Post-synthetic functionalization and ligand exchange reactions in gold(i) phenylthiolate-based coordination polymers

Article abstract of DOI:10.1039/d0nj03833d

Gold thiolate coordination polymers (CPs) are anisotropic materials with 1D or 2D networks exhibiting a large palette of photoluminescence properties. In this paper, we show that, from both lamellar acid and ester, [Au(p-SPhCO2X)]n CPs (X = H, Me), it is possible to perform post-synthesis esterification or saponification reactions. Three new 2D phases with X = Na, K and Cs were isolated. In addition, ligand exchange reactions were carried out from 1D [Au(p-SPh)]n CP and 2D [Au(p-SPhCO2X)]n CPs (X = H, Me) and the transformations from 1D to 2D structures and vice versa point out a mechanism of dissolution and recrystallization that is governed by the nature of the ligands and the presence of weak interactions. The obtained compounds exhibit solid state and RT photoemission characteristic of their structure. This journal is

Full text of DOI:10.1039/d0nj03833d

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Post-synthetic functionalization and ligand
exchange reactions in gold(I) phenylthiolate-based
coordination polymers†
Cite this: New J. Chem., 2020,
44, 17970
b
Larysa Okhrimenko,a Cynthia Cibaka Ndaya,a Alexandra Fateeva,
Gilles Ledouxc
a
and Aude Demessence
*
Gold thiolate coordination polymers (CPs) are anisotropic materials with 1D or 2D networks exhibiting a
large palette of photoluminescence properties. In this paper, we show that, from both lamellar acid and
ester, [Au(p-SPhCO2X)]n CPs (X = H, Me), it is possible to perform post-synthesis esterification or
saponification reactions. Three new 2D phases with X = Na, K and Cs were isolated. In addition, ligand
exchange reactions were carried out from 1D [Au(p-SPh)]n CP and 2D [Au(p-SPhCO2X)]n CPs (X = H, Me)
and the transformations from 1D to 2D structures and vice versa point out a mechanism of dissolution
and recrystallization that is governed by the nature of the ligands and the presence of weak interactions.
The obtained compounds exhibit solid state and RT photoemission characteristic of their structure.
Received 30th July 2020,
Accepted 25th September 2020
DOI: 10.1039/d0nj03833d
rsc.li/njc
predict the structure of the resulting compound or the size
of the nanoparticle; (ii) by ligand exchange reaction from a
Introduction
Hybrid organic/inorganic materials offer the advantage of designing preformed material, where it is assumed that the structure of
multifunctional compounds where each part brings its own the starting compound is preserved but it requires a two-step
properties.1 The inorganic component can be a metal, a cluster pathway.4 Two mechanisms are proposed for ligand exchange
or a nanoparticle with its own physical properties (magnetic, reactions: (i) the associative mechanism or topotactic process,
electric, optic, catalytic, etc.) and the organic part acts as a where the ligand exchange does not involve the rearrangement
linker in the case of coordination polymers or protecting of the inorganic part, and (ii) the dissociative mechanism or
agent for nanoparticles and it can also exhibit some intrinsic the dissolution/recrystallization process which consists of the
properties (optic, conductivity) or chemical functionality total or partial dissolution of the compound, followed by the
(hydrophobicity, external reactive organic groups). The control coordination of the new incoming ligand, this process can
of the external functionalization of hybrid nanoparticles or either give an isostructural phase or a new one.5 Knowing the
clusters is of tremendous importance for molecular recognition difficulty to control the size of nanoparticles, many reports use
in the medical domain.2 The addition of specific organic ligand exchange with preformed gold nanoparticles. In the case
molecules or functions in coordination polymers can bring of gold thiolate clusters, Aun(SR)m, that are atomically well
additional properties and preferential affinity for gas adsorp- defined particles and for some of them structurally known,
