Solid-State C-S Coupling in Nickel Organochalcogenide Frameworks as a Route to Hierarchical Structure Transfer to Binary Nanomaterials

Article abstract of DOI:10.1021/acs.inorgchem.0c01352

In this work, the transfer of the flexible and easily tunable hierarchical structure of nickel organochalcogenides to different binary Ni-based nanomaterials via selective coupling of organic units was developed. We suggested the use of substituted aryl groups in organosulfur ligands (SAr) as traceless structure-inducing units to prepare nanostructured materials. At the first step, it was shown that the slight variation of the type of SAr units and synthetic procedures allowed us to obtain nickel thiolates [Ni(SAr)2]n with diverse morphologies after a self-assembly process in solution. This feature opened the way for the synthesis of different nanomaterials from a single type of precursor using the phenomenon of direct transfer of morphology. This study revealed that various nickel thiolates undergo selective C-S coupling under high-temperature conditions with the formation of highly demanding nanostructured NiS particles and corresponding diaryl sulfides. The in situ oxidation of the formed nickel sulfide in the case of reaction in an air atmosphere provided another type of valuable nanomaterial, nickel oxide. The high selectivity of the transformation allowed the preservation of the initial organochalcogenide morphologies in the resulting products.

Full text of DOI:10.1021/acs.inorgchem.0c01352

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Article
Solid-State C−S Coupling in Nickel Organochalcogenide
Frameworks as a Route to Hierarchical Structure Transfer to Binary
Nanomaterials
Alexey S. Kashin, Alexey S. Galushko, Evgeniya S. Degtyareva, and Valentine P. Ananikov*
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ABSTRACT: In this work, the transfer of the flexible and easily
tunable hierarchical structure of nickel organochalcogenides to
different binary Ni-based nanomaterials via selective coupling of
organic units was developed. We suggested the use of substituted
aryl groups in organosulfur ligands (SAr) as traceless structure-
inducing units to prepare nanostructured materials. At the first step,
it was shown that the slight variation of the type of SAr units and
synthetic procedures allowed us to obtain nickel thiolates
[Ni(SAr)2]n with diverse morphologies after a self-assembly process
in solution. This feature opened the way for the synthesis of
different nanomaterials from a single type of precursor using the
phenomenon of direct transfer of morphology. This study revealed that various nickel thiolates undergo selective C−S coupling
under high-temperature conditions with the formation of highly demanding nanostructured NiS particles and corresponding diaryl
sulfides. The in situ oxidation of the formed nickel sulfide in the case of reaction in an air atmosphere provided another type of
valuable nanomaterial, nickel oxide. The high selectivity of the transformation allowed the preservation of the initial
organochalcogenide morphologies in the resulting products.
stability of the metal−sulfur core, which makes the synthesis of
these compounds simple and easily reproducible. However,
chemical transformations involving coordination polymers of
metal thiolates usually proceed on defects or low-coordination
surface sites21,22 and often include leaching of small thiolate
species in solution.18−20 Therefore, the preferable manner of
core group activation is destruction of polymeric structure,
which seriously complicates the modification of these materials
without alteration of their micro- and nanoscale properties.
Previously published papers devoted to the synthesis of
nickel thiolates18,28 have outlined the general tendencies in the
synthesis of nanostructured coordination polymers. It was
shown that the nature of the substituents in the organic groups
of nickel thiolates was responsible for the size and shape of the
resulting thiolate particles. At the same time, the question
about the possibility of preparing coordination polymers with
the same composition and different structures was only slightly
elucidated. Therefore, during the first step of this study, we
decided to optimize the nickel thiolate synthesis conditions
INTRODUCTION
■
Nanostructured inorganic architectures on the basis of
transition metal sulfides made an outstanding contribution to
materials science. Their unique electronic properties and wide
possibilities for tuning the morphology and composition of
nanocrystals allowed the creation of efficient photo- and
electrocatalysts,1,2 energy storage materials,3 sensors and
biological labels,4−6 light-emitting devices,7−10 room-temper-
ature ferromagnetics,11 and high-capacity materials for lithium,
sodium, and magnesium ion batteries.12−14
Introduction of organic moieties in the transition metal
sulfides opened up new horizons for the preparation of
functional materials. For example, the high redox activity of
organic dithiolato ligands attached to the transition metal
atoms can be employed in the production of hydrogen via
photocatalytic hydrogen evolution reaction.15 Metal clusters
with thiolate ligands are promising materials for optoelectronic
and photovoltaic devices.16 Polymeric thiolate structures based
on transition metal units bound by organic sulfur-containing
bridges not only possessed pronounced band-like electronic
properties17 but also demonstrated excellent performance in
catalytic C−S cross-coupling reactions18,19 and heterofunction-
alization of unsaturated carbon−carbon bonds,20−22 which
form the base of modern organosulfur chemistry.23−27 The key
feature associated with the structure of polymeric thiolates is
the high affinity of sulfur atoms for metal centers and the
Received: May 8, 2020
https://dx.doi.org/10.1021/acs.inorgchem.0c01352
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and to find the possible ways to prepare particles with different
morphologies.
compounds with different substituents in the aromatic rings
(Figure 1).
