An Alkynyl-Stabilized Pt5Ag22 Cluster Featuring a Two-Dimensional Alkynyl–Platinum “Crucifix Motif”

Article abstract of DOI:10.1002/chem.201704643

The “staple motif” has been widely applied to depict and predict the structures of thiolate or alkynyl-protected gold nanoclusters. By contrast, the composition, dimensions, configuration, and functionality of the platinum-ligand motif has remained completely unknown. Herein, we report the synthesis and crystal structure of a novel luminescent Pt₅Ag₂₂(C≡CPh)₃₂ (1) cluster, in which two-dimensional and two-functional alkynyl–platinum “crucifix motif” was observed. Such a crucifix motif with one Pt center and four alkynyl groups in the same plane acts as a two-dimensional unit in the cluster and functions as both a protective cover and an intermediate joint.

Full text of DOI:10.1002/chem.201704643

A Journal of
Accepted Article
Title: An Alkynyl-stabilized Pt₅Ag₂₂ Cluster Featuring Two-Dimensional
Alkynyl-Platinum "Crucifix Motif"
Authors: Hui Shen and Tsutomu Mizuta
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To be cited as: Chem. Eur. J. 10.1002/chem.201704643
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An Alkynyl-Stabilized Pt5Ag22 Cluster Featuring Two-Dimensional
Alkynyl–Platinum “Crucifix Motif”
Hui Shen, Tsutomu Mizuta*
Abstract: The “staple motif” has been widely applied to depict and
predict the structures of thiolate or alkynyl-protected gold
In addition to the classical Aux(SR or C≡CR)x+1 staple motif, other
nanoclusters. By contrast, the composition, dimensions, configuration, motifs with different dimensions and configurations were
and functionality of the platinum-ligand motif has remained completely
unknown. Herein, we report the synthesis and crystal structure of a
novel luminescent Pt5Ag22(C≡CPh)32 (1) cluster, in which two-
dimensional and two-functional alkynyl-platinum “crucifix motif” was
observed. Such a crucifix motif with one Pt center and four alkynyl
groups in the same plane acts as a two-dimensional unit in the cluster
and functions as both a protective cover and an intermediate joint.
discovered in thiolate- or alkynyl-protected, atomically precise
NCs, such as the octameric ring in Au20(SR)16,[26] mount-like
Ag2S5 motif in Ag44(SR)30,[27-28] distorted dimeric–RS-Ag-SR-Ag-
SR- staple-derivative motif in [PtAg24(2,4-SPhCl2)18]2-,[29] and μn (n
= 2,3,4,5) bonding motifs between thiolate or alkynyl and M (M =
Au, Ag, or Cu) in many other ligand-protected M (M = Au, Ag, or
Cu) NCs.[30-32] For metals other than Au, Ag, or Cu, such as Pt, Pd,
Ir, Rh, and Ni, the dimensions and configurations of ligand-metal
motifs for NCs remain completely unknown due to scarce single-
crystal structure. The only exception is the structure of thiolate-
constructed nickel NCs, Ni4(PET)8 and Ni6(PET)12, but no special
structure was observed.[33] In previous studies, the binding motifs
of these noble metals with thiolates or alkynyls were simply
deduced to be metal–thiolate, metal–acetylide (M–C≡) or metal–
vinylidene (M=C=C) bonds based on spectroscopic or other
measurements.[34-38] However, the absence of direct structural
identification for these binding modes has hindered further
advances in the study and understanding of ligand-protected non-
M (M=Au, Ag or Cu) NCs.
