLEDGMENTS
gold, the reaction between Au Cd (CHT) and Au-CHT is
named the quasi-antigalvanic reaction.
reactions are also validated by cyclic voltammetry measurements
■
26
4
22
d,10a,11
9
The redox
The authors thank the Natural Science Foundation of China
(Grants 21222301, 21771186, 21829501, 21603234, 21701179,
21171170, and 21528303), the Key Program of the 13th five-
year plan, CASHIPS (KP-2017-16), the CASHIPS Director’s
Fund (BJPY2019A02), the CAS/SAFEA International Partner-
ship Program for Creative Research Teams, and the Innovative
Program of the Development Foundation of Hefei Center for
Physical Science and Technology (Grant 2017FXCX002) for
financial support.
I
(Figure S14). More interestingly, when the Au -CHT complex
was replaced by a Pt(CHT)2 complex (see Supporting
Information for the reaction details), another dealloyed cluster,
Au (CHT) , with an entirely different structure was
1
6
1
8
14
obtained (see Figure 4, and for the composition identification
and Pt exclusion, see Figure S15). This finding indicates that the
dealloying process is reactant-ion-dependent, which not only is
interesting but also provides versatile tuning of the metal
nanoparticles.
In summary, we synthesized a novel Cd-alloyed metalloid
gold cluster and precisely characterized it mainly with ESI-MS
and XRC, which revealed a new Cd-alloying mode: Cd atoms
occupy the parent cluster and change the kernel structure,
resulting in the formation of a novel staple structure,
Au Cd (SR) . The alloying not only influences the interior
structure but also alters the exterior crystallographic arrange-
ment from the 2H to 4H phase array. Cd alloying effectively
tunes the stability and optical properties of the parent cluster.
Interestingly, it was found that the as-obtained Cd-alloyed
metalloid gold clusters can be dealloyed by a quasi-antigalvanic
reaction with the structure changed or unchanged and that
dealloying is a reactant-ion-dependent process. Overall, our
REFERENCES
■
(
1) (a) Ferrando, R.; Jellinek, J.; Johnston, R. L. Nanoalloys: From
Theory to Applications of Alloy Clusters and Nanoparticles. Chem. Rev.
2008, 108, 845−910. (b) Yuan, X.; Dou, X.; Zheng, K.; Xie, J. Recent
Advances in the Synthesis and Applications of Ultrasmall Bimetallic
Nanoclusters. Part. Part. Syst. Charact. 2015, 32, 613−629. (c) Kwak,
K.; Choi, W.; Tang, Q.; Kim, M.; Lee, Y.; Jiang, D. E.; Lee, D. A
molecule-like PtAu (SC H ) nanocluster as an electrocatalyst for
3
2
8
2
4
6
13 18
hydrogen production. Nat. Commun. 2017, 8, 14723. (d) Chen, G.;
Zhao, Y.; Fu, G.; Duchesne, P. N.; Gu, L.; Zheng, Y.; Weng, X.; Chen,
M.; Zhang, P.; Pao, C.-W.; Lee, J.-F.; Zheng, N. Interfacial Effects in
Iron-Nickel Hydroxide-Platinum Nanoparticles Enhance Catalytic
Oxidation. Science 2014, 344, 495−499. (e) Huang, X.; Zhao, Z.;
Cao, L.; Chen, Y.; Zhu, E.; Lin, Z.; Li, M.; Yan, A.; Zettl, A.; Wang, Y.
M.; Duan, X.; Mueller, T.; Huang, Y. High-performance transition
C
DOI: 10.1021/acs.inorgchem.9b00125
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
metal-doped Pt Ni octahedra for oxygen reduction reaction. Science
(7) (a) Desireddy, A.; Conn, B. E.; Guo, J.; Yoon, B.; Barnett, R. N.;
Monahan, B. M.; Kirschbaum, K.; Griffith, W. P.; Whetten, R. L.;
Landman, U.; Bigioni, T. P. Ultrastable silver nanoparticles. Nature
2013, 501, 399−402. (b) Dhayal, R. S.; Liao, J. H.; Liu, Y. C.; Chiang,
3
2
(
015, 348, 1230−1234.