In this work, we describe the high-temperature solid-state
C−S coupling reaction in nickel thiolate coordination
polymers [Ni(SAr)2]n, which opened the way for the direct
transfer of morphology from nickel thiolates to different nickel-
based nanomaterials during temperature-induced modification.
It was revealed that under an inert atmosphere at temperatures
of approximately 300−700 °C, nickel thiolates selectively
decompose with the formation of corresponding diaryl sulfide
and nanosized nickel sulfide. Tuning of the reaction
atmosphere allows us to widen the scope of the transformation.
Nanosized nickel oxide can be readily synthesized from
[Ni(SAr)2]n under an air atmosphere by in situ oxidation of
the formed nickel sulfide. Retention of the initial thiolate
morphologies in the resulting nickel-containing particles clearly
demonstrates the preservation of the Ni−S core structure
during the C−S coupling. The studies of temperature-induced
reactions were preceded with the optimization of the nickel
thiolate preparation method, which allowed us to propose the
general procedure for the preparation of nanomaterials with
different morphologies from a single set of reagents. The
discovered process opened the way for selective modification
of sulfur-containing metal−organic architectures and formed
the basis for the new method for the synthesis of structurally
defined nickel oxides and sulfides, which can find numerous
applications in the production of solar cells, batteries,
supercapacitors, and catalysts.29−35
In the case of the unsubstituted nickel thiophenolate, the
XRD pattern consisted of several broad peaks, which indicated
the formation of a highly dispersed phase. Highly ordered
structures featured by several narrow intense peaks in
diffractogtams were detected for p-NH2- and p-Cl-substituted
thiolates. In the first case, the high crystallinity was caused by
additional coordination of amino groups to nickel atoms upon
formation of the framework. The formation of the same
ordered structure in the case of the p-Cl-substituted compound
clearly demonstrated that the chains of coordination polymers
can form such structures even in the absence of strongly
coordinating atoms. In contrast, the change of the p-Cl
substituent to p-Br and the p-NH2 group to p-OH led to the
formation of the mixture of different phases that make
obtained materials less promising as starting compounds for
the synthesis of nanostructured architectures. Comparison of
the XRD patterns for nickel thiolates with the XRD pattern for
crystalline Ni(acac)2 clearly demonstrated the complete
conversion of the starting material in all cases. On the basis
of diffraction data and previously published electron
microscopy measurements,18 the nickel thiolate with p-Cl
groups in the aromatic rings was chosen as a model compound
for the optimization of the synthesis conditions.
In the model system, [Ni(S-p-ClC6H4)2]n was prepared
from the nickel acetylacetonate and the corresponding thiol
with the use of different solvents and thiol loadings (Table 1).
All reactions were carried out at room temperature.
RESULTS AND DISCUSSION
During the first step of optimization, the different quantities
of thiol were used for the reaction to determine the ratio
between the nickel precursor and the thiol required for the
preparation of nickel thiolate with a high yield and a regular
morphology. The stoichiometric ratio (1:2) and 1:3 and 1:5
thiol loadings were employed (Table 1, entries 1−3,
respectively). In all cases, the reaction proceeded smoothly
and the product with the desired morphology was obtained,
which was verified by electron microscopy (see Figures S1−
S6); however, an at least 1.5-fold excess of thiol was required
to reach product yields of approximately 90−95%. The right
choice of solvent usually plays an important role in the
synthesis of nanostructured materials, because the nature of
the medium determines the stability of the disperse phase in
the colloidal system and controls the regularities of growth and
self-assembly at the solid−liquid interface. The screening of
solvents in the studied synthesis of nanostructured materials
revealed the key role of the medium in the nickel-containing
species assembly. The best yields of the product (78−95%)
were obtained with the use of low-polar organic solvents
(Table 1, entries 3−5), and a comparable reaction system
efficiency was observed in the case of some oxygen-containing
liquids like THF, ethyl acetate, and methanol (Table 1, entries
6−8, respectively). Application of nonpolar hydrocarbons like
toluene allowed us to isolate the product in satisfactory 57%
yield (Table 1, entry 9), whereas the use of DMF, DMSO, or
acetonitrile resulted in poor thiolate yields of <40% (Table 1,
entries 10−12). It is worth mentioning that regardless of the
nature of employed media the substitution reactions between
nickel acetylacetonate and thiol took place immediately after
mixing of the reagents, but at the same time, the rate of self-
assembly of soluble particles differed notably. This feature of
the employed system was responsible not only for the product
yield but also for the synthesized particle morphology, which
■
To choose the appropriate model system for the reaction
optimization, a number of nickel thiolates were synthesized
and subjected to X-ray powder diffraction analysis (XRD) to
find the structures with the highest order among the prepared
particles. The desired compounds were obtained by the
reaction of nickel acetylacetonate with the corresponding thiol
in solution (Scheme 1). The studied sequential trans-
Scheme 1. Stepwise Formation of Nickel Thiolate Particles
from Soluble Nickel Salt and the Corresponding Aromatic
Thiol
formations included ligand substitution, polymeric chain
growth, and assembly of nanostructured materials, which
resulted in all cases in the formation of solid products with
almost quantitative yields. The morphologies of the isolated
particles were fully consistent with the published data.18
After the synthesis, nickel-containing coordination polymers
were analyzed by XRD, which demonstrated the considerable
variations in the crystallinity and degree of ordering for the
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Figure 1. X-ray powder diffraction data for nickel thiolates [Ni(SAr)2]n with different substituents in the aromatic rings. The diffractogram of the
Ni(acac)2 control sample is also provided.