tion or generate a catalytic centre.3 There are two synthetic the ligand exchange offers the possibility to bring about a new
approaches to obtain new and complex functionalized hybrid external functionality.6 By determining their formula, it has
materials: (i) by direct reaction to form the target compound been shown that ligand exchange reactions involved the same
and functionalize it at the same time, with the advantage being composition through an associative substitution mechanism.7
a one-step reaction but the drawback being the difficulty to Partially exchanged ligand species have also been isolated
for Au102(SR)44, Au25(SR)18, or Au24Pd(SR)18 clusters and
confirm that the gold core remains the same.8 Nevertheless,
a
´
Univ. Lyon, Universite Claude Bernard Lyon 1, Institut de recherches sur la
depending on the incoming thiol molecule, some ligand
exchange mechanisms can also be dissociative. This has been
catalyse et l’environnement de Lyon (IRCELYON), UMR 5256 CNRS, Villeurbanne,
France. E-mail: aude.demessence@ircelyon.univ-lyon1.fr
b
c
9
shown for Au38(SR)24 clusters that transform into Au36(SR0)24
´
`
`
Univ. Lyon, Universite Claude Bernard Lyon 1, Institut Lumiere Matiere (ILM),
or Au25(SR)18 clusters that generate Au28(SR0)20,10 and also
Au144(SR)60 that change into Au133(SR0)52.11 In parallel to these two
associative and dissociative exchange mechanisms occurring in gold
thiolate clusters, we study here the post-functionalization and ligand
UMR CNRS 5306, Villeurbanne, France
´
´
Univ. Lyon, Universite Claude Bernard Lyon 1, Laboratoire des Multimateriaux et
Interfaces (LMI), UMR CNRS 5615, Villeurbanne, France
† Electronic supplementary information (ESI) available: FT-IR spectroscopy,
PXRD, TGA and photoemission analyses. See DOI: 10.1039/d0nj03833d
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Fig. 1 Representations of the structures of [Au(p-SPhCO2H)]n (a), [Au(p-SPhCO2Me)]n (b) and [Au(SPh)]n (c). Pink, Au(I); yellow, S; red, O; gray, C.
Hydrogen atoms are omitted for clarity.
exchange reactions for their analogues: the gold thiolate coor- Experimental
dination polymers (CPs), [Au(SR)]n.12 One article reports the
dynamic ligand exchange processes occurring in gold thiolate
Chemicals
Tetrachloroauric acid trihydrate (HAuCl4ꢀ3H2O, Z49% Au basis)
and methanol (Chromasolvs) were purchased from Sigma-
Aldrich Company. 4-Mercaptobenzoic acid (495%) was pur-
chased from TCI. The glassware used in the synthesis were
cleaned with aqua regia (aqua regia is a very corrosive product
and should be handled with extreme care), then rinsed with
copious amounts of deionised water and dried overnight
prior to use. All reactions were carried out under atmospheric
conditions.
colloidal species.13 Here, a series of crystalline solids of gold
para-substituted phenylthiolate CPs are studied to evaluate
the effect of the para-substituent on the structure and photo-
luminescence properties of CPs. Thus, the first part concerns
the esterification and saponification of [Au(p-SPhCO2H)]n
and [Au(p-SPhCO2Me)]n CPs, respectively. [Au(p-SPhCO2H)]n
(Fig. 1a) has been reported as a lamellar CP forming helical –
Au–S–Au–S– chains with para-mercaptobenzoic acid in the
interlamellar space interacting with each other through
catemeric hydrogen bonds.14 This CP exhibits low emission
centered at 665 nm at RT. [Au(p-SPhCO2Me)]n (Fig. 1b) is
also described as a lamellar compound, but in this case the
gold–sulfur chains are in a zig-zag shape and there is neither
interpenetration nor weak interactions between the linker
molecules.15 This esterified CP shows bright emission at
645 nm at RT due, in part, to the presence of short aurophilic
interactions. In the second part, ligand exchange between these
two 2D CPs and the 1D [Au(SPh)]n CP (Fig. 1c) is presented to
probe the associative and/or dissociative mechanisms that are
involved. The structure of [Au(SPh)]n is made of two interdigi-
tated helical –Au–S–Au–S– chains and the CP displays moderate
photoemission at RT centered at 684 nm.16 The different
reactions carried out are presented in Scheme 1.
