Unusual penta- and hexanuclear Ni(ii)-based silsesquioxane polynuclear complexes

Article abstract of DOI:10.1039/c6dt00113k

Fine-tuning of the reaction between alkali metal siloxanolate [PhSi(O)ONa]_n and [Ni(NH₃)₆]Cl₂ allowed us to design new hexa- [(PhSiO_1,5)₁₂(NiO)₆(H₂O)(DMSO)₉] (1) and pentanuclear [(PhSiO_1,5)₁₀(NiO)₅(NaOH)(DMF)₇] (2) cage-like silsesquioxanes. Their specific structures were studied by single crystal X-ray diffraction and topological analyses. Compound 2 is the first example of a pentanuclear "cylinder"-like metallasilsesquioxane. Magnetic property investigations demonstrate the presence of a slow relaxation of the magnetization, induced by spin glass-like behavior in both cases.

Full text of DOI:10.1039/c6dt00113k

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Levitsky, Dalton Trans., 2016, DOI: 10.1039/C6DT00113K.
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Unusual penta- and hexanuclear Ni(II)-based silsesquioxane
polynuclear complexes
Received 00th January 20xx,
Alexey N. Bilyachenko,*a,b Alexey I. Yalymov,a Alexander A. Korlyukov,a,c Jérôme Long,d Joulia Lar-
ionova,*d Yannick Guari,d Anna V. Vologzhanina,a Marina A. Es’kova,a Elena S. Shubina,a Mikhail M.
Levitsky*a
Fine tuning of the reaction between alkali metal siloxanolate [PhSi(O)ONa]n and [Ni(NH3)6]Cl2 allowed to design new hexa-
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
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[(PhSiO1,5)12(NiO)6(H2O)(DMSO)9] (1) and pentanuclear [(PhSiO1,5)10(NiO)5(NaOH)(DMF)7] (2) cage-like silsesquioxanes. Their
specific structures were studied by single crystal X-ray diffraction and topological analysis. Compound 2 is the first example
of pentanuclear “Cylinder”-like metallasilsesquioxane. Magnetic properties investigations demonstrate the presence of a
slow relaxation of the magnetization induced by spin glass-like behavior in both cases.
magnetic behaviour.5 Being interested in further study of
magnetic properties of CLMSs including transition metal ions,
we turned to Ni(II)-containing polyhedral silsesquioxanes.
Introduction
Metal-containing silsesquioxanes of polyhedral geometry,
called also cage-like metallasilsesquioxanes (CLMSs), are an
intensively studied class of molecular materials due to their
unique ability to form unprecedented molecular architectures1
and to exhibit high activity in different catalytic
applications.1f,1g,2 In turn, CLMSs are attractive platforms for
estimation of exchange interactions of metal ions, “trapped” in
siloxane matrix,3 including rare case of CLMSs, containing
metal ions in different oxidation states.4 Indeed, rational
approaches (e.g. using of trisilanols1c or non-condensed
cubane silsesquioxanes1e as initial reagents) allow to design
isolated architectures of desired nuclearity and in controlled
fashion containing transition metal ions or lanthanides
assembled through the silicon atoms. Surprisingly, magnetic
properties investigations on these materials are not abundant
and we can cite here only few examples, including studies of
Fe-3b-f, i, Co-3e, Cu-3g, Mn-3h or Cr-containing4 CLMSs. Recently,
Importantly, no information concerning potential of such
compounds in demonstration of slow dynamic of the
magnetization was provided despite that cage-like nickel(II)-
containing silsesquioxanes might be promising objects for
exhibiting such dynamic of the magnetization. Generally, this
statement is due to known ability of several Ni(II)-containing
discrete architectures to manifest Single Molecule Magnet
(SMM) behaviour.6 Nevertheless, all known examples of Ni-
based CLMSs’ magnetic studies revealed only ferro- and
antiferromagnetic interactions in Sandwich-like (Ni4 and Ni6)7-,
(Co2/Ni4)8-, (Fe2/Ni4)9-CLMSs without the presence of
a
magnetic ordering.