2) Jin, R.; Zeng, C.; Zhou, M.; Chen, Y. Atomically Precise Colloidal
Metal Nanoclusters and Nanoparticles: Fundamentals and Oppor-
+
tunities. Chem. Rev. 2016, 116, 10346−10413.
M. H.; Kahlal, S.; Saillard, J. Y.; Liu, C. W. [Ag {S P(OiPr) } ] : An
2
1
2
2 12
(
3) (a) Schnepf, A.; Schno
̈
ckel, H. Metalloid Aluminum and Gallium
Eight-Electron Superatom. Angew. Chem., Int. Ed. 2015, 54, 3702−
3706. (c) Negishi, Y.; Nakazaki, T.; Malola, S.; Takano, S.; Niihori, Y.;
Kurashige, W.; Yamazoe, S.; Tsukuda, T.; Hakkinen, H. A Critical Size
for Emergence of Nonbulk Electronic and Geometric Structures in
Dodecanethiolate-Protected Au Clusters. J. Am. Chem. Soc. 2015, 137,
1206−1212. (d) Tian, S.; Li, Y. Z.; Li, M. B.; Yuan, J.; Yang, J.; Wu, Z.;
Jin, R. Structural isomerism in gold nanoparticles revealed by X-ray
crystallography. Nat. Commun. 2015, 6, 8667. (e) Alhilaly, M. J.;
Bootharaju, M. S.; Joshi, C. P.; Besong, T. M.; Emwas, A. H.; Juarez-
Mosqueda, R.; Kaappa, S.; Malola, S.; Adil, K.; Shkurenko, A.;
Clusters: Element Modifications on the Molecular Scale? Angew. Chem.,
Int. Ed. 2002, 41, 3532−3552. (b) Schno
̈
ckel, H. Structures and
Properties of Metalloid Al and Ga Clusters Open Our Eyes to the
Diversity and Complexity of Fundamental Chemical and Physical
Processes during Formation and Dissolution of Metal. Chem. Rev. 2010,
1
10, 4125−4163. (c) Lu, Y.; Chen, W. Sub-nanometre sized metal
clusters: from synthetic challenges to the unique property discoveries.
Chem. Soc. Rev. 2012, 41, 3594−3623. (d) Knoppe, S.; Burgi, T.
Chirality in Thiolate-Protected Gold Clusters. Acc. Chem. Res. 2014, 47,
3
+
1
318−1326. (e) Yamazoe, S.; Koyasu, K.; Tsukuda, T. Nonscalable
Oxidation Catalysis of Gold Clusters. Acc. Chem. Res. 2014, 47, 816−
24. (f) Chakraborty, I.; Pradeep, T. Atomically Precise Clusters of
Noble Metals: Emerging Link between Atoms and Nanoparticles.
sler,
Hakkinen, H.; Eddaoudi, M.; Bakr, O. M. [Ag (SPhMe ) (PPh ) ] :
67 2 32 3 8
Synthesis, Total Structure, and Optical Properties of a Large Box-
Shaped Silver Nanocluster. J. Am. Chem. Soc. 2016, 138, 14727−14732.
(f) Yang, H.; Wang, Y.; Chen, X.; Zhao, X.; Gu, L.; Huang, H.; Yan, J.;
Xu, C.; Li, G.; Wu, J.; Edwards, A. J.; Dittrich, B.; Tang, Z.; Wang, D.;
Lehtovaara, L.; Hakkinen, H.; Zheng, N. Plasmonic twinned silver
nanoparticles with molecular precision. Nat. Commun. 2016, 7, 12809.
(g) Zeng, C.; Chen, Y.; Kirschbaum, K.; Lambright, K. J.; Jin, R.
Emergence of hierarchical structural complexities in nanoparticles and
their assembly. Science 2016, 354, 1580−1584. (h) Gan, Z.; Chen, J.;
Wang, J.; Wang, C.; Li, M. B.; Yao, C.; Zhuang, S.; Xu, A.; Li, L.; Wu, Z.