The syntheses of the CPs [Au(p-SPhCO2H)]n,14
15
16
[Au(p-SPhCO2Me)]n and [Au(SPh)]n were performed following
the procedures reported previously. The ligand p-HSPhCO2Me has
been obtained via the esterification of p-mercaptobenzoic acid.17
Synthetic procedures
Esterification of [Au(p-SPhCO2H)]n (1). The insoluble
powder of [Au(p-SPhCO2H)]n (50 mg) was stirred in an acidic
mixture of 60 ml of MeOH with few drops of H2SO4 under reflux
(set temperature: 120 1C) for 2 days (10) and 7 days (1). The
resulting white powder was thoroughly washed with MeOH and
dried under vacuum.
Saponifications of [Au(p-SPhCO2Me)]n (2, 3 and 4). The
insoluble powder of [Au(p-SPhCO2Me)]n (50 mg) was stirred in
an aqueous solution of NaOH (60 ml, 145 equiv.) at 80 1C for
one week. The resulting white powder, compound 2, was
thoroughly washed with water and dried under vacuum. The
same reactions were carried out with KOH aqueous solution
(60 ml, 145 equiv.) under reflux for 72 h and CsOH aqueous
solution (60 ml, 145 equiv.) under reflux for 72 h. The resulting
white powders, compounds 3 and 4, respectively, are thor-
oughly washed with water and dried under vacuum.
Exchange reactions
Compound 5. In a 20 ml vial, 40 mg of [Au(p-SPhCO2Me)]n
(0.110 mmol, 1 equiv.) was mixed with 3 ml of HSPh (29 mmol,
263 equiv.). The vial is closed and heated at 120 1C for 6 h.
Scheme 1 Pathways of the different esterification, saponification and
ligand exchange reactions carried out. The numbers correspond to the
obtained compounds after reactions.
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The solid was then filtered, washed with acetone and dried Shining droplets of bulk gold were observed at the end of the
under an ambient atmosphere.
experiments.
Compound 6. In a 20 ml vial, 28 mg of [Au(SPh)]n (0.091 mmol,
SEM images were obtained with an FEI Quanta 250 FEG
1 equiv.) was mixed with 46 mg of p-HSPhCO2Me (0.275 mmol, scanning electron microscope in the microscopy centre of Lyon
3 equiv.) in 10 ml of water. The vial was closed and heated at 1 University. Samples were mounted on a stainless pad and
120 1C for 20 h. The solid was then filtered, washed first with sputtered with carbon to prevent charging during observation.
water and then with acetone, and dried under an ambient
atmosphere.
The photoemission studies were performed on homemade
apparatus. The sample was illuminated using an EQ99X laser
Compound 7. In a 20 ml vial, 44 mg of [Au(p-SPhCO2Me)]n driven light source filtered using a Jobin Yvon Gemini
(0.120 mmol, 1 equiv.) was mixed with 126 mg of p-HSPhCO2H 180 monochromator. The exit slit from the monochromator
(0.817 mmol, 7 equiv.) in 10 ml of water. The vial was closed was then reimaged on the sample using two 100 m focal length,
and heated at 100 1C for 20 h. The solid was then filtered, 2 inch diameter MgF2 lenses. The whole apparatus was cali-
washed with acetone and dried under an ambient atmosphere. brated by means of a Newport 918D Low power calibrated
Compound 8. In a 20 ml vial, 31 mg of [Au(SPh)]n photodiode sensor over the range of 190–1000 nm. The resolu-
(0.101 mmol, 1 equiv.) was mixed with 90 mg of p-HSPhCO2H tion of the system is 4 nm. The emitted light from the sample
(0.584 mmol, 6 equiv.) in 10 ml of water. The vial was closed was collected using an optical fiber connected to a Jobin-Yvon
and heated at 120 1C for 20 h. The solid was then filtered, Triax 320 monochromator equipped with a cooled CCD detec-
washed first with water and then with acetone, and dried under tor. At the entrance of the monochromator different long pass
an ambient atmosphere.
filters can be chosen in order to eliminate the excitation light.