The most recent description of CLMS structures formation
given in1g postulates that aggregation of cage
metallasilsesquioxane is governed by several factors, e.g.
silicon/metal(s) ratio, nature of solvent(s), presence of mono-
or bidentate ligands. It is known that despite the kaleidoscopic
variety in CLMS cores described to date (Cubane, Bird Cage,
Lantern, Cooling Tower etc.), many of obtained CLMSs,
including M(II) ions, belong to Cylinder family with two major
types of nuclearity – 4 and 6.1g We suggested that the use of
synthetic approaches, mentioned above, let to obtain other
forms of Prismatic CLMSs. Our first investigations were
devoted to the synthesis of Ni(II)-containing CLMSs in the
presence of different solvents. We were interested in such
variation because recently some of us have shown that the
nature of solvent molecules may highly influence structural
parameters of Cu(II)-based CLMSs.2h Consequently, we report
here crystal structures and magnetic properties investigation
of two new Cylinder Ni(II)-CLMSs of different nuclearity. A
particular emphasis is given on the determination of the
magnetic regime in these systems.
we reported the first example of
a CLMS architecture
displaying an unusual slow dynamic of the magnetization
arising from the interaction between three crystallographically
independent Co(II) ions arranged in a triangular fashion with a
spin frustration giving rise to an appearance of a spin glass-like
a.A.N.Nesmeyanov Institute of Organoelement Compounds of Russian Academy of
Sciences, Vavilov str., 28, Moscow, Russia. E-mails:bilyachenko@ineos.ac.ru
(A.N.B.), levitsk@ineos.ac.ru (M.M.L.)
b.People's Friendship University of Russia, Miklukho-Maklay Str., 6, 117198
Moscow, Russia
c.Pirogov Russian National Research Medical University, Ostrovitianov str., 1,
Moscow, Russia
d.Institut Charles Gerhardt de Montpellier (ICGM), UMR5253, Equipe IMNO,
Université de Montpellier, Site Triolet, Place Eugène Bataillon, 34095 Montpellier
cedex 5, France. E-mail: joulia.larionova@univ-montp2.fr
† Electronic Supplementary Information (ESI) available. See
DOI: 10.1039/x0xx00000x
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Results and Discussion
Synthesis and Crystal Structure
The exchange reaction between sodium phenylsiloxanolate
[PhSi(O)ONa]n (formed in situ from PhSi(OEt)3 and sodium
hydroxide) and [Ni(NH3)6]Cl2 precursors in two different
solvents, DMSO and DMF, induces a formation of two new
CLMSs of different nuclearity. In the first case, the hexanuclear
[(PhSiO1,5)12(NiO)6(H2O)(DMSO)9]
pentanuclear [(PhSiO1,5)10(NiO)5(DMF)7]
obtained with 43 % and 38 % yield, respectively (Scheme 1).
1
and in the second, the
2
architectures were
Figure 2. Top. Molecular structure of hexanuclear
[(PhSiO1,5)12(NiO)6(H2O)(DMSO)9] CLMS
1. Color code: Ni,
green; O, red; Si, yellow. Phenyl groups at the silicon atoms
and DMSO molecules are omitted for clarity. Bottom. Crystal
packing of CLMS 1.
Similar synthesis in the DMF media leads to pentanuclear
Cylinder [(PhSiO1,5)10(NiO)5(DMF)7] CLMS (Figure 3). The
shortest intramolecular distance Ni…Ni is 2.70 Å. Crystal
packing of is shown on Figure 3 (bottom). The shortest
intermolecular Ni- Ni distance (between the polynuclear
complexes) is 10.34 Å. Noteworthy that compound joins very
rare family of pentanuclear CLMSs10 and is the first example of
the Ni(II)-containing CLMS with the odd number of nickel
atoms.
2
2
2
Figure 1. Schematic representation of the synthetic strategy
employed
for
designing
of
and
hexanucelar
pentanuclear
[(PhSiO1,5
[(PhSiO1,5
)
12(NiO)6(H2O)(DMSO)9]
1
)10(NiO)5(DMF)7] 2 phenylsilsesquioxanes.
Structural peculiarities of
1
and
2
were established by single
presents a
crystals X-ray diffraction analysis. Compound
typical1g hexanuclear cylinder-like type of CLMSs molecular
1
geometry (Figure 2, top). The main difference between
compound
CLMSs1g is the nature of the encapsulated entity. The inner
void of captures a water molecule (unfortunately, the
1 and early described hexanuclear cylindrical
1
hydrogen atoms bonded to the oxygen atoms cannot be
located) instead of classically encapsulated agents, such as Cl-
.