The “staple motif” that was first identified in the thiol-protected
gold nanoparticle Au102(p-MBA)44 (p-MBA=SPh-p-COOH),
depicts the bridge conformation of two thiols with three gold atoms
on the cluster surface.[1] The discovery of this motif not only
refreshed the conventional view of the gold–thiol interface but also
provided an efficient and accurate guide for predicting and
determining the structure of other thiolate-protected gold
nanoclusters (NCs).[2-4] In the past decade, surprisingly versatile
staple motifs have been observed. Experimentally, the
monomeric staple motif is now accepted to be a common surface
structure unit4 and other elongated homologs such as dimeric,[5-7]
trimeric,[8] and tetrameric[9-10] staple motifs have also been
identified. Theoretically, Jiang et al. showed that the formation of
the abovementioned Aux(SR)x+1 staple motifs can obviously lower
the binding energy of RS- on the gold surface and thus increase
the stability of NCs.[11] Based on the staple motif hypothesis, a
variety of Aun(SR)m NCs with known compositions and unknown
structures have been predicted.[12-17] Moreover, in some particular
On the other hand, there is rich chemistry on metal (such as Au,
Ag, Cu or Pt)-ligand (thiolate or alkynyl) complexes or small
clusters,[39] from which some interesting implications can be found
when comparing with ligand-protected nanoclusters. For instance,
structures of “staple motif” (RS-M-SR or R-C≡C-M-C≡CR, M=Au
or Ag) in ligand-protected Au or Ag nanoclusters, actually, have
been well recognized in organometallics much earlier,[39a-e] which
implies there are some intrinsic similarities of metal-ligand
structures between metal complexes and ligand-protected
nanoclusters.[40] That is to say, from non-M (M=Au, Ag or Cu)-
ligand complexes or small clusters, it is possible to deduce
structure of a non-M (M=Au, Ag or Cu)-ligand motif, for example,
a Pt-ligand motif, in ligand-protected metal nanoclusters. Indeed,
some traces on the structure of the Pt-ligand motif have appeared
cases,
such
as
for
Au25(SR)18 ,
– [12] Au38(SR)24,[13] and
Au24(SR)20[14], the calculated model was found to be quite close to
the experimental X-ray structure, implying the generality of the
staple motif in thiolate-protected gold NCs. Similarly, the “staple
motif” concept has been applied for deducing and describing
novel alkynyl-protected coinage NCs as well. Jiang et al.
investigated the interfacial binding of PhC≡C- groups on an ideal
Au20 cluster and suggested that the formation of a monomeric or
a V-shaped dimeric staple motif became energetically preferred
over the other binding modes.[18] More importantly, Wang et al.
and Zheng et al. directly observed the staple motif configuration
by single-crystal X-ray analysis.[19-25] Considering all staple motifs,
we can readily see that various Aux(SR)x+1 or Aux(C≡CR)x+1 staple
motifs can be categorized as one-dimensional (1D) oligomers
Aux(SR or C≡CR)x+1 with variable number of gold atoms and
ligands.
in
consideration
of
well-recognized
Pt(C≡CR)4-based
complexes.[39f-l] Nevertheless, compared with the staple motif,
there are still some doubts on such a unit, for example: whether a
larger cluster can be constructed from the Pt(C≡CR)4 unit? What
is the dimeric configuration of Pt(C≡CR)4 unit? How about the
functionalities of such unit? and so on.
Herein, we reveal the motif structure of alkynyl–Pt for the first time
by determining the single-crystal structure of a luminescent
Pt5Ag22(C≡CPh)32 (1) cluster. This cluster exhibits four unique
characteristics: (1) it is a large one in the family of alkynyl-
stabilized platinum-silver clusters; (2) the Pt atom in cluster 1 has
no obvious center preference; (3) the cluster is luminescent; (4)
more importantly, in this cluster, we observed an alkynyl–Pt
intersecting crucifix motif with two functionalities.
[a]
Prof. Dr. T. Mizuta, H. Shen
Department of Chemistry
Graduate School of Science, Hiroshima University
Kagamiyama 1-3-1, Higashi-hiroshima 739-8526, Japan
E-mail: mizuta@sci.hiroshima-u.ac.jp
Supporting information for this article is given via a link at the end of
the document.
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Cluster 1 was synthesized via the reduction of PhC≡CAg and
H2PtCl6·6H2O by NaBH4 in dichloromethane. Crystals suitable for
X-ray diffraction measurement were obtained by vapor diffusion
of ether to dichloromethane solution (see supporting information
for details). The cluster composition, as revealed by single-crystal
X-ray structural analysis, is Pt5Ag22(C≡CPh)32. Both cold-spray
mass spectrometry and elemental analysis unambiguously
verified the composition.
or eight Ag atoms per unit and thus obtain a coverage that is two
or four times higher than that of the monomer staple motif. From
Figure 1D (top and bottom), we can see that a dimeric crucifix
motif can be constructed by connecting two monomeric motifs
together via two Ag atoms. Moreover, two functionalities are
present for these five crucifix motifs: four act as single-sided
protective covers (crucifix motifs with the magenta Pt atom) and
the other one functions as a double-sided intermediate joint
(crucifix motif with the red Pt atom). Based on Figure 1D, we
describe 1 as dimeric crucifix motifs clamped mono-capped
square antiprismatics, which are further combined by a double-
sided monomeric crucifix motif.