The resolution of the detection system is 2 nm.
Materials and methods
Results and discussion
Esterification reaction
Powder X-ray diffraction (PXRD) experiments were carried out
on a Bruker D8 Advance A25 diffractometer using Cu Ka In order to study the post-functionalization of gold(I) thiophenolate-
radiation equipped with a 1-dimensional position-sensitive based compounds, the esterification of the 2D layered
detector (Bruker LynxEye). XR diffraction patterns were [Au(p-SPhCO2H)]n coordination polymer was tested first. Its
recorded between 41 and 901 (2y) with 0.021 steps and 0.5 s interlayer distance of 1.48 nm corresponds to two non-
per step (28 min for the scan). The divergence slit was fixed to interpenetrated p-SPhCO2H molecules interacting through
0.21 and the detector aperture to 189 channels (2.91).
catemeric hydrogen bonds (Fig. 1a).14 To esterify the carboxylic
The infrared spectra were obtained from a Bruker Vector 22 acid groups, the insoluble [Au(p-SPhCO2H)]n solid was stirred
FT-IR spectrometer with KBr pellets at room temperature and in a solution of methanol under reflux in the presence of
registered from 4000 to 400 cmꢁ1
.
sulphuric acid acting as a catalyst. After two days of reaction,
Thermo-gravimetric analyses (TGA) were performed with a compound 10 was isolated and new peaks on the PXRD pattern
TGA/DSC 1 STARe System from Mettler Toledo. Around 2 mg of appear with predominant 00l reflections characteristic of a
the sample was heated at a rate of 10 1C minꢁ1, in a 70 ml lamellar compound (Fig. 2a). The first peak was localized at
alumina crucible, under an air atmosphere (20 ml minꢁ1). 4.751 (2y) which corresponds to an interlamellar distance of
Fig. 2 (a) Powder X-ray diffraction patterns of the starting [Au(p-SPhCO2H)]n solid (black), compounds 10 (orange) and 1 (red) furnished from the
esterification of [Au(p-SPhCO2H)]n after 2 and 7 days of stirring, respectively. The asterisks correspond to a second lamellar phase of [Au(p-SPhCO2Me)]n.
The diagrams are compared to the simulated pattern of [Au(p-SPhCO2Me)]n (grey). (b) PXRD patterns of [Au(p-SPhCO2Na)]n (2, blue), [Au(p-SPhCO2K)]n
(3, purple) and [Au(p-SPhCO2Cs)]n (4, pink) compounds furnished from the saponification of the [Au(p-SPhCO2Me)]n solid (black).
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1.86 nm; this increase of 0.38 nm is in good accordance
with the replacement of hydrogen atoms by methyl groups.
In addition the new peaks match the reflections of the simu-
lated structure of [Au(p-SPhCO2Me)]n (Fig. 2a).15 From the
PXRD diagram of 10, it is clear that after 2 days the esterification
is not complete and the major product remains [Au(p-SPhCO2H)]n.