1g The shortest intramolecular distance Ni…Ni is 2.92 Å. Crystal
packing of
1 is shown on Figure 2 (bottom). The shortest
intermolecular Ni- Ni distance (between the polynuclear
complexes) is 13.44 Å. Additional discussion of structural
parameters of 1 is provided below (Table 1).
Figure 3. Top. Molecular structure of pentanuclear
[(PhSiO1,5)10(NiO)5(DMF)7] CLMS 2. Color code: Ni, green; O, red; Si,
yellow, Na, orange. Phenyl groups at silicon atoms and molecules of
solvates (DMF) are omitted in the sake of clarity. Bottom. Crystal
packing of CLMS 2.
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Table 1. Average values of selected bonds and interatomic distances
in 1 and 2.
An assembly of such non-trivial pentanuclear complexes
became possible due to an involvement of DMF molecules,
which are specific ligands with high basicity. Presumably, at
2 (L = OH),
1 (L = H2O)
the first stage of compound
1 formation, four molecules of
M= Na
DMF coordinate to sodium ion and, in the same time, to two
Ni(II) ions of metallasilsesquioxane cyclic fragments. Thus,
unusual synthone is formed, where coordination number of
the sodium ion is increased to 6 (due to an additional
coordination of Na+ to oxygen atoms in Si-O-Ni moieties).
Noteworthy, metallasilsesquioxane cycles in this synthone are
oriented each to other by the angle of 107.6о, which
corresponds to the inner angle value for the regular pentagon
(108о) (Figure 4 A). It seems that further assembly, resulting in
an arising of regular pentanuclear Cylinder-like cage, is
strongly assisted by the presence of an OH- counterion. The
latter is situated in the inner void of cage and coordinates to
Ni(II) ions (Figure 4, B). Three DMF molecules additionally
coordinate three nickel ions, resulting in realization of an
hexacoordinate environment of all Ni(II) sites.
Ni…Ni
2.946(1)
2.016(3)
2.7265(4)
2.0329(2)
Ni-O (siloxanolate
atoms)
Ni-L (encapsulated
ligand)
2.938(7)
1.598(3)
1.630(3)
2.061(2)
1.597(2)
Si-O (siloxanolate
atoms)
Si-O (atoms of
siloxane cycle)
1.636(2)
2.394(2)
M-O
Also, taking in mind an importance of the mutual disposition of
nickel(II)-containing complexes for magnetic behavior of
synthesized complexes, we were interested in a topological
analysis of CLMSs
1 and 2. Recently some of us reported the
first example of such study on copper(II)-containing
silsesquioxanes of different nuclearity.2h Simplification of the
molecular graph to obtain the graph of Ni-containing skeleton
keeping the complexes connectivity was carried out with the
ToposPro package.12 Following the procedure of a metal
complexes notation described previously13 one would obtain
that penta- and hexanuclear compounds
1 and 2 form 4M5-1
and 5M6-1 discrete polynuclear complexes, respectively
(Figure 4), in terms of the NDk-m notation.13 Here, N is a set of
coordination numbers of topologically non-equivalent nodes
(N = 2 for 2-connected nodes), D is the dimensionality (D = M
for discrete polynuclear complexes), k is the number of metal
atoms in the polynuclear complexes (k = 5 or 6), and m is a
classification number to distinguish topologically distinct
polynuclear complexes with equal NDk parameters.
Figure 4. Schematic representation of an assembly of pentanuclear
[(PhSiO1,5)10(NiO)5(DMF)7] CLMS 2 assisted by DMF molecules.
A
comparison of structural parameters of hexa- and
pentanuclear complexes and is provided in Table 1. It
should be noticed that the mean Ni…Ni distance in is much
1
2
2
shorter than the one observed for 1. It is comparable to the
distances observed for decanuclear nickel(II)-based CLMS,
reported by some of us previously.11
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Figure 6. Temperature dependence of
magnetic field for
magnetisation performed at 1.8 K for 1 and 2.
