Thermodynamic-Driven Self-Assembly: Heterochiral Self-Sorting and Structural Reconfiguration in Gold(I)-Sulfido Cluster System

Article abstract of DOI:10.1021/jacs.6b03844

By employing chiral precursors, a new class of chiral gold(I)-sulfido clusters with unique structures has been constructed. Interestingly, pure enantiomers of the precursors are found to self-Assemble into chiral hexa-and decanuclear clusters sequentially, while a racemic mixture of them has resulted in heterochiral self-sorting of an achiral meso decanuclear cluster. Chirality has determined not only the symmetry and structures but also the photophysical behaviors of these clusters. The racemic mixture of decanuclear clusters undergoes rearrangement and heterochiral self-sorting to give a meso decanuclear cluster. The thermodynamic-driven heterochiral self-sorting of gold(I) clusters provides a means to develop controlled self-Assembly that may be of relevance to the understanding of chirality in nature.

Full text of DOI:10.1021/jacs.6b03844

Communication
pubs.acs.org/JACS
Thermodynamic-Driven Self-Assembly: Heterochiral Self-Sorting and
Structural Reconfiguration in Gold(I)−Sulfido Cluster System
Liao-Yuan Yao, Terence Kwok-Ming Lee, and Vivian Wing-Wah Yam*
Institute of Molecular Functional Materials (Areas of Excellence Scheme, University Grants Committee (Hong Kong)) and
Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. China
*
S Supporting Information
examples on heterochiral self-sorting reported in the organic
10e,12a,b
ABSTRACT: By employing chiral precursors, a new class
of chiral gold(I)−sulfido clusters with unique structures
has been constructed. Interestingly, pure enantiomers of
the precursors are found to self-assemble into chiral hexa-
and decanuclear clusters sequentially, while a racemic
mixture of them has resulted in heterochiral self-sorting of
an achiral meso decanuclear cluster. Chirality has
determined not only the symmetry and structures but
also the photophysical behaviors of these clusters. The
racemic mixture of decanuclear clusters undergoes
rearrangement and heterochiral self-sorting to give a
meso decanuclear cluster. The thermodynamic-driven
heterochiral self-sorting of gold(I) clusters provides a
means to develop controlled self-assembly that may be of
relevance to the understanding of chirality in nature.
systems,
heterochiral self-sorting involving metal−organ-
12c
ic assemblies has been much less explored and rarely reported.
Furthermore, to our knowledge, it is not common to have both
sequential self-assembly and heterochiral self-sorting in the same
artificial system, not even to mention the gold(I) cluster system.
The importance of hydrogen bonding in nature and the
comparable energy of aurophilic interactions to hydrogen
bonding have enabled the gold(I) assemblies to serve as a
promising alternative in artificial systems, especially for those that
are of relevance to biological processes, such as self-assembly and
self-discrimination. Herein, we successfully develop an un-
precedented chiral polynuclear μ -sulfido gold(I) cluster system.
3
By employing chiral chlorogold(I) precursors, the chiral hexa-
and decanuclear clusters that share the same [Au S] basic
3
building blocks have been assembled sequentially. Surprisingly,
by replacing the enantiomers of chiral precursors with a racemic
mixture, a different meso achiral decanuclear gold(I) μ -sulfido
3
1
mong the family of gold complexes, the study of gold(I)
cluster, rather than a racemic mixture of chiral decanuclear
clusters, was obtained instead through heterochiral self-sorting.
The chirality of these clusters has not only determined their
symmetry and structures but also reveals their attractive
structure-dependent photophysical properties. Most interest-
ingly, the racemic mixture of chiral decanuclear clusters has been
found to undergo rearrangement and self-sorting to give the
achiral meso-cluster in solution, indicating the thermodynamic
nature of the heterochiral self-sorting, which provides a basis for
the future exploration of various potential applications and for
the future design of new biomimetic artificial systems.
