Concentration- And Solvation-Induced Reversible Structural Transformation and Assembly of Polynuclear Gold(I) Sulfido Complexes

Article abstract of DOI:10.1021/jacs.0c04677

A series of polynuclear gold(I) sulfido complexes of bis(diphenylphosphino)amine ligands has been synthesized and characterized. A rather small variation in the conformation of the bis(diphenylphosphino)amine ligands has led to distinct differences in the identity of the polynuclear gold(I) sulfido complexes formed. Unprecedented concentration-dependent and solvation-dependent reversible cluster-to-cluster transformation between a dodecanuclear gold(I) sulfido complex (LMe-Au12) and a hexanuclear gold(I) sulfido complex (LMe-Au6) has been observed. The transformation process has been monitored not only by 1H and 31P{1H} NMR spectroscopy but also by UV-vis absorption spectroscopy and high-resolution electrospray ionization mass spectrometry (HR-ESI-MS) in the solution state. This work has provided a simple approach to achieve structure modulation of gold(I) sulfido complexes and an understanding of supramolecular transformations via external stimuli.

Full text of DOI:10.1021/jacs.0c04677

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Concentration- and Solvation-Induced Reversible Structural
Transformation and Assembly of Polynuclear Gold(I) Sulfido
Complexes
Liang-Liang Yan, Liao-Yuan Yao, and Vivian Wing-Wah Yam*
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ABSTRACT: A series of polynuclear gold(I) sulfido complexes of
bis(diphenylphosphino)amine ligands has been synthesized and
characterized. A rather small variation in the conformation of the
bis(diphenylphosphino)amine ligands has led to distinct differ-
ences in the identity of the polynuclear gold(I) sulfido complexes
formed. Unprecedented concentration-dependent and solvation-
dependent reversible cluster-to-cluster transformation between a
dodecanuclear gold(I) sulfido complex (LMe-Au12) and a
hexanuclear gold(I) sulfido complex (LMe-Au6) has been observed.
1
The transformation process has been monitored not only by H
and 31P{1H} NMR spectroscopy but also by UV−vis absorption
spectroscopy and high-resolution electrospray ionization mass
spectrometry (HR-ESI-MS) in the solution state. This work has provided a simple approach to achieve structure modulation of
gold(I) sulfido complexes and an understanding of supramolecular transformations via external stimuli.
regulation of supramolecular structures.1,2,11,49,50 Although
INTRODUCTION
■
there have been reports on concentration-induced isomer-
In nature, some fundamental biomacromolecules can sponta-
ization of metal−ligand assemblies,1,2,10,51,52 similar works have
neously change their structures through the introduction of
not been explored in the gold(I) sulfido complex system.
external stimuli or changes in the microenvironment, which is
The use of monodentate phosphine ligands to construct
usually referred to as “supramolecular transformations”.1
monolayer-protected gold nanoclusters could be traced back to
Studying the stimuli-responsive behavior not only can help
the 1960s. In 1969, Mason and co-workers first reported the
to uncover the foundation of biological functions but also can
Au11 structure, [Au11(PPh3)7(SCN)3], which could be
enable the design of artificial systems that are capable of
considered as an incomplete icosahedral structure.53 Mingos
changing their properties in response to external physical or
and co-workers later reported the icosahedral Au13 nanocluster,
chemical stimuli.1,2 In recent years, there has been a growing
[Au13(PMe2Ph)10Cl2](PF6)3, by reduction of the gold(I)
interest in the understanding and control of structural
precursor [(PMe2Ph)AuCl] with [Ti(η-C6H5Me)2].54 Teo
transformation and assembly of molecules induced by various
and co-workers reported the Au39 cluster, [Au39(PPh3)14Cl6]-