χ
T under a 1000 Oe DC
and 2. Inset: Field dependence of the
1
Compound 1 exhibits the χ
T value of 11.06 cm3.K.mol-1 at 300 K,
which is higher than the theoretical value of 8.26 cm3.K.mol-1
expected for six high-spin independents square pyramidal NiII
ions.21 This discrepancy could arise from the occurrence of
ferromagnetic interactions which are still operative at room
4M5-1
5M6-1
Figure 5. The Ni-containing polynuclear complexes connected by
the oxygen bridged atoms in (a) 1 and (b) 2 and the graphs for the
corresponding polynuclear complexes’ connectivity (c, d).
temperature. The thermal dependence of
when the temperature decreases until reaching a maximum at 10 K
with a
T value of 45.00 cm3.K.mol-1. This confirms the occurrence
χT reveals an increase
Based on
a database of topological representations of
χ
polynuclear nickel compounds14 containing 318 compounds
and 126 different topological motifs, only two and four
compounds with the 4M5-1 and 5M6-1 topologies,
respectively, were published before. The family of 4M5-1
polynuclear complexes contains also [Ni5(μ5-S)(μ3-S)2(μ2-S)(μ-
of ferromagnetic interactions between the Ni2+ ions, although the
value is considerably higher than the value of 23.15 cm3.K.mol-1
expected for S = 6 species that would result from a ferromagnetic
coupling between all Ni2+ ions. Such deviation may be rationalized
through the presence of intermolecular dipolar interactions
mediated, for example, through the π-stacking. Below 10 K, a
CH3COO)(PPh3)5]PF6·C7H8·0.5CH2Cl2 and [Ni5(μ-SSitBu3)5(μ5-
S)].16 The hexanuclear nickel(II)-containing polynuclear
15
complexes of the 5M6-1 topology were found also in [Ni6(μ6- decrease of
S)(μ-S)2(η3-allyl)6],17
[Ni6(μ6-Hal)(μ3-Hal)2(μ-Hal)6(μ-phip)3]
χT occurs and most likely originates from the zero-field
splitting. The field dependence of the magnetization at 1.8 K (Inset
of Figure 6) leads to a value of 8.50 ꢀB under 70 kOe, although the
system does not reach a clear saturation, indicating the presence of
a magnetic anisotropy. In order to probe the occurrence of a slow
relaxation of the magnetization, the zero-field cooled/field cooled
(ZFC/FC) procedure was performed. In the ZFC experiment, the
sample was cooled in the absence of a static magnetic field and the
magnetization was then recorded as a function of temperature
under a 50 Oe magnetic field. The FC magnetization data were
collected after cooling the sample with the same field. The ZFC
curve shows a narrow peak with a maximum at Tmax = 6.2 K, while
the FC curve increases. The ZFC/FC curves coincide for high
temperatures and begin to separate at 7 K (Figure 7). An increasing
of the applied dc field induces a shift of the ZFC curve maximum
(phip = 3,5-bis(2,6-diisopropylphenyliminoacetyl)-1H-pyrazole;
Hal = Cl;18 Hal = Br19) and [Ni6(amox)6(μ6-O)(μ3-OH)2]Cl2·6H2O
(amox = 4-amino-4-methyl-2-pentanone oxime).20 Thus, μ5 or
μ6 coordination in the nickel polynuclear complexes is possible
for Hal-, S2- and O2- anions.
Thus, the use of different solvent media, when corresponding
solvent could play an assisting role in the cage formation, lets
us to design hexa
Ni(II)-based CLMSs. It was shown that hexagon-like disposition
of nickel ions in is characterized by longer Ni…Ni distances
1- and (for the first time) pentanuclear 2
1
that found in pentagon-like organisation of nickel ions in 2.
Magnetic properties investigations
towards lower temperature. Consequently,
a clear magnetic
The magnetic properties of compounds 1 and 2 were investigated
irreversibility occurs which is characteristic of the presence of a
slow relaxation of the magnetization. This behavior is confirmed by
monitoring the relaxation dynamics of the magnetization with AC
magnetic measurements.
using SQUID magnetometry.
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FC
50 Oe
200 Oe
400 Oe
700 Oe
1000 Oe
2500 Oe
5000 Oe
10
χ
0
2
4
6
8
10
T
/ K
Figure 7. ZFCcurves with various applied magnetic fields for 1 and
FC curve for a 50 dc field.