Therefore, the reaction time has been extended to 7 days. In
that case, [Au(p-SPhCO2Me)]n becomes the major product, but
still approximately 15% (as deduced from the PXRD pattern) of
[Au(p-SPhCO2H)]n is present (Fig. 2a). Besides, small peaks
corresponding to another lamellar compound with a first
reflection at 4.981 (2y) start to appear (o5%), which could
correspond to another [Au(p-SPhCO2Me)]n phase (Fig. 2a). The
mixture of the two acidic and esterified phases in 1 was also
confirmed by FT-IR spectroscopy (Fig. S1 and S2, ESI†). Indeed,
on the spectrum of 1, both the antisymmetric vibrations of the
carbonyl for the ester and the carboxylic acid groups are present
at 1720 and 1690 cmꢁ1, respectively. In addition, hydrogen
bonds between the acids are still present with large bands at
2555 and 2670 cmꢁ1. Different synthetic conditions have been
attempted in order to generate a complete esterification of
[Au(p-SPhCO2H)]n, but with harsher conditions the formation
of bulk gold was observed and water removal by the use of a
Dean Stark did not allow complete esterification either. This
observation indicates that [Au(p-SPhCO2Me)]n is more easily
obtained by direct synthesis from HAuCl4 and p-HSPhCO2H
in methanol, when redox reaction and esterification take
place simultaneously.15 Also the presence of hydrogen bonds
between the carboxylic acids generating a 3D network increases
the stability of [Au(p-SPhCO2H)]n. In addition, compound 1
exhibits bright yellow emission with a maximum band centered
at 660 nm (lex = 320 nm at room temperature and in the solid-
state) (Fig. S3, ESI†). This intense luminescence is related to the
compound [Au(p-SPhCO2Me)]n, which shows a quantum yield
(QY) of B70% compared to [Au(p-SPhCO2H)]n having a QY of
less than 1% at RT.14,15
Fig. 3 SEM pictures of (a) [Au(p-SPhCO2Na)]n (2) and (b) [Au(p-SPhCO2K)]n
(3) compounds issued from the different saponification reactions of
[Au(p-SPhCO2Me)]n. The scale bar represents 5 mm.
(Fig. S5 and S6, ESI†). Indeed, on the three spectra, the
antisymmetric vibrations of CO are shifted from 1720 cmꢁ1 to
1540 cmꢁ1. The small difference between the anti- and sym-
metric stretching bands of CO2 (Dn = 140 cmꢁ1) is characteristic
of cations chelated by carboxylate groups.18 The three com-
pounds present also intense and large bands of O–H stretching
due to the solvation and hydration of the samples. From SEM
pictures (Fig. 3), the crystallites of the compounds furnished
from the saponification reactions are thin plates of around
1–5 mm size for 2 and 3 corresponding to the morphology of
the starting material [Au(p-SPhCO2Me)]n, which may indicate
that their lamellar structures are isoreticular. The TGA results
show that the three compounds start to decompose from 350 1C
(Fig. S7, ESI†). In addition, compounds 2 and 3 are photolumi-
nescent showing their emission maxima at 670 and 648 nm,
respectively (Fig. 4). The brighter emission of 3 is really close to
that of the starting solid [Au(p-SPhCO2Me)]n, suggesting simi-
larities in the gold-containing inorganic layer.15
The possibility of performing esterification and saponification
reactions proves the remarkable stability of gold(I) thiophenolate-
based compounds under extreme conditions of acidic and basic
media under reflux for several days.
Exchange reaction
Saponification reactions
To gain more insights into the mechanism of post-functionalization,
ligand exchange reactions between the three structurally different
Saponification of [Au(p-SPhCO2Me)]n was carried out with
several alkali hydroxide solutions used as a base: NaOH, KOH
and CsOH. From PXRD (Fig. 2b), the saponification of the
ester-based compound with NaOH and KOH leads to new
and highly crystalline compounds [Au(p-SPhCO2Na)]n (2) and
[Au(p-SPhCO2K)]n (3) with interlamellar distances of 1.76 and
1.77 nm, respectively. In the case of [Au(p-SPhCO2Cs)]n (4), the
compound exhibits also a layered structure with an interlayer
distance of 1.93 nm, but it is poorly crystalline. The slight
increase of the interlamellar distances for the three compounds
is in accordance with the ionic radii of Na+, K+ and Cs+ (116, 152
and 181 pm, respectively) (Fig. S4, ESI†). These new interla-
mellar distances obtained after saponifications are close to the
one of [Au(p-SPhCO2Me)]n (1.86 nm) and suppose that the
ligands are not interpenetrated. From PXRD the three phases
are pure without the presence of the starting material or
bulk gold (Fig. 3). The full conversion of the ester into the
alkali carboxylate salt was also confirmed by FT-IR spectroscopy
Fig. 4 Emission spectra of [Au(p-SPhCO2Na)]n
SPhCO2K)]n 3 (purple) recorded in the solid state at room temperature
with lex = 320 nm.