stimuli, which are usually associated with the manipulation of
Cl2, with a hexagonal close-packed layered structure.55
noncovalent interactions.3−7 Metal−ligand coordination bonds
Murray and co-workers reported the subnanometer
have been extensively employed in the construction of stimuli-
monolayer-protected clusters (MPCs), [Au13(PPh3)4(S-
responsive assemblies owing to their dynamic and reversible
(CH2)11CH3)2]Cl2 and [Au13(PPh3)4(S(CH2)11CH3)4], with
features.1,2,6−17 Polynuclear gold(I) complexes represent an
mixed ligands by using the dodecanethiolate ligands to replace
interesting class of metallosupramolecular system based on
some of the monodentate phosphine ligands.56 The mono-
metal−ligand coordination bonds and gold(I)···gold(I) inter-
actions, the latter of which has been termed aurophilic
interaction by Schmidbaur and co-workers.18−21 This attractive
interaction enables the polynuclear gold(I) complexes to
possess a variety of configurations and to show rich structure-
correlated photophysical properties.20−48 Apart from modulat-
ing the photophysical properties via changes in the structural
properties by molecular design, variation in the concentration
also represents an effective way to alter and control the process
of supramolecular self-assembly and the formation and
dentate phosphine ligands, such as PPh3, PiPr3, PMePh2, and
PMe3, have also been used to construct the polynuclear gold(I)
Received: April 29, 2020
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A

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Scheme 1. Structural Modulation of Gold(I) Sulfido Complexes
sulfido complexes.57−59 Since 1999, our group has focused on
the design and synthesis of polynuclear gold(I) complexes that
are bridged by diphosphine ligands and the μ3-sulfido
ligands.26,60−65 Polynuclear gold(I) species have emerged to
be one of the most prevalent systems in the gold family owing
to their relative ease of synthesis and their highly stable
nature.26,60−65 In recent years, our group has demonstrated the
interesting phenomenon of polynuclear gold(I)-based cluster-
to-cluster transformations.66−69 However, to the best of our
knowledge, to accomplish reversible interconversion between
gold(I) sulfido complexes is still a formidable challenge. On
the basis of our previous studies, the distances between two
phosphorus atoms in the phosphine ligands have been found
to play an important role in regulating the structures of gold(I)
sulfido complexes. A series of decanuclear and hexanuclear
gold(I) sulfido complexes with various bridging bis-
(diphenylphosphino)amine (PNP) ligands has been success-
fully accomplished (Scheme 1).26,60,64,65 However, a dodeca-
nuclear gold(I) sulfido cluster was obtained instead by using
bis(diphenylphosphino)methane (dppm) as the ligand,63
which has a similar P−P distance (∼3.1 Å) as PNP ligands
(Scheme 1). Given the ready functionalization of the PNP
ligand at the amino nitrogen, modification of substituents with
different steric effects at the N atom may lead to a control of
the nuclearity of the polynuclear gold(I) sulfido complexes. It
is envisaged that the steric effect of the R groups on the N
atom of the diphosphine ligands is crucial to regulate the bite
distance of the bridging ligand and hence the structure of these
clusters.
the solid state. Moreover, one of the dodecanuclear gold(I)
sulfido complexes (LMe-Au12) shows reversible concentration-
modulated interconversion cluster-to-cluster transformation,
the process of which has been monitored by 1H NMR,
31P{1H} NMR, and high-resolution electrospray ionization
mass spectrometry (HR-ESI-MS). The present work demon-
strates that a fine-tuning of the steric effect of the ligand can
have a significant impact on the regulation of the structure of
gold(I) sulfido complexes.