A
clusters, being one of the most important classes, has
attracted considerable attention in recent decades. In the
polynuclear gold(I) assemblies, aurophilic interactions have not
only supported their diverse cluster architectures, but also have
endowed them with attractive structure-dependent photo-
which are also frequently observed in
metal nanoparticles and quantum dots. Recently, besides the
structures, there has also been an emerging interest in the
2
3
4
−6
physical behavior,
7
2e,4d,5c,f
applications of gold(I) clusters, such as luminescence,
1
c,2a,8a
5e,6a,f
catalysis,
ment,
chemosensing,
structural rearrange-
5
f,6b,d
6c
1b,5b
1a,b,8b
nanoaggregates, medicine,
biomimetics,
Reaction of R- or S-[BINAP(AuCl)
with H S in dichloromethane/ethanol/pyridine using a
procedure previously reported by us for nonchiral luminescent
2
] (1R or 1S) (Figure 1a)
and so on. The stability and ready availability of polynuclear
2
2b,4b−d,6a−d
sulfido gold(I) complexes
have enabled them to be
one of the most attractive candidates for various application
studies.
Supramolecular self-assembly and chiral self-sorting behaviors
are ubiquitous in nature. For instance, the quaternary structure
of proteins is constructed in a stepwise manner by noncovalent
interactions, while the chiral double helical structure of DNA is
self-sorted through hydrogen bonding. Artificial systems with an
understanding of the control of size and shape as well the
handedness can help to provide insights into the mechanism of
the precise control and organization as well as the recognition
behavior and the origin of chirality in nature. Sequential self-
assembly has been widely observed in polymers and in
nanoscience. It is still a major challenge to have a precise
control over homochiral and heterochiral self-sorting of the
4b−d,6a−d
gold(I) clusters
gave rise to chiral decanuclear gold(I)
clusters (2R or 2S). The dicationic molecular peak (m/z =
2293.6) in electrospray ionization mass spectrometry (ESI-MS)
9
establishes their chemical formula as [Au10(R-BINAP)
(μ -
4 3
S) ]Cl (2R) or [Au (S-BINAP) (μ -S) ]Cl (2S) (Figure S1).
4
2
10
4
3
4
2
4
c,6b−d
31
1
Unlike previous decanuclear gold(I) clusters,
NMR spectra of 2R and 2S both show two singlets at δ 24.3 and
8.4 ppm (see Figure S1 inset), rather than a pair of doublets as
the P{ H}
3
reported previously, indicating the adoption of a different
structure. Single crystal X-ray analyses of 2R and 2S reveal their
unique four-leaf clover-shaped decanuclear structures (Figure
10
1
b). In these chiral decanuclear clusters, the six Au(I) atoms in
1
1
Received: April 14, 2016
9
b,c,12a
systems.
Although there have been a limited number of
©
XXXX American Chemical Society
A
DOI: 10.1021/jacs.6b03844
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Journal of the American Chemical Society
Communication
different phosphorus environments in the same BINAP ligand.
Based on these results, a local chiral C symmetry has been
3
assigned to 3R and 3S.
Decanuclear clusters 2-meso and 2R/S, having the same
chemical formula but different structures and symmetry (Figure
S5), have provided an excellent opportunity for the exploration
of interesting structure-dependent photophysical properties. The
chiral decanuclear gold(I) clusters, 2R and 2S, only absorb UV
light with wavelengths of less than 400 nm, with an absorption
shoulder at about 339 nm and their solutions are colorless
1
(
Figure 2a and Figure S6). In contrast, a lower energy LMMCT
Figure 1. (a) Chiral BINAP-based dinuclear precursors, 1R and 1S. (b)
X-ray structures of chiral decanuclear gold(I)−sulfido clusters, 2R and
2S (Au, yellow; S, red; P, orange; H and C, white; for clarity, the BINAP
rings are shown in black (below plane of paper) and blue (above paper)
and the counter-anions and solvent molecules are omitted.).
the middle are located on nearly one plane to form a rectangle.
Compared to the contacts (ca. 3.0 Å) at the short edges of the
rectangle, relatively long Au···Au distances (ca. 3.3 Å) are found
between the two central gold(I) atoms (Tables S1 and S2). The
other four Au(I) atoms are attached above or below the
rectangular plane by Au−S bonds and Au···Au interactions
Figure 2. (a) UV−vis spectra of 1R, 2R, 2-meso, and 3R. (b) CD spectra
of chiral gold(I) complexes, 1R, 1S, 2R, 2S, 3R, and 3S. (c) Emission
spectra of 2R and 3R in solution. (d) Solid state emission spectra of 2R,
(
Tables S1 and S2). The decanuclear cluster can also be viewed
as containing two sets of double triangles, each of which has two
Au S] pyramids sharing one common gold(I) atom. Both the
2
-meso, and 3R at room temperature (the inset shows the photographs
[
of their emission color).