Table 1. Optimization of the Conditions for Nickel Thiolate
Nanostructured Material Synthesis
were detected by electron microscopy. SEM measurements
were supplemented by X-ray powder diffraction studies to
analyze the phase composition of the prepared materials.
Analysis of the obtained XRD patterns (see Figure S7) showed
that the samples isolated from chlorinated solvents had a
similar phase composition, but in some other cases (for
example, in the case of tetrahydrofuran and DMSO), the
notable amounts of impurities were detected along with the
main phase. Therefore, as a summary of the findings described
above, the synthesis in chlorinated solvents is the most
promising method for the preparation of nickel thiolates
because it allows the preparation of the well-structured
materials with high yields and purities.
In the next step, the chemical properties of prepared
coordination polymers were studied with an eye on the
synthesis of nickel-containing nanostructured materials using
thiolate particles as a template. The emphasis was placed on
the development of selective methods for temperature-induced
modification in the solid phase. For the evaluation of the
optimal reaction conditions, a number of nickel thiolates
synthesized from Ni(acac)2 in CH2Cl2 were subjected to
thermogravimetric analysis (TGA), which has revealed the
features of the behavior of the prepared materials at
temperatures of ≤1200 °C in an argon atmosphere. The first
derivatives of TGA curves clearly reflected the difference in the
rate of nickel thiolate decomposition and in the temperature
profiles of the reactions depending on the nature of
substituents in the aromatic rings (Figure 3A). In the case of
the unsubstituted thiophenolate, the reaction took place at a
relatively low temperature and had the highest rate among all
carried out processes. The maximum rate was observed at 273
°C. It can be explained by the high volatility of the organic
products of the reaction, which can be easily removed from the
reaction mixture even upon moderate heating. In the presence
of heavier substituents in organic fragments of nickel
coordination polymers, an increase in decomposition temper-
ature was observed. Therefore, the maximum decomposition
rate was observed at 309 or 375 °C for p-Cl- or p-OH-
substituted thiolates, respectively. The profiles of the differ-
a
entry
Ni(acac)2:ArSH
solvent
CH2Cl2
CH2Cl2
CH2Cl2
DCE
CHCl3
THF
ethyl acetate
CH3OH
toluene
DMF
yield (%)
1
2
3
4
5
6
7
8
1:2
1:3
1:5
1:5
1:5
1:5
1:5
1:5
1:5
1:5
1:5
1:5
79
91
95
82
78
78
76
68
57
39
20
3
9
10
11
12
DMSO
CH3CN
a
Based on the weight of the isolated precipitate.
was clearly shown by electron microscopy (SEM) analysis of
the prepared materials (Figure 2).
Particles isolated from chlorinated solvents and tetrahy-
drofuran appeared as well-ordered microsized aggregates of
nanoscale two-dimensional nickel thiolate sheets. The size of
aggregates varied in the range of 5−10 μm, and the type of
aggregation was determined by the nature of the solvent.
Meshy structures with the minor amount of lamellar inclusions
were detected in the case of methylene chloride (Figure 2A).
The stacks forming biconcave microparticles were obtained
after the reaction in chloroform (Figure 2B). Synthesis in 1,2-
dichloroethane (DCE) resulted in fan-shaped aggregates
(Figure 2C). Holey round-shaped particles precipitated from
the tetrahydrofuran (Figure 2D). The microcrystalline product
with the size of individual crystals of ∼1 μm was formed in the
case of the use of DMSO as a solvent (Figure 2E). Dense
aggregates without a specific morphology were obtained in
DMF, acetonitrile, and methanol (Figure 2F). For other
solvents, the mixtures of particles with different morphologies
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Figure 2. SEM images of the [Ni(S-p-ClC6H4)2]n particles prepared in different solvents: (A) CH2Cl2, (B) CHCl3, (C) DCE, (D) THF, (E)
DMSO, and (F) CH3OH.
Figure 3. (A) DTG curves for nickel thiolates with various substituents in aromatic rings. (B, C) Energy dispersive X-ray (EDX) spectra for the
initial nickel thiolates (colored blue) and samples after TGA (colored red) in the case of thiolates containing (B) p-Br and (C) p-Cl substituents.