RESULTS AND DISCUSSION
■
Synthesis, Characterization, and Structure Determi-
nation. Reaction of [Au2Cl2(LEt)] with H2S in dichlorome-
thane−pyridine led to a lucid yellow solution that afforded a
yellow−green solid after evaporation. Yellow−green block
crystals of LEt-Au10 were obtained by slow vapor diffusion of
diethyl ether into its dichloromethane solution in 2 weeks. The
31P{1H} NMR spectrum of the yellow−green crystals in
CDCl3 showed a pair of doublets at δ = 84.56 and 81.69 ppm
(Figure S2), which is very similar to those observed for the
previously reported propeller-like structures of Au10 clus-
ters.64,66 HR-ESI-MS analyses revealed a molecular ion peak at
m/z = 1875.5584 (Figure S3), corresponding to the molecular
ion [Au10(LEt)4(μ3-S)4]2+ ([LEt-Au10]2+). The formation of
[Au10(LEt)4(μ3-S)4Cl2] has been further confirmed by single-
crystal X-ray diffraction studies. Complex LEt-Au10 crystallizes
̅
in the tetragonal P421c space group. The complex cation
adopts a propeller-shaped structure, with a gold macrocycle
containing eight gold atoms with a digold unit at the core,
bridged by four PNP ligands and four sulfur atoms (Figures 1a
and S4). The structure possesses an S4 point group, which is
the same as the previously reported Au10 clusters with PNP
ligands.26,64 Intramolecular Au(I)···Au(I) distances are in the
range of 2.98−3.33 Å (Table S2), comparable to those
reported in other gold(I) μ3-sulfido complexes.62−64,66−70
Reaction of [Au2Cl2(LMe)] with H2S in dichloromethane−
pyridine also led to a clear yellow solution. However, two kinds
of yellow−green crystals with different morphologies were
obtained at different stages by vapor diffusion of diethyl ether
into the dichloromethane solution. Yellow−green rectangular
In this work, a series of chlorogold(I) precursors based on
bis(diphenylphosphino)amine ligands, Ph2PN(R)PPh2 (where
R = CH3CH2 (LEt); R = CH3 (LMe); R = H (LH)) (Scheme 1)
with a systematic decrease in the steric effect, has been
employed to synthesize polynuclear gold(I) sulfido complexes.
Intriguingly, a systematic decrease in the steric effect of the
PNP ligands has dictated the nuclearity of the polynuclear
gold(I) sulfido complexes, ranging from decanuclear to
dodecanuclear gold(I) sulfido complexes (LEt-Au10, LMe
-
Au10, LMe-Au12, and LH-Au12). For LMe, a mixture of both
the decanuclear and the dodecanuclear gold(I) sulfido
complexes (LMe-Au10 and LMe-Au12) was clearly observed in
B
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yellow−green precipitate, which could be dissolved by adding
methanol to the reaction medium. Pale yellow−green block
crystals of LH-Au12 were isolated by vapor diffusion of diethyl
ether into its methanol solution. HR-ESI-MS analyses
confirmed that the molecular ion peak at m/z = 1201.0350
(Figure S7) corresponds to the molecular ion [Au12(LH)6(μ3-
S)4]4+ ([LH-Au12]4+). The formation of the [Au12(LH)6(μ3-
S)4]Cl4 structure was further confirmed by single-crystal X-ray
diffraction studies. Complex LH-Au12 crystallizes in the
monoclinic P21/c space group. There are four Au3S units
surrounded by six PNP ligands to form a metallamacrobicyclic
structure (Figures 1d and S8). The majority of Au···Au
distances in complex LH-Au12 lie in the range of 2.97−3.37 Å
(Table S11), suggesting remarkable intramolecular Au···Au
interactions. However, the 31P{1H} NMR spectrum of the pale
yellow−green crystals in CD3OD shows three singlets with the
same integral ratio at δ = 68.49, 70.36, and 70.65 ppm (Figure
S10) rather than two singlets in a ratio of 1:2 reported in a
similar metallamacrobicyclic Au12 structure based on dppm
ligands.63 The presence of a local C2h symmetry in the solution
state may be the reason for the presence of three kinds of
chemical environments for the P atoms.
It is worth noting that, when the steric effect decreases from
ethyl to methyl on the PNP ligand, a mixture of decanuclear
and dodecanuclear gold(I) μ3-sulfido complexes is obtained.
To our knowledge, this is the first example of isolating both the
decanuclear and dodecanuclear gold(I) complexes in one pot,
which is different from the isolation of a mixture of hexanuclear
and decanuclear gold(I) complexes as in the past,26 possibly
proceeding via a different mechanism. In addition, only the
dodecanuclear gold(I) μ3-sulfido complex is observed when
the steric effect is further decreased from methyl to hydrogen
on the PNP ligand. These results establish the important role
of the substituent on the N atom of the diphosphine ligands in
controlling the nuclearity of the polynuclear gold(I) sulfido
complexes.
Figure 1. Crystal structures of cluster cations of (a) LEt-Au10, (b)
L
anions, and hydrogen atoms are omitted for clarity (gray, C; blue, N;
purple, P; yellow, Au; orange, S).