3
chiral cluster molecules and their decanuclear gold(I) cores
possess a local chiral D symmetry. Chiral gold(I) clusters with
absorption shoulder at 364 nm, with a tail in the visible region at
about 400−450 nm is observed in the UV−vis absorption
spectrum of the achiral decanuclear cluster 2-meso, giving a
yellow solution (Figure S6). The CD-silence of 2-meso has
confirmed its achiral nature. Conversely, the CD spectra of 2R
and 2S display intense Cotton effects and a mirror image
relationship in the range of 250−380 nm, which establishes their
chiral configurations (Figure 2b). Besides the chiral BINAP
ligands, the chiral metal cores are believed to also contribute to
the origin of the CD signals of the chiral clusters.
2
chiral metal cores in the same symmetry group are not very
common. The chirality has been transferred from and amplified
by the axial chiral BINAP ligands to the gold(I) cluster cores.
Surprisingly, reaction of rac-[BINAP(AuCl) ] (1-rac) and H S
2
2
under the same conditions is found to give a new cluster complex
as a yellow solid of more distinct color and different NMR
response (Figure S2). The molecular formula and the structure
of this complex have been finalized by X-ray single crystal
structure analysis as [Au (R-BINAP) (S-BINAP) (μ -S) ]Cl
2
1
0
2
2
3
4
(
2-meso), a novel meso decanuclear gold(I)−sulfido cluster
Chiral decanuclear gold(I) clusters 2R and 2S show structured
3
supported by alternating R- and S-BINAP ligands (Figure S3).
Different from the chiral decanuclear gold(I) clusters (2R and
and long-lived IL luminescence in dichloromethane, with
photoluminescence quantum yield of around 2% (Figure 2c
and Table S6). In contrast, meso decanuclear cluster 2-meso is
nonemissive in solution (Figure S6) but gives a dual green and
orange emission in the solid state both at ambient temperature
and at low temperature (77 K) upon excitation (Figure 2d and
Table S6). The low-energy emission band for 2-meso and 3R/S
at around 610−620 nm has been assigned as triplet ligand-to-
2
S), complex 2-meso consists of a propeller-shape assembly with
ideal S point group symmetry both in the solution and crystal
4
states. Similar to the previously reported decanuclear clusters
4c,6b−d
with nonchiral diphosphine ligands,
2-meso also possesses
a Au core with a Au macrocycle containing a Au chain at the
10
8
2
center. They adopt the same propeller-shape structure with S4
symmetry, indicating the optimality of this structure pattern.
Occasionally, during the recrystallization of 2S for single
crystal analysis, colorless prism crystals are found; one of the
crystals was picked for X-ray single crystal determination, which
reveals its identity as a unique hexanuclear gold(I) cluster,
3
metal charge transfer excited state ( LMCT) modified by metal···
4
c,6b
metal interactions,
whereas the structured emission
13
commonly observed in the BINAP systems is assigned as
triplet metal-perturbed intraligand ( IL) phosphorescence.
3
Altering combinations of the chiral ligands affects their structural
pattern, symmetry, and Au(I)···Au(I) interactions, leading to
unusual and unique structure-dependent photophysical proper-
ties and emission origins (Figure 2).