The fourth crystallographic closest packing unveiled in the gold
nanocluster crystal. Nat. Commun. 2017, 8, 14739. (i) Kenzler, S.;
Schrenk, C.; Schnepf, A. Au108S24(PPh ) : A Highly Symmetric
8
Chem. Rev. 2017, 117, 8208−8271. (g) Mayer, K.; Wessing, J.; Fas
̈
T. F.; Fischer, R. A. Intermetalloid Clusters: Molecules and Solids in a
Dialogue. Angew. Chem., Int. Ed. 2018, 57, 14372−14393.
(4) (a) Brust, M.; Walker, M.; Bethell, D.; Schiffrin, D. J.; Whyman, R.
Synthesis of Thiol-derivatised Gold Nanoparticles in a Two-phase
Liquid-Liquid System. J. Chem. Soc., Chem. Commun. 1994, 7, 801−802.
(b) Wu, Z.; Suhan, J.; Jin, R. One-pot synthesis of atomically
monodisperse, thiol-functionalized Au25 nanoclusters. J. Mater. Chem.
2
009, 19, 622−626. (c) Wu, Z.; MacDonald, M. A.; Chen, J.; Zhang, P.;
Jin, R. Kinetic Control and Thermodynamic Selection in the Synthesis
3
16
of Atomically Precise Gold Nanoclusters. J. Am. Chem. Soc. 2011, 133,
Nanoscale Gold Cluster Confirms the General Concept of Metalloid
Clusters. Angew. Chem., Int. Ed. 2017, 56, 393−396. (j) Sakthivel, N. A.;
Theivendran, S.; Ganeshraj, V.; Oliver, A. G.; Dass, A. Crystal Structure
of Faradaurate-279: Au279(SPh-tBu)84 Plasmonic Nanocrystal Mole-
cules. J. Am. Chem. Soc. 2017, 139, 15450−15459. (k) He, L.; Yuan, J.;
Xia, N.; Liao, L.; Liu, X.; Gan, Z.; Wang, C.; Yang, J.; Wu, Z. Kernel
Tuning and Nonuniform Influence on Optical and Electrochemical
Gaps of Bimetal Nanoclusters. J. Am. Chem. Soc. 2018, 140, 3487−
3490. (l) Huang, R. W.; Dong, X. Y.; Yan, B. J.; Du, X. S.; Wei, D. H.;
Zang, S. Q.; Mak, T. C. W. Tandem Silver Cluster Isomerism and Mixed
Linkers to Modulate the Photoluminescence of Cluster-Assembled
Materials. Angew. Chem., Int. Ed. 2018, 57, 8560−8566. (m) Kurasawa,
M.; Arisaka, F.; Ozeki, T. Asymmetricallyfused polyoxometalate-silver
alkynide composite cluster. Inorg. Chem. 2015, 54, 1650−1654.
(n) Chen, J.; Zhang, Q.-F.; Williard, P. G.; Wang, L.-S. Synthesis and
Structure Determination of a New Au20 Nanocluster Protected by
Tripodal Tetraphosphine Ligands. Inorg. Chem. 2014, 53, 3932−3934.
9
(
670−9673.
5) (a) Jadzinsky, P. D.; Calero, G.; Ackerson, C. J.; Bushnell, D. A.;
Kornberg, R. D. Structure of a Thiol Monolayer-Protected Gold
Nanoparticle at 1.1 Å resolution. Science 2007, 318, 430−433.
(b) Heaven, M. W.; Dass, A.; White, P. S.; Holt, K. M.; Murray, R.
W. Crystal Structure of the Gold Nanoparticle [N(C H ) ]-
8
17 4
[
(
Au (SCH CH Ph) ]. J. Am. Chem. Soc. 2008, 130, 3754−3755.
2
5
2
2
18
c) Zhu, M.; Aikens, C. M.; Hollander, F. J.; Schatz, G. C.; Jin, R.