The temperature dependence of the in-phase (
χ') and the out-of-
phase ( '') components of the alternating current susceptibility
χ
were measured in the zero-dc field and reveals a frequency
dependence indicating an occurrence of a slow relaxation of the
Figure 8. Temperature dependence of the in-phase (
χ
') (top) and
magnetization (Figure 8). The maxima of
temperatures as the frequency increases. For instance,
maximum at 7.2 K, while the maximum of '' is observed at 6.4 K
with a 100 Hz frequency. Additionally, the '' intensity increases
χ'' shift to higher
out-of-phase susceptibtilies (
1.
χ") (bottom) under a zero dc-field for
χ' exhibits a
χ
χ
To check the occurrence of a spin glass-like behaviour, of the
temperature dependence of the AC susceptibilities (at the
frequency of 500 Hz) were measured for the different dc fields
(Figure 9). The peak's maxima and intensities of both, the in-phase
and the out-of-phase susceptibilities shift to lower temperature
with increasing fields.
with frequencies up to 100 Hz before decreasing for higher values.
The frequency dependence of the ac susceptibilities can originate
from either a Single-Molecule Magnet or a spin glass-like behavior.
The frequency dependence of the ac susceptibility show very broad
peaks (Figure S1) that indicates a distribution of the relaxation time.
Similarly, the Cole-Cole plots (Figure S2) show curves that deviate
strongly from perfect semo-circles expected in the case of a narrow
distribution of relaxation process. Such wide distribution of
relaxation processes may originate from a spin-glass behavior which
is further confirmed by calculating the Mydosh parameter
ϕ (ϕ =
(Tmax – Tmin)/(Tmax×log max-log min)), which indicates the amplitude
ν
ν
of the out-of-phase peaks’ shift with frequency. This parameter is
equal to 0.049, which is lower than the values observed for classical
superparamagnets (> 0.1) and suggests the occurrence of a spin
glass behavior. This is further confirms when looking at the
Arrhenius law,
τ = τ0exp(Ueff/kBT), where Ueff is the average energy
barrier for the reversal of the magnetization, τ0 is the attempt time
and kB is the Boltzmann constant. The best Arrhenius law fit of the
blocking temperatures obtained from the
χ’’ maxima for different
observation times =1/2π (with being the frequency of the
τ
ν
ν
oscillating field) gives the Ueff and τ0 values equal to 300.89 K and
3.55.10-23 s, respectively. The τ0 value obtained is clearly too low
than those expected for pure superparamagnetic systems (10-8–10-
12 s) and has not a physical meaning.
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The magnetic behaviour of compound 2 reveals also the presence
of the spin glass-like behaviour. The experimental room
temperature χ
T value of compound 2 is equal to 6.02 cm3.K.mol-1,
which is slightly higher than the one of 5.51 cm3.K.mol-1 expected
for the five independent octahedral Ni(II) sites (S = 1, g = 2.1). Upon
cooling, χT continuously decreases to reach a small plateau around
12 K (1.63 cm3.K.mol-1) before strongly decreasing to a value of 1.00
cm3.K.mol-1 at 1.8 K (Figure 6). While the former decrease originates
from dominant antiferromagnetic interactions between the spin
carriers, the decrease at low temperature may be imputed to the
occurrence of a zero-field splitting and/or intermolecular dipolar
interactions. The presence of a plateau with a non-zero value of the
χT product may indicate the occurrence of a spin frustrated system
in accordance with the topology of the polynyclear complex. The
field dependence of the magnetization at 1.8 K reveals a fast
increase at low fields before showing a linear dependence to reach
the value of 1.43 ꢀB under a 70 kOe field (Inset of Figure 6). To
probe the occurrence of a spin glass behavior, the dynamic
behavior was studied with alternating current (AC) measurements.
The temperature dependence of the in-phase (
phase ( '') susceptibilities reveal a clear frequency dependence.
While the maximum of ' shifts to higher temperature with
increasing frequencies, no maximum can be observed for '' in the
χ') and the out-of-
χ
χ
χ
temperature range available (Figure 11). This precludes an in-depth
analysis of the relaxation mechanisms. However, it can be observed
than the intensity of the out-of-phase signal increases with
frequency, which does not correspond to what is usually observed
for pure superparamagnetic systems and suggests also the
presence of a spin glass-like behavior.