[
Au (S-BINAP) (μ -S)Cl ]Cl (3S) (Figure S3). This hexanu-
6 3 3 3
clear cluster contains three S-BINAP ligands, six Au(I) atoms,
and one sulfide atom, resembling the shape of a “clover”. The
3
1
1
P{ H} NMR spectra of the hexanuclear clusters show a pair of
The structure analysis shows that in hexanuclear clusters 3R
doublets with P−P coupling (Figures S2 and S4), indicating the
and 3S not all Cl−Au(I) coordination has been replaced by S−
B
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Communication
Au(I) coordination. This indicates that the hexanuclear gold(I)
clusters are available to undergo additional reaction and
assembly. For better control of the stoichiometric addition,
lithium sulfide was used instead of hydrogen sulfide as the sulfide
source. Upon addition of lithium sulfide, a pair of doublets and a
pair of singlets are observed at δ 26.0 and 35.7 ppm and δ 25.8
3
1
1
and 35.6 ppm sequentially in P{ H} NMR spectra (Figure 3a),
Figure 4. (a) Illustration of possible combinations of the chiral ligands
during random assembly. (b) Scheme showing self-sorting from the
racemic precursor and chiral cluster. (c) Proposed energy profile during
the assembly process. (d) Self-discrimination between precursors 1R
and 1-rac during the assembly, starting from 1R/1S = 3:1 (also 1R/1-rac
=
1:1) mixture. (e) Displacement reaction via heterochiral self-sorting.
structural reconfiguration and heterochiral self-sorting from a
mixture of 2R and 2S to meso decanuclear cluster 2-meso have
been monitored by UV−vis spectroscopy in solution, and the
growth of absorbance at around 400 nm is characteristic of the
existence of heterochiral self-sorting (Figure S8).
From these studies, 2-meso is found to be thermodynamically
more stable than the racemic mixture of enantiomers 2R and 2S.
This provides the driving force for the highly selective
heterochiral self-sorting-induced structural reconfiguration.
The slow reaction rate may be attributed to the higher energy
barrier between the racemic and the meso gold(I) clusters caused
by aurophilic interactions. Since 3R and 3S tend to undergo
disproportionation reaction to their precursors as revealed by
NMR studies, the chiral hexanuclear gold(I) clusters are
supposed to be the kinetic metastable intermediates, and their
energy levels are proposed to be between those of 1R/S and 2R/
S (Figure 4c). Not only the photophysical behaviors but also the
stability and reactivity have been influenced by the structures and
symmetry of these gold(I) clusters, which are dramatically
distinct between the homochiral and heterochiral clusters.
To further reveal the thermodynamic nature of the
heterochiral self-sorting, the following experiments have been
designed and carried out. A mixture of 1R and 1S in a mole ratio
3
1
1
Figure 3. (a) P{ H} NMR monitoring of the assembly process (1 mM
in CDCl ). (b) UV−vis (upper) and CD (lower) spectral changes upon
the addition of Li S to 1S (11 μM in CHCl ). (c) Scheme showing the
self-assembly process from dinuclear precursor 1S to hexanuclear cluster
S and to decanuclear cluster 2S. All the equivalents of Li S here, such as
3
2
3
3
2
1
/3, 2/3, and 3/3, are based on the precursor 1S.
indicating the formation of hexanuclear cluster 3S and
decanuclear cluster 2S. When the amount of sulfide reaches an
equivalent of 1S, signals characteristic of 1S and 3S disappear
completely, and only signals due to 2S remain. UV−vis along
with CD spectral changes are also observed during the assembly
process, corresponding to the sequential formation of hexa- and
decanuclear clusters (Figure 3b). Similar sequential assembly
process has been observed for their R enantiomers (Figure S7).
The hexagold(I) clusters 3R and 3S are key intermediates in the
assembly of chiral clusters 2R and 2S. The main framework of
of 3:1 (also 1R/1-rac = 1:1) under a H S atmosphere results in
2
nearly equal equivalents of 2R and 2-meso (Figure 4d), which can
31
1
be revealed by P{ H} NMR analysis. Additionally, stirring two
equivalents of 1S with 2R in solution for several days leads to the
appearance of two negative peaks at around 310 and 340 nm in
the CD spectra, indicative of the disappearances of 2R and the
presence of 1R (Figure S9). Meanwhile, the corresponding UV−
vis spectra show a growth in absorbance in the range of 350−425
nm, indicating the formation of complex 2-meso (Figure S10).
This suggests that R-BINAP has replaced half of the original S-
BINAP ligands on 2R, leading to the formation of meso cluster 2-
meso and release of chiral precursor 1R in the solution (Figure
4e). These results are in line with the energy profile and further
demonstrate the thermodynamic nature of this heterochiral self-
sorting.