Correlating the Crystal Structure of A Thiol-Protected Au Cluster and
2
5
Optical Properties. J. Am. Chem. Soc. 2008, 130, 5883−5885. (d) Liu,
C.; Li, T.; Li, G.; Nobusada, K.; Zeng, C.; Pang, G.; Rosi, N. L.; Jin, R.
Observation of Body-Centered Cubic Gold Nanocluster. Angew. Chem.,
Int. Ed. 2015, 54, 9826−9829. (e) Liao, L.; Zhuang, S.; Wang, P.; Xu, Y.;
Yan, N.; Dong, H.; Wang, C.; Zhao, Y.; Xia, N.; Li, J.; Deng, H.; Pei, Y.;
Tian, S. K.; Wu, Z. Quasi-Dual-Packed-Kerneled Au (2, 4-DMBT)
4
9
27
Nanoclusters and the Influence of Kernel Packing on the Electro-
5
+
chemical Gap. Angew. Chem., Int. Ed. 2017, 56, 12644−12648.
(o) Sheong, F. K.; Zhang, J. X.; Lin, Z. An [Au ] Approach to the
13
(6) (a) Wu, Z.; Wang, M.; Yang, J.; Zheng, X.; Cai, W.; Meng, G.;
Study of Gold Nanoclusters. Inorg. Chem. 2016, 55, 11348−11353.
(p) Nguyen, T.-A. D.; Cook, A. W.; Wu, G.; Hayton, T. W.
Subnanometer-Sized Copper Clusters: A Critical Re-evaluation of the
Synthesis and Characterization of Cu (MPP) (HMPP = 2-Mercapto-
Qian, H.; Wang, H.; Jin, R. Well-Defined Nanoclusters as Fluorescent
Nanosensors: A Case Study on Au (SG) . Small 2012, 8, 2028−2035.
2
5
18
(b) Antonello, S.; Perera, N. V.; Ruzzi, M.; Gascon, J. A.; Maran, F.
8
4
Interplay of Charge State, Lability, and Magnetism in the Molecule-like
5-n-propylpyrimidine). Inorg. Chem. 2017, 56, 8390−8396. (q) Liu, J.
W.; Feng, L.; Su, H. F.; Wang, Z.; Zhao, Q. Q.; Wang, X. P.; Tung, C.
H.; Sun, D.; Zheng, L. S. Anisotropic Assembly of Ag52 and Ag76
Nanoclusters. J. Am. Chem. Soc. 2018, 140, 1600−1603. (r) Yan, B. J.;
Du, X. S.; Huang, R. W.; Yang, J. S.; Wang, Z. Y.; Zang, S. Q.; Mak, T. C.
W. Self-Assembly of a Stable Silver Thiolate Nanocluster Encapsulating
a Lacunary Keggin Phosphotungstate Anion. Inorg. Chem. 2018, 57,
4828−4832. (s) Takano, S.; Hirai, H.; Muramatsu, S.; Tsukuda, T.
Au (SR) cluster. J. Am. Chem. Soc. 2013, 135, 15585−15594.
25
18
(c) Chen, Y. S.; Choi, H.; Kamat, P. V. Metal-Cluster-Sensitized Solar
Cells. A New Class of Thiolated Gold Sensitizers Delivering Efficiency
Greater Than 2%. J. Am. Chem. Soc. 2013, 135, 8822−8825. (d) Yi, C.;
Tofanelli, M. A.; Ackerson, C. J.; Knappenberger, K. L., Jr. Optical
Properties and Electronic Energy Relaxation of Metallic Au144(SR)60
Nanoclusters. J. Am. Chem. Soc. 2013, 135, 18222−18228. (e) Knoppe,
S.; Wong, O. A.; Malola, S.; Hakkinen, H.; Burgi, T.; Verbiest, T.;
Ackerson, C. J. Chiral Phase Transfer and Enantioenrichment of
Thiolate-Protected Au102 Clusters. J. Am. Chem. Soc. 2014, 136, 4129−
2
+
Hydride-Doped Gold Superatom (Au H) : Synthesis, Structure, and
9
Transformation. J. Am. Chem. Soc. 2018, 140, 8380−8383. (t) Huber,
M.; Schnepf, A.; Anson, C. E.; Schnockel, H. Si@Al [N(2, 6-
̈
56
4132. (f) Zhang, X. D.; Luo, Z.; Chen, J.; Shen, X.; Song, S.; Sun, Y.;
iPr C H )SiMe ] : The Largest Neutral Metalloid Aluminum Cluster,
2 6 3 3 12
Fan, S.; Fan, F.; Leong, D. T.; Xie, J. Ultrasmall Au10−12(SG)10−12
Nanomolecules for High Tumor Specificity and Cancer Radiotherapy.