ential TG (DTG) curves in the case of these substituents were
similar to the DTG curves for nickel thiophenolate, although
their broadening and the appearance of additional features
were observed, which indicates the stepwise removal of organic
residues. This effect was especially pronounced in the case of
the p-Br-substituted compound. The DTG curve for this
sample contained a series of extrema in a wide temperature
range from 100 to 700 °C. A similar multistage decomposition
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is observed in the case of the amino group as a substituent. To
establish the changes in the chemical composition of nickel
thiolates after thermal treatment, samples were analyzed before
and after TGA using the X-ray microanalysis technique (EDX),
which showed an increase in the weight fraction of sulfur and
nickel in the sample, which suggests that nickel sulfide is
predominantly formed as a decomposition product of nickel
thiolates in an inert atmosphere. A comparison of the spectra
of the initial nickel thiolates containing p-Br and p-Cl
substituents with the spectra of their decomposition products
allowed one to conclude that the organic fragments were
completely removed during the thiolate treatment. Peaks
corresponding to bromine and chlorine atoms, for example, in
benzene rings, were not observed in the spectra of the treated
samples, although they were present as intense peaks in the
spectra of the initial coordination polymers with p-Br (Figure
3B) and p-Cl (Figure 3C) substituents. Thus, as a result of
TGA, the key information was obtained for the creation of
temperature programs for the scaling of nickel thiolate
conversion.
On the basis of TGA data, the optimal temperature
programs were proposed for the further study of the process.
For the reaction in an argon atmosphere, the working
temperature was chosen to match the conditions required for
almost all studied materials except strongly deviating nickel
thiolate with a p-Br substituent. Therefore, in the general
procedure reactions were carried out at 500 °C; for [Ni(S-p-
BrC6H4)2]n, the temperature was increased to 800 °C (Scheme
2). At the same time, starting from 200 °C, the heating rate
Synthesis was performed in the air flow at different
temperatures from 600 to 800 °C (Scheme 2). All reactions
proceeded smoothly with the formation of NiO as a main
product, which was confirmed by X-ray microanalysis (see
Figures S13−S19) and comparison of practical and theoretical
weight losses (Scheme 2). However, the use of relatively low
reaction temperatures led to the appearance of the sulfide
product in the obtained material. In the case of [Ni(S-p-
ClC6H4)2]n at 600 °C, approximately 2−3% of NiS was formed
as a side product. The quantity of the impurities can be
decreased to trace amounts of <1% by increasing the
temperature to 700−800 °C (see Figures S13−S15). It is
important to mention that for all temperatures the mass loss
values for [Ni(S-p-ClC6H4)2]n were almost identical and
perfectly matched the theoretical value (Scheme 2).
To establish the main reaction pathway leading to the
formation of nickel sulfide from nickel thiolate coordination
polymers in an inert atmosphere, GC-MS analysis of the
products deposited from the gas phase after the thermal
decomposition of [Ni(SAr)2]n particles was carried out. For all
tested compounds, the formation of the corresponding diaryl
sulfide Ar2S via C−S coupling was observed. In the case of
unsubstituted nickel thiophenolate and nickel thiolates with p-
Cl and p-NH2 substituents, the disulfide product was the only
organic compound detected in a notable amount (see Figures
S20−S25). The picture was more complicated for the thiolate
bearing p-OH groups. As in the previous cases, two organic
groups in thiolate underwent C−S coupling, which expectedly
gave the diaryl sulfide product; however, the simultaneous
appearance of phenol and 4-mercaptophenol was clearly shown
by GC-MS (see Figures S26−S29). Possibly, after C−S
coupling, under high-temperature conditions the free phenolic
moieties partially reduced the carbon−sulfur bonds in the
product with formation of new aromatic species. The increase
in the reaction temperature to 800 °C in the case of p-Br-
substituted nickel thiolate led to the facile cleavage of carbon−
sulfur and carbon−bromine bonds and the appearance in
addition to diaryl sulfide of a few more initially unexpected
organic products as 1,4-dibromobenzene and 4′-bromo-4-
mercaptobiphenyl (see Figures S30−S33). On the basis of the
observations made, one can conclude that despite the existence
of some side transformations, the solid-phase C−S coupling is
a predominant process occurring during nickel thiolate thermal
treatment, which is in excellent agreement with the formal
stoichiometry of the reaction.
The morphology of the solid materials obtained in an argon
atmosphere was examined by SEM, which has shown that the
most promising regular structures were formed from [Ni(S-p-
ClC6H4)2]n as a starting compound (Figure 4A). The
homogeneous structure with no specific morphology was
formed in the case of unsubstituted nickel thiophenolate; in
the case of p-Br-substituted thiolate, the need to increase the
reaction temperature to 800 °C led to the partial melting of the
product and, accordingly, to the loss of the initial structure (see
Figure S34). Due to the removal of organic fragments from the
particles of nickel thiolates, their size decreased, on average,
from 500 to 200−300 nm in the case of nickel thiophenolate
(see Figure S34) and from 10−20 to 5−10 μm in the case of p-
Cl-substituted nickel thiolate (Figure 4A). It is noteworthy that
in both cases, after the reaction the microparticles showed a
clearly defined nanostructure, which was not typical for the
initial thiolates. From the SEM data, one can clearly see the
structural subunit of the prepared nanoparticles with a size of
Scheme 2. Temperature-Induced Modification of Nickel
a
Thiolates in an Argon or an Air Atmosphere
a
The main products proposed on the basis of X-ray microanalysis are
shown. The weight loss percentage is provided for each experiment.