Me-Au10, (c) LMe-Au12, and (d) LH-Au12. Phenyl rings, counter-
crystals (LMe-Au12) are obtained at an earlier stage than the
yellow−green block crystals (LMe-Au10). The crystal structures
of complexes LMe-Au10 and LMe-Au12 were confirmed by X-ray
single-crystal diffraction studies. Complex LMe-Au10 crystallizes
in the monoclinic P2/n space group and also adopts a
propeller-like Au10 cluster structure (Figures 1b and S5).
However, complex LMe-Au12 crystallizes in the triclinic P1
̅
space group and consists of two ship-type Au6 units bridged by
six PNP ligands and four μ3-sulfido atoms to give a
metallamacrobicyclic structure, similar to the previously
reported Au12 clusters based on the dppm ligand (Figures 1c
and S6).63 Short intramolecular Au(I)···Au(I) distances in the
range of 2.92−3.28 Å (Tables S5 and S8) are suggestive of the
presence of aurophilic interactions for complexes LMe-Au10 and
LMe-Au12.
Photophysical Studies. Because complexes LEt-Au10 and
LMe-Au10 have the same Au10 core, the electronic absorption
data for complexes LEt-Au10 and LMe-Au10 in methanol at 298
K show similar absorption patterns with the low-energy
absorption shoulders at around 400 nm (Figure 2a), which are
tentatively assigned as ligand-to-metal charge transfer (LMCT;
S → Au) transitions modified by Au(I)···Au(I) interactions.
Unlike the studies where reactions of H2S with chlorogold-
(I) precursors would give rise to clear yellow solutions in a
dichloromethane−pyridine system, the reaction of
[Au2Cl2(LH)] with H2S in the same solvent system led to a
Figure 2. (a) UV−vis spectra of [LEt-Au10]Cl2, [LMe-Au10]Cl2, [LMe-Au6]Cl2 (obtained from the transformation of [LMe-Au12]Cl4 to [LMe-Au6]Cl2
in solution state at 10−5 M concentration), and [LH-Au12]Cl4 in methanol. (b) Normalized solid-state emission spectra of [LEt-Au10]Cl2, [LMe
Au10]Cl2, [LMe-Au12]Cl4, and [LH-Au12]Cl4 at 77 K.
-
C
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Figure 3. 31P{1H} NMR spectral changes by (a) varying the initial concentration of LMe-Au12 from 4 × 10−3 to 4 × 10−5 M and (b) increasing the
concentration of LMe-Au12 from 1 × 10−4 to 8 × 10−4 M in CD3OD.
However, complex LH-Au12 shows a different UV−vis
absorption spectrum in methanol at 298 K with a low-energy
absorption shoulder at around 370 nm (Figure 2a). Excitation
of these complexes in the solid state at 77 K results in a dual
green and orange−red luminescence. The high-energy
emission in the green region is attributed to the metal-
perturbed ligand-centered phosphorescence, while the low-
energy emission in the orange−red region is assigned to
originate from a triplet ligand-to-metal charge-transfer excited
state (3LMCT) modified by metal···metal interactions, as
suggested from previous studies (Figure 2b).26
dodecanuclear species, to a new hexanuclear species (LMe-
Au6). As the temperature is further increased to 298 K, signals
characteristic of LMe-Au12 drop in intensity while those of LMe-
Au6 increase, indicating that more LMe-Au12 has been
transformed to LMe-Au6. However, HR-ESI-MS data obtained
under more dilute conditions (10−7 M) only indicated the
existence of LMe-Au6 (Figure S14). It is likely that the
concentration of complex LMe-Au12 in methanol may have an
influence on the core structures of these gold(I) sulfido
clusters. A concentration-dependent NMR study was under-
taken, with the concentration-triggered cluster transformation
1
Concentration-Dependent Reversible Cluster Trans-
formation between LMe-Au6 and LMe-Au12. The 31P{1H}
NMR spectrum of the yellow−green crystals of complex LMe-
Au12 in CD3OD (6 × 10−4 M) unexpectedly showed three
singlets with the same integral ratio at δ = 86.7, 89.3, and 89.5
ppm and a more intense singlet signal at δ = 79.8 ppm,
indicating the coexistence of LMe-Au12 and a new species LMe-
Au6 in deuterated methanol solution (Figure S13). According
to the 31P{1H} NMR, HR-ESI-MS, and previous studies
(Figures S13 and S14),26 the structure of LMe-Au6
([Au6(LMe)3(μ3-S)2]2+) was identified as a hexanuclear
complex with a distorted heterocubane core (Scheme 1).