Adv. Mater. 2014, 26, 4565−4568. (g) Du, B.; Jiang, X.; Das, A.; Zhou,
Q.; Yu, M.; Jin, R.; Zheng, J. Glomerular barrier behaves as an
atomically precise bandpass filter in a sub-nanometre regime. Nat.
Nanotechnol. 2017, 12, 1096−1102.
a Molecular Model for a Silicon-Poor Aluminum-Silicon Alloy? Angew.
Chem., Int. Ed. 2008, 47, 8201−8206. (u) Weinert, B.; Muller, F.;
Harms, K.; Clerac, R.; Dehnen, S. Origin and Location of Electrons and
Protons during the Formation of Intermetalloid Clusters [Sm@
3
‑
Ga H3−2xBi10+x] (x = 0, 1). Angew. Chem., Int. Ed. 2014, 53, 11979−
3‑x
11983.
D
DOI: 10.1021/acs.inorgchem.9b00125
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
(
8) (a) Gao, Y.; Shao, N.; Pei, Y.; Zeng, X. C. Icosahedral Crown Gold
11773−11776. (f) Li, M.-B.; Tian, S.-K.; Wu, Z. Improving the
Nanocluster Au Cu with High Catalytic Activity. Nano Lett. 2010,
Catalytic Activity of Au Nanocluster by Peeling and Doping. Chin. J.
43
12
25
1
0, 1055−1062. (b) Yang, H.; Wang, Y.; Huang, H.; Gell, L.;
Lehtovaara, L.; Malola, S.; Hakkinen, H.; Zheng, N. All-thiol-stabilized
Ag44 and Au Ag nanoparticles with single-crystal structures. Nat.
Chem. 2017, 35, 567−571. (g) Liu, X.; Astruc, D. From Galvanic to
Anti-Galvanic Synthesis of Bimetallic Nanoparticles and Applications in
Catalysis, Sensing, and Materials Science. Adv. Mater. 2017, 29,
1605305.
̈
12
32
Commun. 2013, 4, 2422. (c) Kumara, C.; Aikens, C. M.; Dass, A. X-ray
C r y s t a l S t r u c t u r e a n d T h e o r e t i c a l A n a l y s i s o f
(11) Yao, C.; Tian, S.; Liao, L.; Liu, X.; Xia, N.; Yan, N.; Gan, Z.; Wu,
Z. Synthesis of fluorescent phenylethanethiolated gold nanoclusters via
pseudo-AGR method. Nanoscale 2015, 7, 16200−16203.
(12) Dong, H.; Liao, L.; Zhuang, S.; Yao, C.; Chen, J.; Tian, S.; Zhu,
M.; Liu, X.; Li, L.; Wu, Z. A novel double-helical-kernel evolution
pattern of gold nanoclusters: alternate single-stranded growth at both
ends. Nanoscale 2017, 9, 3742−3746.
−
Au25‑xAg (SCH CH Ph) Alloy. J. Phys. Chem. Lett. 2014, 5, 461−
x
2
2
18
466. (d) Wang, S.; Jin, S.; Yang, S.; Chen, S.; Song, Y.; Zhang, J.; Zhu,
M. Total structure determination of surface doping [Ag Au (SR) ]-
4
6
24
32
(
BPh ) nanocluster and its structure-related catalytic property. Sci.