The theoretical weight loss percentage (calculated for NiS or NiO
formation in the reaction in an argon or air atmosphere, respectively)
is given in parentheses.
was slowed to exclude the distortion of the structure of the
resulting materials during the rapid decomposition of nickel
thiolates. As in the case of the TGA experiment, calculations
based on the material weight loss (Scheme 2) as well as X-ray
microanalysis of the obtained samples (see Figures S8−S12)
confirmed the formation of nickel sulfide, which, however,
contained notable amounts of oxidized NiSxOy species due to
the reaction of the product surface with oxygen impurities in
the reaction chamber or due to product degradation during the
storage.
The facile oxidation of thiolate decomposition products even
with oxygen traces inspired us to modify the procedure and to
carry out the reaction in air to spread the proposed
methodology on the synthesis of nanosized nickel oxide.
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Figure 4. SEM images of the nanomaterials obtained after temperature-induced modification of nickel thiolate [Ni(S-p-ClC6H4)2]n in (A) an argon
atmosphere at 500 °C and in an air atmosphere at (B) 600 °C and (C) 800 °C. XPS spectra in the Ni 2p3/2 region for the corresponding nickel-
based nanomaterials (D−F, respectively).
approximately 20−30 nm. The porous material was synthe-
sized from a hydroxy-substituted nickel coordination polymer;
however, a high degree of aggregation of particles in the
starting compound led to their sticking in the final product
with formation of the sponge with an irregular structure. Upon
conversion of the amino-substituted compound, the surface of
the obtained material was notably smoothed, perhaps, by
minor amounts of nonvolatile organic side products (see
Figure S35). Electron microscopy analysis of the materials
synthesized in an air flow revealed the trends in the nickel
thiolate particles morphology alteration during the reaction
under oxidative conditions. The microlevel morphology of the
particles prepared from p-Cl- and p-Br-substituted nickel
thiolates was generally preserved. The average size of the
particles was approximately 5−10 μm for nickel oxide prepared
from p-Cl-substituted nickel thiolate at 600 °C (Figure 4B),
700 °C (see Figure S36), and 800 °C (Figure 4C) and 2−4 μm
for NiO prepared from [Ni(S-p-BrC6H4)2]n at 800 °C (see
Figure S37). The synthesis at a relatively low temperature of
600 °C led to the appearance of the nanostructure of the
product with a subunit size of approximately 20−30 nm.
Reactions at higher temperatures resulted in the increase in
subunit size due to the coalescence of the formed nickel-
containing species. At 700 °C, this parameter reached 30−50
nm and at 800 °C increased to several hundreds of
nanometers. Large particles reflecting the initial crystalline
structure were detected in the case of [Ni(S-p-NH2C6H4)2]n
thermolysis at 800 °C (see Figure S37). Nevertheless, these
particles consisted of well-ordered subunits with sizes of
approximately 50−200 nm. The thermal treatment of nickel
thiophenolate and p-OH-substituted nickel thiolate at the same
temperature resulted in the formation of poorly ordered
materials with less expressed nanostructure (see Figure S38).
To determine the chemical state of nickel atoms in the
resulting products, the prepared materials were analyzed by X-
ray photoelectron spectroscopy (XPS). The typical spectrum
for nanomaterials synthesized in an inert argon atmosphere
consisted of three peaks in the Ni 2p3/2 region (Figure 4D; see
also Figures S39−S41). According to the literature data,36−38
the main peaks observed at 853.1−853.3 eV as well as small
satellites that appeared at 860.3−860.9 eV were attributed to
the nickel sulfide. In addition to NiS, the partially oxidized
form of this material was detected on the sample surface. The
values of Ni 2p3/2 binding energies for oxygen-containing
species were 855.2−855.5 eV, which allowed us to propose
their sulfate-like structure36 with a formal elemental
composition of NiSxOy. It is important to mention that the
appearance of this type of impurities on the surface is common
for the nickel sulfide nanomaterials exposed to an air
atmosphere.38 XPS data for the products prepared in an air
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a
Scheme 3. Developed Approach for the Hierarchical Structure Transfer to Ni-Based Binary Nanomaterials
a
(A) Synthesis of the nickel thiolate template with a unique morphology stabilized and controlled by organic SAr groups. (B) Structure transfer to
binary nanomaterials via C−S coupling reaction accompanied by (C) formation of aryl sulfide, which can be recycled.
atmosphere at 600 °C (Figure 4E) and 800 °C (Figure 4F, see
also Figures S42−S45) confirmed the formation of nickel oxide
as it was proposed on the basis of EDX analysis and weight loss
measurements. In all cases, the XPS spectra in the Ni 2p3/2
region had a complex structure with three main lines. The pairs
of peaks at 853.7−853.9 and 855.4−855.8 eV were attributed
to the split Ni 2p3/2 line of NiO, whereas the latter
components with maxima at 860.8−861.2 and 862.1−866.3
eV (low-intensity component) were assigned to the Ni 2p3/2
satellite of NiO.36,39,40 It is important to mention that the fine
structure of the typical nickel oxide XPS spectrum can be even
more complicated, and a number of additional components
can be extracted during precise fitting.39 As a result of the
current stage, the scope of the reaction was expanded to
nanosized nickel oxide synthesis with a slight modification of
the experimental procedure.