Figure 9. Temperature dependence of the in-phase (a) and out-of-
phase susceptibilities (b) measured with various dc magnetic fields
for 1.
6.5
6.0
5.5
Consequently, the spin glass-like behavior observed in 1 and 2 may
originate from: (i) the freezing of the spins in each individual CLMS
molecule, which may be caused by a particular arrangement of the
Ni(II) ions in hexa- and pentagonal topology, and/or (ii) the
presence of dipolar interactions between the CLMS molecules.
Indeed, a particular geometrical arrangement of Ni(II) ions linked
through two types of bridging oxygen atoms including peripheral
and central ones may lead to different magnetic exchange pathway
resulting in a spin frustration (see Figures 2-3). Such a phenomenon
has previously been observed in the case of Co(II)-based triangular
CLMS presenting a relatively large inter-complex separation of 14.5
Å. The shortest intermolecular Ni…Ni distances is equal to 13.54
and 10.34 Å for 1 and 2, respectively. For this reason, it is
reasonable to conclude that in the case of 1, the observed spin
glass-like regime originates rather from a spin frustration in each
complex, even if we cannot completely exclude an influence of
dipolar interactions, while for compound 2, the dipolar interactions
play more important role, as previously observed in a trinuclear
x
a
m
T
5.0
4.5
0
20
40
60
80
100
H 2/3 / Oe
Figure 10. Field dependence of the temperature maximum of χ" as
a function of the magnetic field (Almeida-Thouless line) for 1.
The temperature maximum of
corresponds to the Almeida-Thouless line and is frequently nickel (II) based complex.23
associated with
spin glass-like behavior (Figure 10).5,22
χ
" decreases linearly with H2/3 which
a
Extrapolation at H = 0 Oe gives a freezing temperature of 6.7 K,
close to the value for the maximum of the ZFC curve of 6.2 K (Figure
7). Consequently, compound 1 clearly shows a spin glass-like
behavior.
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The solvents (Merck) and other chemicals (Sigma-Aldrich) were
used without further purification
0.55
0.50
0.45
0.40
10 Hz
100 Hz
500 Hz
1000 Hz
1500 Hz
Synthesis
[(PhSiO1,5)12(NiO)6(H2O)(DMSO)9] 1:
PhenyltriethoxysilanePhSi(OEt)3 (1 g, 4.16 mmol) water (0.149
g, 8.28 mmol), sodium hydroxide (0.166 g, 4.15 mmol) in 18 ml
of MeOH were placed into flask, provided by magnetic stirrer
and condenser. After total dissolution of sodium hydroxide
mixture was heated at reflux for 2 hours, then cooled down to
room temperature. Afterwards 55 ml of DMSO and nickel
hexamine chloride Ni(NH3)6Cl2 (0.482 g, 2.08 mmol) were
added at once. The reaction mixture was brought to reflux
along with simultaneous partial distillation of the solution. As
15 mL of solvents were distilled off, the rest of reaction
mixture was heated under reflux for 3.5 h, then cooled to
room temperature. After overnight stirring the mixture was
filtered into an evaporation flask. The flask was equipped with
a septum and needle to allow solvents to evaporate under a
slow current of nitrogen. Immediately after yellow-colored
crystals began to form, the flask was transferred to the cool
place and stored there until the crystal fraction growth (~ 3
weeks) ceased, as visually determined. A few selected single
crystals were used for the X-ray study (for details, see below).
Yield: 0.26 g, 38%; elemental analysis calcd (%) for
χ
0.35
0.30
0.12
0.10
0.08
0.06
0.04
χ
0.02
0.00
2
3
4
T
/ K
Figure 11. Temperature dependence of the in-phase (χ') and out-of-
phase (χ") susceptibilities under a zero-dc field for compound 2.