4 2
Adv. 2015, 1, No. e1500441. (e) Yao, C.; Chen, J.; Li, M.-B.; Liu, L.;
Yang, J.; Wu, Z. Adding Two Active Silver Atoms on Au Nanoparticle.
2
5
Nano Lett. 2015, 15, 1281−1287. (f) Li, Q.; Wang, S.; Kirschbaum, K.;
(13) Pyykko, P.; Atsumi, M. Molecular Single-Bond Covalent Radii
for Elements 1−118. Chem. - Eur. J. 2009, 15, 186−197.
(14) (a) Nag, A.; Chakraborty, P.; Bodiuzzaman, M.; Ahuja, T.;
−
Lambright, K. J.; Das, A.; Jin, R. Heavily doped Au25‑xAg (SC H )
x
6
11 18
nanoclusters: silver goes from the core to the surface. Chem. Commun.
3‑
2
016, 52, 5194−5197. (g) Bootharaju, M. S.; Joshi, C. P.; Parida, M. R.;
Antharjanam, S.; Pradeep, T. Polymorphism of Ag29(BDT)12(TPP)
4
cluster: interactions of secondary ligands and their effect on solid state
luminescence. Nanoscale 2018, 10, 9851−9855. (b) Gan, Z.; Chen, J.;
Liao, L.; Zhang, H.; Wu, Z. Surface Single-Atom Tailoring of a Gold
Nanoparticle. J. Phys. Chem. Lett. 2018, 9, 204−208.
Mohammed, O. F.; Bakr, O. M. Templated Atom-Precise Galvanic
Synthesis and Structure Elucidation of a [Ag Au(SR) ] Nanocluster.
−
2
4
18
Angew. Chem., Int. Ed. 2016, 55, 922−926. (h) Zeng, J. L.; Guan, Z. J.;
Du, Y.; Nan, Z. A.; Lin, Y. M.; Wang, Q. M. Chloride-Promoted
Formation of a Bimetallic Nanocluster Au Ag and the Total
(15) Liu, X.; Yuan, J.; Yao, C.; Chen, J.; Li, L.; Bao, X.; Yang, J.; Wu, Z.
8
0
30
Crystal and Solution Photoluminescence of MAg (SR) (M = Ag/
Structure Determination. J. Am. Chem. Soc. 2016, 138, 7848−7851.
24
18
Pd/Pt/Au) Nanoclusters and Some Implications for the Photo-
(i) Li, Q.; Luo, T.-Y.; Taylor, M. G.; Wang, S.; Zhu, X.; Song, Y.;
luminescence Mechanisms. J. Phys. Chem. C 2017, 121, 13848−13853.
Mpourmpakis, G.; Rosi, N. L.; Jin, R. Molecular “surgery” on a 23-gold-
atom nanoparticle. Sci. Adv. 2017, 3, No. e1603193. (j) Wan, X. K.;
Cheng, X. L.; Tang, Q.; Han, Y. Z.; Hu, G.; Jiang, D. E.; Wang, Q. M.
Atomically Precise Bimetallic Au Cu Nanocluster with an
(16) Das, A.; Liu, C.; Byun, H. Y.; Nobusada, K.; Zhao, S.; Rosi, N.;
Jin, R. Structure Determination of [Au (SR) ]. Angew. Chem., Int. Ed.
18
14
2015, 54, 3140−3144.
1
9
30
Icosidodecahedral Cu30 Shell and an Alkynyl-Cu Interface. J. Am.
Chem. Soc. 2017, 139, 9451−9454. (k) Yao, Q.; Feng, Y.; Fung, V.; Yu,
Y.; Jiang, D. E.; Yang, J.; Xie, J. Precise control of alloying sites of
bimetallic nanoclusters via surface motif exchange reaction. Nat.