Taking into account the foregoing, one can conclude that
nickel thiolates [Ni(SAr)2]n with different p-substituents can
be used as precursors and templates for the preparation of
nickel-containing binary nanomaterials. It is essentially in this
context that the variation of the substituent can significantly
change the morphology of the initial thiolate and final product.
For example, unsubstituted nickel thiophenolate and nickel
thiolate with hydroxyl groups appeared as aggregates of small
particles without a specific shape. These compounds were
readily transformed to the nanosized binary materials, which,
however, had only one level of organization in full accordance
with the stated principle of morphology transfer. The similar
behavior was observed for the p-NH2-substituted nickel
thiolate. Additional coordination of amino groups to nickel
atoms allowed generation of the coordination polymer with
more regular structure, but no extra structural levels were
created at microscale; therefore, the morphology transfer
resulted in the formation of simply aggregated nanosized
particles. The picture was completely different in the case of
halogen-containing nickel thiolates, which can be characterized
as compounds with an easily tunable and diverse morphology.
The use of these compounds for annealing opened the way for
the creation of nanomaterials with a complex hierarchical
structure, which was the main goal of this study. Possibly,
electron-withdrawing properties of chlorine and bromine
substituents driving the charge redistribution in the aromatic
rings as well as their potential for additional coordination
contribute to noncovalent interactions of the π−π stacking
type between aromatic moieties, which stabilize the hier-
archical structure of nickel thiolates.
The substituent effect was further studied on an additional
set of nickel thiolates. First, the influence of the substituent
position in the aromatic rings on the morphology of nickel
thiolates was evaluated. For this purpose, thiolates with o-Cl,
m-Cl, o-Br, and m-Br substituents were synthesized and their
morphology was studied by electron microscopy (see Figure
S46) and compared with the morphology of p-substituted
analogues. It was established that a strong steric effect resulted
in the complete disappearance of regular structure in the case
of o-substituted thiolates and a notable morphology alteration
in the case of m-substituted thiolates. The formation of
aggregated flakes with sizes of approximately 1 μm was
detected for [Ni(S-m-ClC6H4)2]n, and in the case of [Ni(S-m-
BrC6H4)2]n, small particles approximately 100−300 nm in
diameter were observed. Therefore, the spatial arrangement of
substituents is an important factor that is responsible for the
thiolate hierarchical structure stabilization. An interesting
observation was made for the nickel thiolate synthesized
from 2-aminothiophenol. The resulting compound appeared as
submicrocrystalline powder with individual crystal sizes
approximately 200−300 nm (see Figure S46) and had a light
yellow-green color atypical for [Ni(SAr)2]n coordination
polymers. The prepared material was characterized earlier by
X-ray absorption spectrocsopy,18 and its properties can be
explained by formation of a monomeric crystalline complex
with a chelating SAr ligand. Finally, two dithiols, 1,4-
benzenedithiol and 4,4′-dimercaptobiphenyl, were used for
nickel thiolate synthesis. Depending on the ligand structure,
two completely different types of morphology were observed
(see Figure S46). Particles obtained with the use of 1,4-
benzenedithiol had diameters of approximately 50−100 nm
and were merged into 500−700 nm aggregates. In contrast,
synthesis on the basis of 4,4′-dimercaptobiphenyl gave
perfectly shaped spherical particles with diameters of 300−
400 nm. It is noteworthy that the Ni:S ratio determined by
EDX analysis (see Figures S47 and S48) was approximately 1:4
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for thiolate prepared form 1,4-benzenedithiol and approx-
imately 1:3 for thiolate prepared form 4,4′-dimercaptobiphen-
yl, which indicated the passive role of the second sulfur atom in
the association of the Ni(SAr)2 units in the first case and
partial implementation of linker-type behavior of sulfur-
containing ligands in the second case. It is worth mentioning
that the latter type of growth favored the formation of particles
with a regular morphology. All synthesized thiolates were used
as starting materials for annealing in an air atmosphere at 800
°C. The reaction proceeded smoothly with the formation of
aggregated nickel oxide particles with average sizes of
approximately 100−200 nm, which was demonstrated by
electron microscopy (see Figure S49) and X-ray microanalysis
(see Figures S50−S56). No strong correlations between
structures of initial thiolates and prepared NiO particles were
observed. Thereby, the crucial role in the formation of stable
and tunable hierarchical structure of nickel thiolate, which can
be easily transferred to binary nanomaterials, is played by
noncovalent interactions between aromatic moieties. These
forces can be adjusted by variation of the initial synthesis
conditions of the materials. At the same time, they are strong
enough to form the unique structure of the coordination
polymer and particularly the Ni−S core, and the spatial
separation of core atoms and side aromatic groups allows the
removal of organic substituents without initial morphology
distortion.
anticipate that the approach developed here can also be used
to prepare a number of other metal chalcogenides.
EXPERIMENTAL SECTION
■
General Considerations. Nickel acetylacetonate, thiophenol,
substituted aromatic thiols, and all used solvents were purchased
from commercial sources.