2 (blue) and [Au(p-
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that this ligand exchange reaction involves a complete rearran-
gement of the atoms and implies a dissolution/recrystallization
mechanism.
The inverse reaction was also possible: when p-HSPhCO2Me
was mixed with the 1D [Au(SPh)]n solid, the layered
[Au(p-SPhCO2Me)]n compound, 6, was formed. The complete-
ness of the process was again confirmed by FT-IR with the
appearance of the characteristic ester vibration bands nas(CO2)
and ns(CO2) at 1720 and 1400 cmꢁ1, respectively (Fig. S8, ESI†).
It can be observed from the PXRD pattern that the solid 6
exhibits two lamellar phases with interlamellar distances of
1.85 and 1.76 nm (Fig. 5), where the first phase corresponds to
the reported structure of [Au(p-SPhCO2Me)]n and the second
one may be a similar structure with a different rotation of the
methyl group and/or more interpenetrated ligands. The trans-
formation from a 1D to a lamellar structure was also confirmed
by the formation of thin pellets of around 20 mm size after the
ligand exchange (Fig. 6b).
Each of the two previous solids, [Au(p-SPhCO2Me)]n and
[Au(SPh)]n, was also allowed to react with an excess of the
p-SPhCO2H ligand. In both cases the lamellar [Au(p-SPhCO2H)]n
compounds 7 and 8, respectively, were obtained. On PXRD (Fig. 5)
compound 7 exhibits low crystallinity with the presence of bulk
gold as an impurity and the first reflection corresponds to an
interlamellar distance of 1.50 nm, close to the value expected for
[Au(p-SPhCO2H)]n (1.48 nm). When the exchange reaction was
performed from [Au(SPh)]n, the crystallinity of compound 8 was
better, with an interlamellar distance of 1.48 nm as expected
for the structure of [Au(p-SPhCO2H)]n, and more importantly no
bulk gold was formed even though a slightly higher temperature
was used (120 1C instead of 100 1C) (Fig. 5). From SEM images
(Fig. 6c and d), compounds 7 and 8 can be described as small
pellets of around 1 mm in size. The presence of the carboxylic acid
groups was confirmed by FT-IR spectroscopy with nas(CO2) and
ns(CO2) at 1690 and 1400 cmꢁ1, respectively, and the formation of
hydrogen bonds between the acids with the bands at 2550 and
2670 cmꢁ1 (Fig. S8, ESI†).
Fig. 5 PXRD patterns of compounds
5
([Au(SPh)]n),
6
([Au(p-
SPhCO2Me)]n), 7 ([Au(p-SPhCO2H)]n) and 8 ([Au(p-SPhCO2H)]n) obtained
by ligand exchange reactions. The simulated PXRD diagrams of the
associated compounds are also shown.
gold(I)-phenylthiolate-based coordination polymers, [Au(p-SPhR)]n
with R = H, CO2H and CO2Me, were carried out (Fig. 1).