Commun. 2017, 8, 1555. (l) Deng, G.; Malola, S.; Yan, J.; Han, Y.; Yuan,
P.; Zhao, C.; Yuan, X.; Lin, S.; Tang, Z.; Teo, B. K.; Hakkinen, H.;
Zheng, N. From Symmetry Breaking to Unraveling the Origin of the
Chirality of Ligated Au Cu Nanoclusters. Angew. Chem., Int. Ed. 2018,
1
3
2
5
7, 3421−3425. (m) Jin, S.; Xu, F.; Du, W.; Kang, X.; Chen, S.; Zhang,
J.; Li, X.; Hu, D.; Wang, S.; Zhu, M. Isomerism in Au-Ag Alloy
Nanoclusters: Structure Determination and Enantioseparation of
3
+
[
Au Ag (SR) (dppm) X ] . Inorg. Chem. 2018, 57, 5114−5119.
9
12
4
6 6
(
9) (a) Liao, L.; Zhou, S.; Dai, Y.; Liu, L.; Yao, C.; Fu, C.; Yang, J.; Wu,
Z. Mono-Mercury Doping of Au25 and the HOMO/LUMO Energies
Evaluation Employing Differential Pulse Voltammetry. J. Am. Chem.
Soc. 2015, 137, 9511−9514. (b) Li, Q.; Lambright, K. J.; Taylor, M. G.;
Kirschbaum, K.; Luo, T. Y.; Zhao, J.; Mpourmpakis, G.; Mokashi-
Punekar, S.; Rosi, N. L.; Jin, R. Reconstructing the Surface of Gold
Nanoclusters by Cadmium Doping. J. Am. Chem. Soc. 2017, 139,
1
7779−17782. (c) Yao, C.; Lin, Y.-j.; Yuan, J.; Liao, L.; Zhu, M.; Weng,
L.-h.; Yang, J.; Wu, Z. Mono-cadmium vs Mono-mercury Doping of
Au25 Nanoclusters. J. Am. Chem. Soc. 2015, 137, 15350−15353.
(d) Zhu, M.; Wang, P.; Yan, N.; Chai, X.; He, L.; Zhao, Y.; Xia, N.; Yao,
C.; Li, J.; Deng, H.; Zhu, Y.; Pei, Y.; Wu, Z. The Fourth Alloying Mode
by Way of Anti-Galvanic Reaction. Angew. Chem., Int. Ed. 2018, 57,
4
500−4504. (e) Yang, S.; Chen, S.; Xiong, L.; Liu, C.; Yu, H.; Wang, S.;
Rosi, N. L.; Pei, Y.; Zhu, M. Total Structure Determination of Au (S-
1
6
Adm)12 and Cd Au (StBu) and Implications for the Structure of
1
14
12
Au (SR) . J. Am. Chem. Soc. 2018, 140, 10988−10994.
15
13
(
10) (a) Gan, Z.; Xia, N.; Wu, Z. Discovery, Mechanism, and
Application of Antigalvanic Reaction. Acc. Chem. Res. 2018, 51, 2774−
783. (b) Wu, Z. Anti-Galvanic Reduction of Thiolate-Protected Gold
and Silver Nanoparticles. Angew. Chem., Int. Ed. 2012, 51, 2934−2938.
c) Wang, M.; Wu, Z.; Chu, Z.; Yang, J.; Yao, C. Chemico-Physical
2
(
Synthesis of Surfactant- and Ligand-Free Gold Nanoparticles and Their
Anti-Galvanic Reduction Property. Chem. - Asian J. 2014, 9, 1006−
2
+
1
010. (d) Li, M. B.; Tian, S. K.; Wu, Z.; Jin, R. Cu induced formation
of Au (SC H Ph) and its high catalytic activity for the reduction of 4-
44
2
4
32
nitrophenol at low temperature. Chem. Commun. 2015, 51, 4433−4436.
e) Tian, S.; Yao, C.; Liao, L.; Xia, N.; Wu, Z. Ion-precursor and ion-
dose dependent anti-galvanic reduction. Chem. Commun. 2015, 51,
(
E
DOI: 10.1021/acs.inorgchem.9b00125
Inorg. Chem. XXXX, XXX, XXX−XXX