[(PhSiO1.5)12(NiO)6(H2O)]: Ni 17.46, Si 16.71; found (in
vacuum-dried sample): Ni 17.29, Si 16.45.
a
[(PhSiO1,5)10(NiO)5(NaOH)(DMF)7] 2:
Phenyltriethoxysilane PhSi(OEt)3 (1 g, 4.16 mmol) water (0.149
g, 8.28 mmol), sodium hydroxide (0.166 g, 4.15 mmol) in 18 ml
of MeOH were placed into flask, provided by magnetic stirrer
and condenser. After total dissolution of sodium hydroxide
mixture was heated at reflux for 2 hours, then cooled down to
room temperature. Afterwards 55 ml of DMF and nickel
hexamine chloride Ni(NH3)6Cl2 (0.482 g, 2.08 mmol) were
added at once. The reaction mixture was brought to reflux
along with simultaneous partial distillation of the solution. As
15 mL of solvents were distilled off, the rest of reaction
mixture was heated under reflux for 3.5 h, then cooled to
room temperature. After overnight stirring the mixture was
filtered into an evaporation flask. The flask was equipped with
a septum and needle to allow solvents to evaporate under a
slow current of nitrogen. Immediately after yellow-colored
crystals began to form, the flask was transferred to the fridge
and stored there until the crystal fraction growth (~ 2 weeks)
ceased, as visually determined. A few selected single crystals
were used for the X-ray study (for details, see below). Yield:
0.30 g, 42%; elemental analysis calcd (%) for
[(PhSiO1.5)10(NiO)5(NaOH)]: Ni 17.21, Si 16.47; found (in a
vacuum-dried sample): Ni 17.09, Si 16.29.
Conclusions
New hexanuclear [(PhSiO1,5)12(NiO)6(H2O)(DMSO)9]
1 and
pentanuclear [(PhSiO1,5)10(NiO)5(NaOH)(DMF)7] 2 nickel(II)-
based silsesquioxanes have been obtained by an exchange
reaction between a sodium phenylsiloxanolate [PhSi(O)ONa]n
and NiCl2•6NH3 in the presence of DMSO in the first and DMF
molecules in the second case. We demonstrated that the role
of solvent during the synthesis is crucial for the nuclearity of
the final compound. Thus, this approach allow us to design for
the first time the first example of an unusual pentanuclear
cage-like Ni(II)-based silsesquioxane CLMS. The representation
of the pentanuclear complex assembly, implying
a
coordination of the DMF molecules was proposed. Both
compounds were studied by X-ray diffraction and topological
analysis. Magnetic properties investigations revealed the
presence of a slow relaxation of the magnetization in both
cases induced by
a
spin glass-like behavior which
concomitantly originates from both, the spin frustration in
each polynuclear complex, and dipolar interactions between
the CLMSs molecules.
IR studies
Experimental section
IR studies were carried out using Nujol mulls on a Nicolet 6700
FTIR spectrometer in the 4000–600 см–1 range. Set of signals
for 1-2: 1120 cm−1 (νPh–Si), 940–1100 cm−1 (νasSi–O, νasSi–O–
Starting materials and physical measurements
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Si), 900 cm–1 (νasSi–O in Si–O–M fragment), 720–680 cm−1 (σC–
H of mono-substituted phenyl group).
wR2 [all
reflections]
0.1727
1.033
0.1303
1.101
GOF
Magnetic measurements
Residual
electron
Magnetic susceptibility data were collected with a Quantum
Design MPMS-XL SQUID magnetometer working between 1.8
and 350 K with the magnetic field up to 7 Tesla. The data were
corrected for the sample holder and the diamagnetic
contributions calculated from the Pascal's constants.
2.670/-1.183
1.714/-0.719
density e⋅Å-
3(ρmin/ρmax
)
X-ray
Acknowledgements
X-ray diffraction studies were carried out on Bruker APEX DUO at
120 K (1) and Bruker Smart APEX II (2). The structures were solved
by direct method and refined in anisotropic approximation against
F2. The crystal structure contains strongly disordered solvents
molecules; their contribution to diffraction intensities was excluded
using SQUEEZE procedure implemented in PLATON software.24 All
calculations were carried out with SHELX25 and OLEX226 software.
The experimental parameters and crystal data for 1 and 2 are
summarized in Table 2
This work was supported by the Russian Foundation for basic
research (projects 14-03-31772 and 14-03-00713), the Council
of the President of the Russian Federation (project МD-
3589.2014.3), the French Embassy in Moscow (Programme
André Mazon), the Balard Foundation, the University of
Montpellier, CNRS and the Plateforme d'Analyse et de
Caractérisation (PAC Balard).
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