3
R/S is the [Au S] pyramid, which is also the fundamental
building block of 2R/S (Figure 3c).
3
Attempts have been made to obtain a racemic mixture of chiral
decanuclear gold(I) clusters through homochiral self-sorting
from 1-rac. However, a clear yellow solution instead of a pale
yellow solution of 2R/S is obtained. NMR and ESI−MS studies
indicate that the product is a decanuclear gold(I) cluster with
structure different from that of 2R/S. Theoretically, if the self-
assembly process is completely random, the combination of
BINAP ligands can be (RRRS), (RSRS), (RRSS), and (RSSS)
(
Figure 4a), which is difficult to differentiate. Fortunately, single
crystals are obtained and X-ray analysis finally establishes a meso
decanuclear gold(I) cluster 2-meso with the alternating R- and S-
BINAP ligands (RSRS), revealing the existence of an interesting
heterochiral self-sorting phenomenon (Figure 4b). Most
interestingly, a racemic mixture of 2R and 2S can undergo
further self-sorting into achiral cluster 2-meso through structural
reconfiguration of the clusters in solution (Figure 4b). The
In summary, novel chiral gold(I) clusters and an achiral meso-
cluster are reported in this work. Employing different
combinations of chiral ligands alters the chirality of the resulted
gold(I) complexes, leading to unusual and unique structure-
dependent photophysical properties. Attractive heterochiral self-
sorting and sequential self-assembly are observed and monitored
C
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in this BINAP-based gold(I) cluster system. The assembly
processes and structural reconfiguration are dominated by the
thermodynamic-driven heterochiral self-sorting. The compara-
ble energy of aurophilic interactions to hydrogen bonding has
enabled the chiral gold(I) clusters to undergo self-assembly in a
stepwise fashion and to display heterochiral self-sorting behavior.
Our research would provide a fascinating model for the future
design of novel chiral gold(I) clusters and artificial systems and
also would be beneficial to a better understanding of the
heterochiral self-sorting and assembly processes that occur in
nature.
(b) Schmidbaur, H.; Schier, A. Chem. Soc. Rev. 2012, 41, 370−412.
̈
(c) Pyykko, P. Chem. Rev. 1997, 97, 597−636.
(4) (a) Zeller, E.; Beruda, H.; Kolb, A.; Bissinger, P.; Riede, J.;
Schmidbaur, H. Nature 1991, 352, 141−143. (b) Yam, V. W. W.; Cheng,
E. C. C.; Cheung, K. K. Angew. Chem., Int. Ed. 1999, 38, 197−199.
(c) Yam, V. W. W.; Cheng, E. C. C.; Zhou, Z. Y. Angew. Chem., Int. Ed.
2
000, 39, 1683−1685. (d) Yam, V. W. W.; Cheng, E. C. C.; Zhu, N. Y.
Angew. Chem., Int. Ed. 2001, 40, 1763−1765. (e) Fenske, D.; Langetepe,
T.; Kappes, M. M.; Hampe, O.; Weis, P. Angew. Chem., Int. Ed. 2000, 39,
1857−1860. (f) Tzeng, B. C.; Che, C. M.; Peng, S. M. Chem. Commun.
1997, 1771−1772.
(5) (a) Sevillano, P.; Fuhr, O.; Kattannek, M.; Nava, P.; Hampe, O.;
Lebedkin, S.; Ahlrichs, R.; Fenske, D.; Kappes, M. M. Angew. Chem., Int.
Ed. 2006, 45, 3702−3708. (b) Chui, S. S. Y.; Chen, R.; Che, C. M.
Angew. Chem., Int. Ed. 2006, 45, 1621−1624. (c) Koshevoy, I. O.; Lin, C.
L.; Karttunen, A. J.; Haukka, M.; Shih, C. W.; Chou, P. T.; Tunik, S. P.;
Pakkanen, T. A. Chem. Commun. 2011, 47, 5533−5535. (d) Koshevoy, I.
O.; Chang, Y. C.; Karttunen, A. J.; Selivanov, S. I.; Janis, J.; Haukka, M.;
Pakkanen, T.; Tunik, S. P.; Chou, P. T. Inorg. Chem. 2012, 51, 7392−
ASSOCIATED CONTENT
Supporting Information
■
*
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/jacs.6b03844.