Single-crystal X-ray structural analysis[41] revealed that
1
crystallized in the P21 space group (Table S1) and the unit cell
contains two independent clusters (Figure S1). No other
counterion is found in the crystal structure of cluster 1, indicating
that the cluster is neutral. The full structure of 1 is shown in
Figures 1A and 1B, from which it can be clearly seen that the
For further understanding of the functions of the Pt(C≡CR)4 motif,
it is essential to relate the newly discovered crucifix motif to the
cluster comprises 5 Pt atoms, 22 Ag atoms, and 32 alkynyl groups. classic staple motif. Here, we consider the motif in Au102(p-MBA)44
Two composition features are present in this cluster: first,
compared with Pt-doped Ag NCs, for example, Pt2Ag23Cl7(PPh3)10
(2)[42] and [PtAg24(2,4-SPhCl2)18]2− (3)[29], the five Pt atoms in
cluster 1 show no obvious center preference, which is in sharp
contrast with the Pt acting as the icosahedral center in 2 and 3,
indicating the unique effect of alkynyl on the site selectivity of Pt
atoms. Then, the cluster contains 27 metal atoms, which is quite
as an example. Figures 2A-1 and 2B-1 show the prototype crucifix
motif with its direct-connecting four Ag atoms and the staple motif.
Illustrated in Figure 2A-2 and 2B-2 is the framework vision of the
two prototypes keeping only the metal and the bridged S or C
atoms. Compared to the staple motif (Figure 2B-2), the crucifix
motif with its four Ag atoms can be viewed as an intersecting
staple motif (Figure 2A-2). If we further hide the leg-like metal
atoms (two Au atoms in Figure 2B-2, four Ag atoms in Figure 2B-
1), a one-dimensional strand remains as shown in Figure 2B-3
and a two-dimensional crucifix motif shown in Figure 2A-3. It is
clear that for suturing the protective net for the metal core, the
elementary unit of the staple motif (Figure 2B-3) acts as the
needlework, whereas the crucifix motif (Figure 2A-3) functions as
a patch.
rare in alkynyl-stabilized platinum-silver complexes or clusters.[39f-
l]
Figure 2. Comparison of crucifix and staple motifs. (A-1 and B-1) Prototypes of
a crucifix motif with its connecting four Ag atoms and a staple motif, respectively;
(A-2 and B-2) Framework version of A-1 and B-1, respectively; (A-3 and B-3)
Elementary unit of A-2 and B-2, respectively. Color codes for atoms: magenta
sphere, Pt; cyan sphere, Ag; red sphere, Au; yellow sphere, S; orange sphere,
O; gray sphere, C. All hydrogen atoms are omitted for clarity.
Figure 1. Pt5Ag22(C≡CPh)32 (1). (A) Cross-sectional view of the overall
structure; (B) Vertical view of the overall structure; (C) One of the five crucifix
motifs and its framework; (D) Overall structure showing the formation of the
dimeric crucifix motif and two functionalities of crucifix motifs. Color codes for
atoms: magenta and red spheres, Pt; cyan spheres, Ag; grey spheres, C. All
hydrogen atoms are omitted for clarity.
The dihedral angles of crucifix planes in the two dimeric crucifix
motifs were measured to be 67.38° and 76.39° (Figure S2),
respectively, leading to the expectation that clusters with different
compositions and structures will be obtained if the dihedral angles
were altered. The joint crucifix motif binds with eight Ag atoms in
a double-sided fashion that has not been observed for the staple
motif case. It is also noteworthy that cluster 1 with its four single-
sided crucifix motifs may act as a building block for metal-organic
Furthermore, five novel two-dimensional intersecting crucifix
motifs were observed in cluster 1 (Figures 1A and 1B). For each
of these, one Pt center binds four phenylethynyl groups to form a
planar unit (Figure 1C) that further interacts with other Ag atoms
via the –C≡C– groups. Such a crucifix motif can combine with four
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Ag 3d5/2 and Pt 4f7/2 binding energies of 1 determined by XPS are
368.8 and 73 eV, respectively. These values are larger than those
of the corresponding Ag (367.7 eV) and Pt metals (71.2 eV),
indicating that the metal atoms in 1 are mainly found in the
oxidized state (Figure S6).
frameworks (MOFs) due to the dual bonding capability of these
crucifix motifs. In addition, two types of bonding patterns are
displayed between the PhC≡C ligands and Ag atoms, which are
μ3 − η1, η1, η1, and μ3 − η1, η1, η2, respectively. The average Ag–
Ag bond length in the distorted mono-capped square antiprismatic
(Figure 1D) is 2.96 Å, close to the Ag–Ag bond length (ca. 2.889
Å) in bulk Ag.