X-ray powder diffraction (XRPD) studies were carried out at the X-
ray structural analysis beamline (XSA)43 of the Kurchatov
Synchrotron Radiation Source (National Research Center Kurchatov
Institute) with the use of monochromatic radiation with a wavelength
of 0.8 Å (photon energy of 15498 eV). The two-dimensional
diffraction patterns were collected by a Rayonix SX165 detector and
further integrated into the standard form of I(2θ) dependence using
Dionis software.44
XPS spectra were recorded on an ESCA unit of the NanoPES
beamline of the Kurchatov Synchrotron Radiation Source (National
Research Center Kurchatov Institute) equipped with a high-resolution
SPECS Phoibos 150 hemispherical electron energy analyzer with a
monochromatic Al X-ray source (excitation energy of 1486.61 eV; ΔE
= 0.2 eV).
Thermogravimetric analysis was performed on a Shimadzu DTG-
60H analyzer. The measurements were carried out in an argon
atmosphere within the temperature range of 40−1200 °C. The
heating rate was 20 °C/min.
Organic products of the reactions were identified by GC-MS with
the use of an Agilent Technologies 6890B gas chromatograph (HP-5
ms column) equipped with mass-selective detector MSD 5975; before
the measurements, samples were dissolved in dichloromethane.
For the SEM measurements, the samples were glued to the surface
of a 1 in. aluminum specimen stub by conductive carbon-based
plasticine and coated by a 15 nm layer of carbon. The observations
were carried out using a Hitachi SU8000 field-emission scanning
electron microscope (FE-SEM). Images were acquired in secondary
electron mode at a 2 or 10 kV accelerating voltage. X-ray
microanalysis (EDS-SEM) was performed with the use of an Oxford
Instruments X-max 80 energy dispersive X-ray spectrometer at a 20
kV accelerating voltage.
Synthesis of [Ni(S-p-ClC6H4)2]n with Different Thiol Load-
ings. First, 7.7 mg (0.03 mmol) of Ni(acac)2 was dissolved in 0.5 mL
of dichloromethane and mixed with 0.5 mL of a 4-chlorothiophenol
solution (0.06, 0.09, or 0.15 mmol of thiol) in dichloromethane. The
reaction mixture was kept at room temperature for 15 min until the
product had completely precipitated. The resulting solid nickel
thiolate was separated by centrifugation, washed with dichloro-
methane (3 × 4 mL), and dried under reduced pressure at room
temperature. For the additional experiments devoted to the study of
nickel thiolate properties, the selected procedure was scaled up to 1.5
mmol of Ni(acac)2 loading (see Scaled Procedure for the Synthesis of
Nickel Thiolates).
Synthesis of [Ni(S-p-ClC6H4)2]n in Different Solvents. First,
7.7 mg (0.03 mmol) of Ni(acac)2 was dissolved in 0.5 mL of the
desired solvent (acetonitrile, toluene, THF, methanol, DMSO, DMF,
ethyl acetate, 1,2-dichloroethane, or chloroform) and mixed with 0.5
mL of a 4-chlorothiophenol solution (21.7 mg, 0.15 mmol of thiol) in
the same solvent. The reaction mixture was kept at room temperature
for 15 min until the product had completely precipitated. The
resulting solid nickel thiolate was separated by centrifugation, washed
with chloroform (3 × 4 mL), and dried under reduced pressure at
room temperature. For the additional experiments devoted to the
study of nickel thiolate properties, the selected procedure was scaled
up to 1.5 mmol of Ni(acac)2 loading (see Scaled Procedure for the
Synthesis of Nickel Thiolates).
Scaled Procedure for the Synthesis of Nickel Thiolates. First,
385.4 mg (1.5 mmol) of Ni(acac)2 was dissolved in 6 mL of the
desired solvent and mixed with 7.5 mmol of thiol (neat liquid for
liquid thiols or 6 mL of the chosen solvent for solid thiols). The
reaction mixture was kept at room temperature for 30 min until the
product had completely precipitated. The resulting solid nickel
CONCLUSIONS
■
In summary, the new solid-phase C−S bond formation
reaction involving metal-containing coordination polymers
was found to be an efficient route for the synthesis of nickel-
based nanomaterials via direct hierarchical structure transfer
(Scheme 3). The desired morphology can be achieved on the
initial step of the synthesis of nickel thiolate coordination
polymers by a change in the substituent in the organic ligands
of thiolate or by the choice of the solvent, which has a
pronounced effect on the morphology of the particles grown
from initially formed soluble species (Scheme 3, step A).
Temperature-induced selective conversion of nickel thiolates in
an inert atmosphere led to the exclusive formation of
nanosized nickel sulfide and the corresponding diaryl sulfide.
The switch from an inert to a reactive gas atmosphere allows
the product composition to be changed selectively. Introduc-
tion of oxygen into the reaction system led to the formation of
nickel oxide instead of nickel sulfide. The key feature of the
process is the preservation of the initial thiolate particle
morphology in the final product, which makes possible the
creation of different well-ordered assemblies of nickel-
containing nanoparticles by tuning nickel thiolate synthesis
conditions (Scheme 3, step B). The organic diaryl sulfide
product detected in the reaction in an inert atmosphere can be
used itself as a valuable compound23−25 or reduced to the
corresponding thiol41,42 for further application in the next cycle
of metal thiolate synthesis (Scheme 3, step C).