Upon dissolution of LMe-Au12, a rather rapid structural
transformation from LMe-Au12 to LMe-Au6 is observed at
room temperature. To provide insights into the cluster
transformation process, LMe-Au12 (1.6 × 10−3 M) was
dissolved in CD3OD at low temperature, and the NMR
experiments were also performed at low temperature (Figures
S15 and S16). Variable-temperature 31P{1H} NMR spectral
changes have been monitored from 238 to 298 K (Figure S16).
The 31P{1H} NMR spectrum at 238 K shows three singlets
with the same integral ratio at δ = 85.9, 88.3, and 88.8 ppm,
unambiguously confirming the sole existence of LMe-Au12 in
methanol solution. As the temperature is increased from 238 to
273 K, signals characteristic of LMe-Au12 are downfield-shifted
to δ = 86.3, 89.0, and 89.2 ppm, while new signals at around δ
= 79.4 ppm attributed to the LMe-Au6 complex emerge,
indicating the conversion of LMe-Au12, which exists as a
process monitored by H NMR and 31P{1H} NMR spectral
changes under various initial concentrations of LMe-Au12 from
4 × 10−3 to 4 × 10−5 M in CD3OD (Figures S17 and 3a).
Indeed, higher ratios of LMe-Au6 are obtained from the
solution of LMe-Au12 with a lower initial concentration. When
the initial concentration of LMe-Au12 is reduced to 4 × 10−5 M,
LMe-Au6 emerged as the sole product, implying that LMe-Au12
has almost been completely transformed to LMe-Au6 (Figures
S17 and 3a). Similarly, only LMe-Au6 is observed in the HR-
ESI-MS of LMe-Au12 in methanol solution (Figure S14) at
concentrations lower than 4 × 10−5 M, which further confirms
the NMR observation. In addition, LMe-Au6 is found to convert
back to LMe-Au12 upon increasing the concentration. When the
concentration is increased from 1 × 10−4 to 8 × 10−4 M by
evaporating the CD3OD under reduced pressure with no
heating, a reversible transformation from LMe-Au6 to LMe-Au12
is found to occur (Figure 3b). In addition, when the chloride
counterions are replaced by hexafluorophosphate ions (Figure
S18), [LMe-Au12](PF6)4 also shows concentration-dependent
reversible cluster-to-cluster transformation in CD3CN. Fur-
thermore, [LMe-Au12](PF6)4 is found to be stable for over 5
successive dilution−concentration cycles (Figure S19), sugges-
tive of the highly reversible cluster-to-cluster transformation
processes induced by concentration-switching. On the basis of
these results, it can be established that the concentration of
LMe-Au12 plays a crucial role in modulating the cluster-to-
cluster transformation. This represents the first example of the
reversible transformation between two clusters simply by
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Figure 4. (a) Reversible structural conversion between LMe-Au6 and LMe-Au12. (b) 31P{1H} NMR spectra demonstrating the structural conversion
from LMe-Au6 to LMe-Au12 upon addition of D2O to a sample solution of CD3OD. (c) UV−vis spectral changes upon decreasing (left) and
increasing (right) the volume ratio of CH3OH to H2O. (d) HR-ESI-mass spectrum of complex LMe-Au12 in a solvent mixture of CH3OH and H2O.
Figure 5. HR-ESI-mass spectra of LMe-Au12 (2 × 10−4 mol) mixed with 1 equiv of LH-Au12 in CH3OH solution.
E
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changing the concentration of the gold(I) sulfido complex
under mild conditions.