For this purpose, an excess of an incoming thiol ligand was
used (p-HSPhR with R = H, CO2H and CO2Me). When the
lamellar [Au(p-SPhCO2Me)]n compound was mixed with thio-
phenol, the formation of a crystalline compound, 5, was
observed via PXRD, with a diagram corresponding to the
structure of [Au(SPh)]n with doubly interpenetrated helical
Au–S chains (Fig. 5). The formation of this phase was confirmed
by SEM pictures, showing that the pellets of the starting
materials are transformed into long curved fibers (Fig. 6a) in
good accordance with the 1D structure of [Au(SPh)]n.19 The
complete ligand exchange and purity of compound 5 were also
confirmed by FT-IR showing the disappearance of the CO band
of the ester (Fig. S8, ESI†) and the expected gold content
obtained from the decomposition of the organic part during
TGA (Au calculated: 64.3%, measured: 63.1%) (Fig. S9, ESI†).
The transformation of a 2D CP into a 1D CP clearly points out
In addition, compounds 5 and 6 exhibit photoemission
centered at 684 and 648 nm at RT, corresponding to the
luminescence of [Au(SPh)]n and [Au(p-SPhCO2Me)]n, respec-
tively (Fig. S10, ESI†), while 7 and 8 are only weakly luminescent
at RT like [Au(p-SPhCO2H)]n. These photoluminescence proper-
ties confirm the success of the ligand exchange reactions and
the dissolution–recrystallization mechanism.
Conversely, when starting from the [Au(p-SPhCO2H)]n solid
with an excess of HSPh or p-HSPhCO2Me ligands, no transfor-
mation was observed. This suggests again that the hydrogen
bonds between the carboxylic acid functions are responsible for
the increased stability of this gold thiolate compound and
prevent ligand exchange reactions through this mechanism.
Conclusions
This study shows that the post-functionalisation approach by
either esterification or saponification reactions is possible on
Fig. 6 SEM pictures of compounds 5 (a), 6 (b), 7 (c) and 8 (d) obtained by
ligand exchange reactions.
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O. Lopez-Acevedo, H. Hakkinen and R. W. Murray, J. Phys.
Chem. C, 2010, 114, 8276; (c) A. Fernando and C. M. Aikens,
J. Phys. Chem. C, 2015, 119, 20179.
gold(I) phenylthiolate coordination polymers. The ligand
exchange strategy shows that it implies a complete rearrangement
of the gold thiolate network and proves that the mechanism
involves a dissolution–recrystallization process. Additional experi-
ments, such as in situ SAXS or NMR, would provide an in-depth
understanding of the mechanisms and provide evidence on
whether the ligand exchange occurs before or after the CP
dissociation or if another process is involved.20 In addition, this
work highlights that the structure of gold thiolate compounds is
highly dependent on the functionalisation of the organic ligands
and that weak interactions such as hydrogen bonds, C–Hꢀꢀꢀp
and aurophilic interactions represent the driving forces for the
self-assembly.
¨
8 (a) C. L. Heinecke, T. W. Ni, S. Malola, V. Makinen,
¨
O. A. Wong, H. Hakkinen and C. J. Ackerson, J. Am. Chem.
Soc., 2012, 134, 13316; (b) T. W. Ni, M. A. Tofanelli,
B. D. Phillips and C. J. Ackerson, Inorg. Chem., 2014,
53, 6500; (c) Y. Niihori, Y. Kikuchi, A. Kato, M. Matsuzaki
and Y. Negishi, ACS Nano, 2015, 9, 9347.
9 (a) C. Zeng, C. Liu, Y. Pei and R. Jin, ACS Nano, 2013,
7, 6138; (b) Y. Li, R. Juarez-Mosqueda, Y. Song, Y. Zhang,
J. Chai, G. Mpourmpakis and R. Jin, Nanoscale, 2020,
12, 9423.
10 C. Zeng, T. Li, A. Das, N. L. Rosi and R. Jin, J. Am. Chem. Soc.,
2013, 135, 10011.
Conflicts of interest
11 P. R. Nimmala, S. Theivendran, G. Barcaro, L. Sementa,
C. Kumara, V. R. Jupally, E. Apra, M. Stener, A. Fortunelli
and A. Dass, J. Phys. Chem. Lett., 2015, 6, 2134.