Overall, here we suggest an efficient procedure for
generating a variety of new metal organochalcogenide
morphologies by tuning the molecular level cooperative effect
of organic substituents at the sulfur atom, followed by removal
of organic substituents and transfer of hierarchical structure to
form nanostructured nickel sulfides and oxides. Thus, organic
sulfides play the role of traceless structure-inducing groups. In
the case of highly valuable nanostructured nickel sulfides,
organic thiolates can be regenerated and reused again. We
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thiolate was separated by centrifugation, washed with dichloro-
methane (5 × 10 mL), and dried under reduced pressure at room
temperature.
Russian Federation; orcid.org/0000-0002-6447-557X;
Email: val@ioc.ac.ru
Thermal Decomposition of Nickel Thiolates under an
Argon Atmosphere. Twenty milligrams of nickel thiolate was
placed in a quartz boat and transferred inside a Carbolite Gero EHA
12/300 furnace equipped with a quartz tube for the thermal treatment
in a controlled atmosphere. The tube was sealed and connected to the
argon cylinder with a gas regulator, which created a constant argon
flow (10 L/h). The assembled tube was heated to the target
temperature (800 °C for p-Br-substituted nickel thiolate or 500 °C for
other nickel thiolates) using a two-step temperature program (room
temperature to 200 °C, 20 °C/min, and 200 °C to the target
temperature, 5 °C/min). The tube was kept at the reaction
temperature for 1 h and then allowed to cool to room temperature.
The resulting solid material was further analyzed without additional
treatment. For the preparation of a sufficient amount of product for
further studies and more accurate determination of mass loss values,
the thiolate loading was increased to 70−80 mg.
Authors
Alexey S. Kashin − N. D. Zelinsky Institute of Organic
Chemistry, Russian Academy of Sciences, Moscow 119991,
Russian Federation; orcid.org/0000-0002-9030-1725
Alexey S. Galushko − N. D. Zelinsky Institute of Organic
Chemistry, Russian Academy of Sciences, Moscow 119991,
Russian Federation
Evgeniya S. Degtyareva − N. D. Zelinsky Institute of Organic
Chemistry, Russian Academy of Sciences, Moscow 119991,
Russian Federation; orcid.org/0000-0002-9351-8532
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.inorgchem.0c01352
Notes
Thermal Decomposition of [Ni(S-p-ClC6H4)2]n in an Air Flow
at Different Temperatures. Twenty milligrams of [Ni(S-p-
ClC6H4)2]n was placed in a quartz boat and transferred inside a
Carbolite Gero EHA 12/300 furnace equipped with a quartz tube for
the thermal treatment in a controlled atmosphere. The tube was
sealed and connected to the air compressor, which created a constant
air flow (200 L/h). The assembled tube was heated to the target
temperature (600, 700, or 800 °C) using a two-step temperature
program (room temperature to 200 °C, 20 °C/min, and 200 °C to
the target temperature, 5 °C/min). The tube was kept at the reaction
temperature for 2 h and then allowed to cool to room temperature.
The resulting solid material was further analyzed without additional
treatment. For the preparation of a sufficient amount of the product
for further studies and more accurate determination of mass loss
values, the thiolate loading was increased to 70−80 mg.
Thermal Decomposition of Nickel Thiolates in an Air Flow.
Twenty milligrams of nickel thiolate was placed in a quartz boat and
transferred inside a Carbolite Gero EHA 12/300 furnace equipped
with a quartz tube for the thermal treatment in a controlled
atmosphere. The tube was sealed and connected to the air
compressor, which created a constant air flow (200 L/h). The
assembled tube was heated to 800 °C using a two-step temperature
program (room temperature to 200 °C, 20 °C/min, and 200 to 800
°C, 5 °C/min). The tube was kept at the reaction temperature for 2 h
and then allowed to cool to room temperature. The resulting solid
material was further analyzed without additional treatment. For the
preparation of a sufficient amount of product for further studies and
more accurate determination of mass loss values, the thiolate loading
was increased to 70−80 mg.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
The authors thank RFBR and Moscow city Government for
the financial support (Research Project 19-33-70032). The
authors are grateful to Dr. Ashot V. Arzumanyan and
Konstantin L. Boldyrev (A. N. Nesmeyanov Institute of
Organoelement Compounds, Russian Academy of Sciences)
for the thermogravimetric analysis of the samples. X-ray
powder diffraction (XRPD) and X-ray photoelectron spectros-
copy (XPS) characterization was performed using the scientific
infrastructure facility Kurchatov Synchrotron Radiation Source
of National Research Center Kurchatov Institute (Moscow).
The authors thank Roman D. Svetogorov for the XRPD studies
and Dr. Ratibor G. Chumakov for recording XPS spectra.
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ASSOCIATED CONTENT
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sı
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c01352.
Additional scanning electron microscopy data for nickel
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AUTHOR INFORMATION
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Corresponding Author
Valentine P. Ananikov − N. D. Zelinsky Institute of Organic
Chemistry, Russian Academy of Sciences, Moscow 119991,
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