Au12 may proceed via two possible conversion paths. In one
path, the clusters would undergo dissociation, followed by
rearrangement and reorganization. In another path, the process
involves ligand exchange on the surface of the clusters. A
control experiment involving the mixing of LMe-Au12 (2 × 10−4
mol) with 6 equiv of free LH does not lead to similar
observations, but instead some precipitates are formed. HR-
ESI-mass spectra further confirm the lack of
To provide insights into the concentration-dependent
cluster transformation process, the interconversion between
LMe-Au6 and LMe-Au12 has also been explored by reducing the
solvation by addition of bad solvents to force the complexes
into closer proximity (Figure 4a). Addition of D2O to the
solution of LMe-Au12 with the initial concentration at around 5
× 10−4 M in CD3OD has been monitored by 31P{1H} NMR
spectroscopy (Figure 4b). Upon increasing the content of
D2O, 31P{1H} NMR signals characteristic of LMe-Au6 are
found to decrease while those of LMe-Au12 increase. Finally, at
a volume ratio of CD3OD to D2O of 5:3, LMe-Au6 has almost
been completely converted to LMe-Au12 (Figure 4b).
Furthermore, the opposite transformation process can be
observed after decreasing the ratio of D2O by adding more
CD3OD to the solvent mixture of CD3OD and D2O (Figure
S20). Further supporting evidence comes from the UV−vis
absorption spectral changes (Figure 4c) and HR-ESI-MS data
in mixed solvents (Figures 4d and S21). The absorption
shoulder at around 300−400 nm is found to rise dramatically
by increasing the ratio of H2O (Figure 4c), indicating the
transformation of the complexes in solution from LMe-Au6 to
LMe-Au12. Similarly, the opposite transformation process can
also be observed by increasing the ratio of CH3OH (Figure
4c). The molecular ion peak at m/z = 1221.5565 (Figures 4d
and S21), corresponding to the molecular ion [Au12(LMe)6(μ3-
S)4]4+ mixed with [Au6(LMe)3(μ3-S)2]2+, also indicates the
transformation between LMe-Au12 and LMe-Au6 in mixed
solvents.
On the basis of these results, it can be further confirmed that
LMe-Au12 shows a concentration-dependent reversible trans-
formation process from its dodecanuclear structure to LMe-Au6
of a hexanuclear structure in the solution state. Owing to the
dynamic nature and the reversibility of aurophilic interactions
and Au(I)-S coordination bonds, gold(I) sulfido clusters show
their capability of transformation in the solution state. As soon
as the metastable LMe-Au12 is dissolved in CH3OH, a dynamic
equilibrium between LMe-Au12 and LMe-Au6 emerges. The LMe-
Au12 complex is found to be more stable at higher
concentrations and undergoes transformation to LMe-Au6
with dilution. The change of solvent conditions is believed
to affect the stability and solvation of the polynuclear gold(I)
sulfido complexes, which will govern the reversible trans-
formation process.
[ A u 1 2 ( L H ) n ( L M e
)
6 − n S 4 ] 4 + ( n
=
0 − 6 ) a n d
[Au6(LH)m(LMe)3−mS2]2+ (m = 0−3) species in the supernatant
(Figure S23). Therefore, the cluster-to-cluster transformation
between LMe-Au12 and LH-Au12 may involve initial dissocia-
tion, followed by a rearrangement and reorganization process
upon mixing, instead of ligand exchange. In addition, the
cryospray-ionization-mass spectroscopy (CSI-MS) study of
LMe-Au12 in CH3OH solution shows not only the signal of LMe-
Au6 and LMe-Au12 but also the signal of the [Au3(LMe)2S]+
(LMe-Au3) fragment (Figure S24), which is not detectable in
NMR spectroscopy (Figure S13). It is likely that the structural
conversion between LMe-Au12 and LMe-Au6 proceeds via
dynamic dissociation and reorganization processes involving
a transient LMe-Au3 species that is too short-lived to be
observable in the NMR spectra.
However, LMe-Au10 of the same bridging ligand LMe does
not yield a similar cluster transformation phenomenon. The
31P{1H} NMR spectrum and HR-ESI-MS data of LMe-Au10
show the sole existence of a Au10 cluster without detection of
any traces of other clusters (Figures S26 and S27). On the
basis of these results, it is envisaged that LMe-Au10 once formed
would be thermodynamically stable and would not undergo
further transformation to other species even under high
dilution.
CONCLUSION
■
In summary, a small variation in the conformation of
bis(diphenylphosphino)amine ligands has led to rather distinct
changes in the structure of the polynuclear gold(I) sulfido
complexes. For the first time, a mixture of both the decanuclear
and dodecanuclear gold(I) complexes was obtained. Moreover,
one of the dodecanuclear gold(I) complexes shows an
unprecedented concentration-dependent cluster-to-cluster
transformation, in which the two clusters of dodeca- and
hexanuclear identities could be interconverted by changing the
concentration of the complex. This work has provided a simple
approach to bring about a structural modulation of gold(I)
sulfido complexes by fine-tuning the substituent groups of the
PNP ligands. The occurrence of the interconversion has
provided a system for the study and understanding of
supramolecular transformations in polynuclear gold(I) systems
under the application of external stimuli.
On the basis of our previous works on gold(I) sulfido
clusters,67,68 which show the dynamic nature of gold(I) sulfido
clusters in solution state, it is likely that the transformation
between LMe-Au6 and LMe-Au12 involves changes not only at
the core of the clusters but also at the surface of the clusters.
To investigate the mechanism of structural conversion between
these two clusters, LH-Au12 (2 × 10−4 mol), which does not
undergo transformation in CD3OD, is mixed with 1 equiv of
LMe-Au12 in CD3OD. The 31P{1H} NMR spectrum of the
mixture shows the formation of an intricate mixture of
complexes, consisting of statistical distributions of
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/jacs.0c04677.
■
sı
General synthesis and characterization, X-ray crystallog-
raphy, photophysical properties, and supplementary
figures (PDF)
[ A u 1 2 ( L H ) n ( L M e
)
6 − n S 4 ] 4 + ( n
=
0 − 6 ) a n d
[Au6(LH)m(LMe)3−mS2]2+ (m = 0−3) species (Figure S22).
Further identification of the mixtures has been proved by HR-
ESI-mass spectral studies. A number of peaks corresponding to
multiply charged Au6 or Au12 molecular ions of different
bridging ligands are seen (Figure 5). We speculate that the
cluster-to-cluster transformation between LMe-Au12 and LH-
Crystal data for LEt-Au10 (CIF)
Crystal data for LMe-Au10 (CIF)
Crystal data for LMe-Au12 (CIF)
Crystal data for LH-Au12 (CIF)
F
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AUTHOR INFORMATION
■
Corresponding Author
Vivian Wing-Wah Yam − Institute of Molecular Functional
Materials and Department of Chemistry, The University of
Hong Kong, Hong Kong, P. R. China; orcid.org/0000-
0001-8349-4429; Email: wwyam@hku.hk
Authors
Liang-Liang Yan − Institute of Molecular Functional Materials
and Department of Chemistry, The University of Hong Kong,
Hong Kong, P. R. China; orcid.org/0000-0001-5210-1645
Liao-Yuan Yao − Institute of Molecular Functional Materials
and Department of Chemistry, The University of Hong Kong,
Hong Kong, P. R. China; orcid.org/0000-0003-2119-3895
Complete contact information is available at:
https://pubs.acs.org/10.1021/jacs.0c04677
Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
■
V.W.-W.Y. acknowledges UGC funding administered by The
University of Hong Kong for supporting the Electrospray
Ionization Quadrupole Time-of-Flight Mass Spectrometry
Facilities under the Support for Interdisciplinary Research in
Chemical Science and the support from The University of
Hong Kong under the University Research Committee (URC)
Strategically Oriented Research Theme (SORT) on Functional
Materials for Molecular Electronics. This work has been
supported by the Key Program of the Major Research Plan on
“Architectures, Functionalities and Evolution of Hierarchical
Clusters” of the National Natural Science Foundation of China
(Grant no. 91961202) and a General Research Fund (GRF)
from the Research Grants Council of Hong Kong Special
Administrative Region, P. R. China (HKU17301517). L.-L.Y.
acknowledges the receipt of a postgraduate studentship from
The University of Hong Kong. The Beijing Synchrotron
Radiation Facility (BSRF) is also acknowledged for providing
beamline time of the synchrotron radiation X-ray diffraction
facilities. We also thank the staff of BL17B beamline at the
National Facility for Protein Science (NFPS) of the Shanghai
Synchrotron Radiation Facility (SSRF), Shanghai, P. R. China,
for assistance during data collection. We also thank Dr.
Michael Ho-Yeung Chan, Dr. Anlea Chu, and Dr. Desmond
Yat-Hin Cheng for CSI-MS data collection.
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