In summary, we synthesized a novel luminescent alkynyl-
stabilized Pt5Ag22(C≡CPh)32 cluster, in which a type of alkynyl–Pt
crucifix motif was observed. The crucifix motif comprises one Pt
center and four alkynyl groups, and this motif behaves as a plane
for constructing the cluster. Functionalities of the crucifix motif are
divided into two types according to their sites: the first is a single-
sided protective cover and the second is a double-sided
intermediate joint. Together with the conventional staple motifs,
this crucifix motif comprises a more complete motif family and lays
the foundation for the exploration of other novel clusters.
Then, cold-spray mass measurement and elemental analysis
were performed to confirm the composition and charge of 1. No
mass signal for the cluster was observed when it was measured
directly, confirming its neutral state. However, a prominent peak
at 3425.93 with 2+ charge was successfully observed when the
sample was mixed with the Cs2CO3 solution. The peak can be
assigned to be [Pt5Ag22(C≡CPh)32Cs2]2+, for which the
experimental isotopic pattern was in good agreement with its
simulated pattern (Figure S3). Elemental analysis showed that the
weight percentage of C and H for the sample is 46.27% and
2.08%, respectively, close to the calculated results (C: 46.70%
and H: 2.45%).
Experimental Section
In a typical synthesis, 20.9 mg of PhC≡CAg and 4 mg of H2PtCl6·6H2O
were mixed in 5 mL of dichloromethane and stirred for 20 min. Then 0.56
mg of NaBH4 (dissolved in 0.3 mL of ethanol) was added dropwise to the
mixture under vigorous stirring. The solid dissolved gradually and the
solution turns brown after stirring for 5 min. The brown solution was stirred
for 24 h in the absence of light and some black precipitate appeared at the
bottom. The crude mixture was centrifuged and obtained red supernatant
was dried up to give deep-orange powder. 1 mL of CH2Cl2 was used to
dissolve the powder and obtained solution was filtered. After that, it was
subjected to vapour-diffusion of ether in the dark at room temperature.
Deep-orange block crystals were obtained after 3 days in 36.5% yield
(based on Pt).
Acknowledgements
We thank the Natural Science Center for Basic Research and
Development (N-BARD), Hiroshima University, for the X-ray
diffraction measurement, Professor S. Ishizaka for providing
assistance in the UV-vis measurements, Professor K. Saitow for
the absolute quantum yield and emission measurement,
Professor H. Miyaoka for the XPS measurement, and JEOL for
cold-spray mass measurements.
Figure 3. UV-vis adsorption spectrum of 1 in CH2Cl2. Inset: emission spectrum
of 1 in CH2Cl2 upon excitation at 400 nm; photographs of 1 in the crystal (left);
and CH2Cl2 solution form (right) under UV light.
As shown in Figure 3, the UV-vis absorption spectrum of 1 in
dichloromethane exhibits two broad adsorption peaks at 355 and
377 nm. Furthermore, cluster 1 characteristically emits deep-
orange and yellow light upon excitation in solid and solution form,
respectively. Upon excitation at 400 nm, the solution of 1 in
dichloromethane exhibits a prominent peak at 560 nm (absolute
quantum yield of 24.3%). Following assignments for previous
alkynyl-stabilized Pt-Ag clusters,[39f-l] we assigned the emissive
state of 1 is derived from an MLM'CT [Pt(d)/π(C ≡ CPh) →
Pt(pz)/Ag(sp) /π*(C≡CPh)] state modified by Pt┅Ag and Ag┅Ag
contacts. Note that 1 is quite stable in both solid and solution
forms in the absence of light, and also stable in solid form in the
presence of light, as indicated by the bright emission and
demonstrated by verysimilar emission spectra of the samples
after being stored for months (Figure S4). Strong luminescence
and good stability of the title cluster imply its potential applications
in cluster-based optical devices. The IR spectrum of 1 displays a
peak at 2039 cm−1, verifying the existence of –C≡C– (Figure S5).
Keywords: Alkynes • doping • crucifix motif • nanocluster • two-
dimensional
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COMMUNICATION
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10.1002/chem.201704643
Chemistry - A European Journal
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The “staple motif” has made great
impact on the prediction and
description of ligand-protected Au
and Ag nanoclusters. The motif
structure of other metals with ligands
however, still frustrates us. We
report here is the observation of two-
dimensional alkynyl-Pt crucifix motif
in an alkynyl-stabilized Pt5Ag22
cluster.
Hui Shen, Tsutomu Mizuta*
Page No. – Page No.
An Alkynyl-Stabilized Pt5Ag22
Cluster Featuring Two-Dimensional
Alkynyl–Platinum “Crucifix Motif”
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