Synthesis and characterization, X-ray crystallography,
photophysical studies, and supplementary figures (Figures
S1−S15) (PDF)
Compound 2R (CIF)
Compound 2S (CIF)
Compound 2-meso (CIF)
Compound 3R(CIF)
Compound 3S (CIF)
7
403. (e) Koshevoy, I. O.; Chang, Y. C.; Karttunen, A. J.; Haukka, M.;
Pakkanen, T.; Chou, P. T. J. Am. Chem. Soc. 2012, 134, 6564−6567.
f) Lasanta, T.; Olmos, M. E.; Laguna, A.; Lopez-de-Luzuriaga, J. M.;
(
Naumov, P. J. Am. Chem. Soc. 2011, 133, 16358−16361.
(6) (a) Lee, T. K. M.; Zhu, N. Y.; Yam, V. W. W. J. Am. Chem. Soc. 2010,
1
32, 17646−17648. (b) Yao, L. Y.; Hau, F. K. W.; Yam, V. W. W. J. Am.
Chem. Soc. 2014, 136, 10801−10806. (c) Hau, F. K. W.; Lee, T. K. M.;
Cheng, E. C. C.; Au, V. K. M.; Yam, V. W. W. Proc. Natl. Acad. Sci. U. S. A.
2
014, 111, 15900−15905. (d) Yao, L. Y.; Yam, V. W. W. J. Am. Chem.
Soc. 2015, 137, 3506−3509. (e) Yu, S. Y.; Sun, Q. F.; Lee, T. K. M.;
Cheng, E. C. C.; Li, Y. Z.; Yam, V. W. W. Angew. Chem., Int. Ed. 2008, 47,
AUTHOR INFORMATION
Corresponding Author
wwyam@hku.hk
■
4
551−4554. (f) Jiang, X. F.; Hau, F. K. W.; Sun, Q. F.; Yu, S. Y.; Yam, V.
W. W. J. Am. Chem. Soc. 2014, 136, 10921−10929.
7) (a) Fernando, A.; Dimuthu, K. L.; Weerawardene, M.; Karimova,
*
(
Notes
N. V.; Aikens, C. M. Chem. Rev. 2015, 115, 6112−6216. (b) Nozik, A. J.;
Beard, M. C.; Luther, J. M.; Law, M.; Ellingson, R. J.; Johnson, J. C.
Chem. Rev. 2010, 110, 6873−6890.
The authors declare no competing financial interest.
(8) (a) Pei, X. L.; Yang, Y.; Lei, Z.; Chang, S. S.; Guan, Z. J.; Wan, X. K.;
ACKNOWLEDGMENTS
■
Wen, T. B.; Wang, Q. M. J. Am. Chem. Soc. 2015, 137, 5520−5525.
(b) Mohr, F.; Jennings, M. C.; Puddephatt, R. J. Angew. Chem., Int. Ed.
2004, 43, 969−971.
V.W.-W.Y. acknowledges support from The University of Hong
Kong under the Strategic Research Theme on New Materials.
This work was supported by the ANR/RGC Joint Research
Scheme (A-HKU704/12), the University Grants Committee
Areas of Excellence Scheme (AoE/P-03/08), and a General
Research Fund (GRF) Grant from the Research Grants Council
of the Hong Kong Special Administrative Region, P. R. China
(9) (a) Keizer, H. M.; Sijbesma, R. P. Chem. Soc. Rev. 2005, 34, 226−
2
34. (b) Crego-Calama, M.; Reinhoudt, D. N. Supramolecular Chirality;
Springer-Verlag: Berlin Heidelberg, Germany, 2006. (c) Safont-
Sempere, M. M.; Fernandez, G.; Wurthner, F. Chem. Rev. 2011, 111,
5
(
784−5814.
10) (a) He, Y.; Ye, T.; Su, M.; Zhang, C.; Ribbe, A. E.; Jiang, W.; Mao,
(
HKU 17304715). L.-Y.Y. acknowledges the receipt of a
C. D. Nature 2008, 452, 198−201. (b) O’Leary, L. E. R.; Fallas, J. A.;
postgraduate studentship from The University of Hong Kong.