12 O. Veselska and A. Demessence, Coord. Chem. Rev., 2018,
355, 240.
There are no conflicts to declare.
Acknowledgements
13 S. Li, Y. Yu, J. Liu, S. Xu, S. Zhang, M. Li and S. X.-A. Zhang,
Chem. – Asian J., 2019, 14, 2155.
14 O. Veselska, L. Okhrimenko, N. Guillou, D. Podbevsek,
G. Ledoux, C. Dujardin, M. Monge, D. M. Chevrier,
R. Yang, P. Zhang, A. Fateeva and A. Demessence,
J. Mater. Chem. C, 2017, 5, 9843.
The authors acknowledge the CTm (Centre Technologique
des Microstructures) for providing the scanning electron micro-
scope. AD thanks the Agence Nationale pour la Recherche for
the financial support (FULOR project ANR-13-JS08-0005-01 and
MEMOL project ANR-16-JTIC-0004-01).
ˇ
15 C. Lavenn, N. Guillou, M. Monge, D. Podbevsek, G. Ledoux,
Notes and references
A. Fateeva and A. Demessence, Chem. Commun., 2016,
52, 9063.
16 C. Lavenn, L. Okhrimenko, N. Guillou, M. Monge, G. Ledoux,
C. Dujardin, R. Chiriac, A. Fateeva and A. Demessence,
J. Mater. Chem. C, 2015, 3, 4115.
17 A. Rullo, A. A. Beharry, R. F. Gomez-Biagi, X. Zhao and
M. Nitz, ChemBioChem, 2012, 13, 783.
18 K. Nakamoto, Infrared and Raman Spectra of Inorganic and
Coordination Compounds, John Wiley & Sons, Inc., Hoboken,
New Jersey, USA, 2008.
19 (a) T. Tsuruoka, T. Ohhashi, J. Watanabe, R. Yamada, S. Hirao,
Y. Takashima, A. Demessence, S. Vaidya, O. Veselska,
A. Fateeva and K. Akamatsu, Cryst. Growth Des., 2020,
20, 1961; (b) S. Vaidya, O. Veselska, A. Zhadan, M. Daniel,
G. Ledoux, A. Fateeva, T. Tsuruoka and A. Demessence,
J. Mater. Chem. C, 2020, 8, 8018.
1 (a) C. Sanchez, P. Belleville, M. Popall and L. Nicole, Chem.
Soc. Rev., 2011, 40, 696; (b) C. Sanchez, K. J. Shea and
S. Kitagawa, Chem. Soc. Rev., 2011, 40, 471.
2 P. M. Tiwari, K. Vig, V. A. Dennis and S. R. Singh, Nanomaterials,
2011, 1, 31.
3 P. Deria, J. E. Mondloch, O. Karagiaridi, W. Bury, J. T. Hupp
and O. K. Farha, Chem. Soc. Rev., 2014, 43, 5896.
4 (a) A. Demessence, G. Rogez and P. Rabu, Chem. Mater.,
2006, 18, 3005; (b) M. Kim, J. F. Cahill, H. Fei, K. A. Prather
and S. M. Cohen, J. Am. Chem. Soc., 2012, 134, 18082;
(c) Y. Lin, C. Kong and L. Chen, RSC Adv., 2016, 6, 32598.
5 Y. He, J. Shang, Q. Gu, G. Li, J. Li, R. Singh, P. Xiao and
P. A. Webley, Chem. Commun., 2015, 51, 14716.
6 E. S. Shibu, M. A. Habeeb Muhammed, T. Tsukuda and
T. Pradeep, J. Phys. Chem. C, 2008, 112, 12168.
7 (a) R. Guo, Y. Song, G. L. Wang and R. W. Murray, J. Am. 20 M. J. Van Vleet, T. Weng, X. Li and J. R. Schmidt, Chem. Rev.,
Chem. Soc., 2005, 127, 2752; (b) J. F. Parker, K. A. Kacprzak, 2018, 118, 3681.
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