Dr. Lap Szeto is acknowledged for her assistance in X-ray crystal
data collection. The authors would like to thank Mr. Hao Li and
Prof. Shu-Yan Yu for their assistance in mass spectrometry
measurements.
Bakota, E. L.; Kang, M. K.; Hartgerink, J. D. Nat. Chem. 2011, 3, 821−
8
28. (c) Groschel, A. H.; Schacher, F. H.; Schmalz, H.; Borisov, O. V.;
Zhulina, E. B.; Walther, A.; Muller, A. H. E. Nat. Commun. 2012, 3, 710.
(d) Dressel, C.; Reppe, T.; Prehm, M.; Brautzsch, M.; Tschierske, C.
Nat. Chem. 2014, 6, 971−977. (e) Jedrzejewska, H.; Wierzbicki, M.;
Cmoch, P.; Rissanen, K.; Szumna, A. Angew. Chem., Int. Ed. 2014, 53,
1
3760−13764. (f) Ziegler, M.; Davis, A. V.; Johnson, D. W.; Raymond,
REFERENCES
■
K. N. Angew. Chem., Int. Ed. 2003, 42, 665−668. (g) Scarso, A.; Rebek, J.,
(
1) (a) Schmidbaur, H. Gold: Progress in Chemistry, Biochemistry and
Technology; John Wiley & Sons Ltd: Chichester, England, 1999.
b) Fabian, M. Gold Chemistry: Applications and Future Directions in the
Life Sciences; WILEY-VCH Verla GmbH & Co. KGaA: Weinheim,
Germany, 2009. (c) Laguna, A., Ed. Modern Supramolecular Gold
Chemistry: Gold-Metal Interactions and Applications; Wiley: Weinheim,
Germany, 2008.
Jr. Top. Curr. Chem. 2006, 265, 1−46.
(
11) (a) Yan, X. Z.; Li, S. J.; Cook, T. R.; Ji, X. F.; Yao, Y.; Pollock, J. B.;
(
Shi, Y. H.; Yu, G. C.; Li, J. Y.; Huang, F. H.; Stang, P. J. J. Am. Chem. Soc.
013, 135, 14036−14039. (b) Hudson, Z. M.; Boott, C. E.; Robinson,
2
M. E.; Rupar, P. A.; Winnik, M. A.; Manners, I. Nat. Chem. 2014, 6, 893−
8
2
(
98. (c) Qiu, H. B.; Hudson, Z. M.; Winnik, M. A.; Manners, I. Science
015, 347, 1329−1332.
12) (a) Makiguchi, W.; Tanabe, J.; Yamada, H.; Iida, H.; Taura, D.;
(
2) (a) Schmidbaur, H.; Raubenheimer, H. G.; Dobrzanska, L. Chem.
Soc. Rev. 2014, 43, 345−380. (b) Gimeno, M. C.; Laguna, A. Chem. Soc.
Ousaka, N.; Yashima, E. Nat. Commun. 2015, 6, 7236. (b) Wu, A. X.;
Chakraborty, A.; Fettinger, J. C.; Flowers, R. A., II; Isaacs, L. Angew.
Chem., Int. Ed. 2002, 41, 4028−4031. (c) Claessens, C. G.; Torres, T. J.
Am. Chem. Soc. 2002, 124, 14522−14523.
Rev. 2008, 37, 1952−1966. (c) Puddephatt, R. J. Chem. Soc. Rev. 2008,
3
1
2
7, 2012−2027. (d) Che, C. M.; Lai, S. W. Coord. Chem. Rev. 2005, 249,
296−1309. (e) Yam, V. W. W.; Au, V. K. M.; Leung, S. Y. L. Chem. Rev.
015, 115, 7589−7728.
(
13) Kunkely, H.; Vogler, A. Inorg. Chem. Commun. 1999, 2, 533−535.
(
3) (a) Scherbaum, F.; Grohmann, A.; Huber, B.; Kruger, C.;
Schmidbaur, H. Angew. Chem., Int. Ed. Engl. 1988, 27, 1544−1546.
D
DOI: 10.1021/jacs.6b03844
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX