Hydrogen bond-directed assembly of silsesquioxanes cubes: synthesis of carboxylic acid POSS derivatives and the solid state structure of octa[2-(p-carboxyphenyl)ethyl] silsesquioxane

Article abstract of DOI:10.1039/c6ce02369j

The octa[2-(p-carboxyphenyl)ethyl] and octa[2-(4-carboxy-1,1′-biphenyl)ethyl] silsesquioxane were synthesised under mild reaction conditions upon hydrogenolysis of the corresponding benzyl-ester derivatives. The octa[2-(p-carboxyphenyl)ethyl] silsesquioxane was shown to self-assemble upon formation of carboxylic acid dimers. The presence of eight carboxylic acid functional groups allowed to obtain an ordered silsesquioxane hybrid network. The X-ray crystal structures of the octa-ester and of the octa-acid were determined. The three-dimensional conformation of the ester provided an interpenetrated compact packing of the molecular building blocks without any specific supramolecular interaction. The two-dimensional character of the acid and the directionality of the hydrogen bond pattern of a dimer of acid led to the formation of hydrogen-bonded ribbons. It showed that functionalized silsesquioxane precursors capable of hydrogen bonding are of interest to generate nanostructured materials through self-organization processes. Moreover, the use of carboxylic acid groups is interesting not only because of their ability to form carboxyl dimer structures by hydrogen bonding but also because of their ability to form metal carboxylate derivatives that may lead to new organised hybrid metal organic silica frameworks.

Full text of DOI:10.1039/c6ce02369j

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Hydrogen Bond-Directed Assembly of Silsesquioxanes Cubes: Synthesis
of Carboxylic Acid POSS Derivatives and the Solid State Structure of
Octa[2-(p-carboxyphenyl)ethyl] Silsesquioxane†
Voisin Doria,a Flot David,b Van der Lee Arie,c Dautel Olivier,a,* and Moreau Joel J. E.a,*
5
Received (in XXX, XXX) Xth XXXXXXXXX 200X, Accepted Xth XXXXXXXXX 200X
First published on the web Xth XXXXXXXXX 200X
DOI: 10.1039/b000000x
The octa[2ꢀ(pꢀcarboxyphenyl)ethyl] and octa[2ꢀ(4ꢀcarboxyꢀ1,1’ꢀbiphenyl)ethyl] silsesquioxane
were synthesised under mild reaction conditions upon hydrogenolysis of the corresponding benzylꢀ
10 ester derivatives. The octa[2ꢀ(pꢀcarboxyphenyl)ethyl] silsesquioxane was shown to self assemble
upon formation of carboxylic acid dimers. The presence of eight carboxylic acid functional groups
allowed to obtain an ordered silsesquioxane hybrid network. The Xꢀray crystal structures of the
octaꢀester and of the octaꢀacid were determined. The threeꢀdimensional conformation of the ester
provided an interpenetrated compact packing of the molecular building blocks without any specific
15 supramolecular interaction. The twoꢀdimensional character of the acid and the directionality of the
hydrogen bond pattern of a dimer of acid led to the formation of hydrogenꢀbonded ribbons. It
showed that functionalized silsesquioxane precursors capable of hydrogen bonding are of interest
to generate nanostructured materials through selfꢀorganization processes. Moreover, the use of
carboxylic acid groups is interesting not only because of their ability to form carboxyl dimer
20 strutures by hydrogen bonding but also because of their ability to form metal carboxylate
derivatives that may lead to new organised hybrid metal organic silica frameworks.
50 the
hydrolysisꢀcondensation
reactions
of
organoalkoxysilanes also offered the possibility to direct the
formation of the hybrid silica network. The generation of
layered materials by the use of hydrophobic interactions
during the hydrolysis condensation of alkyl trialkoxysilanes
55 containing 12ꢀ18 carbon atoms in the alkyl groups was first
described by Kuroda et al 21. Our group developed a route to
selfꢀassembled hybrid bridged silsesquioxanes by taking
advantage of intermolecular hydrogen bonding, hydrophobic
or π−π interactions, which assembled the organic fragments
60 and thus directed the hydrolysis and condensation of the
alkoxysilyl groups. Organised solids were generated by the
transcription of the structure of supraꢀmolecular assemblies
of informed precursors into a solid material.22,23,24 This
approach proved to be useful for example in tuning the
65 optical and charge transport properties of organic materials
through the control of the 3ꢀD organisation of the selfꢀ
assembled organic substructures.25,26 Although some
crystalline selfꢀassembled hybrid bridged silsesquioxanes
were reported27,28,29 the medium longꢀrange ordering was
70 most often limited to a lamellar arrangement of the organic
substructures and the silica part of the network was
essentially amorphous. The synthesis of crystalline
silsesquioxane hybrid network still remains a challenge.
The synthesis of crystalline material ꢀ particularly metal–
75 organic frameworks (MOFs)30,31,32,33,34,35 and covalent
organic frameworks (COFs)36,37 ꢀ using molecular precursors
represents a very attractive route. The group of Kuroda
Introduction
The synthesis of solids under mild reaction conditions such
25 as the “chimie douce” approach1,2 allowed the design of a
wide variety of useful materials for applications in such
different fields as energy, environment, transports,
construction or health. Solꢀgel chemistry was extended to
organosilicon precursors 25 years ago upon solꢀgel
30 hydrolysis condensation of an organic molecule that was
functionalized by two or more Si(OR)3. It led to hybrid
organicꢀinorganic silicaꢀbased materials whose composition,
combining organic substructures and siloxane units, was
defined at the molecular level.3,4 Diverse materials
35 containing organic substructures and silicate units were
reported.5,6,7 They are amorphous materials that exhibit a
variety of specific properties: porosity, hydrophobic,
catalytic, optical properties…8,9,10,11,12 They were synthesized
under kinetically controlled conditions, which means that the
40 properties of the materials are dependent on the reaction
conditions during the synthesis.
On the basis of molecular and supraꢀmolecular organic
chemistry, new synthetic strategies have therefore been
developed to achieve the control of the structure of the
45 material at nanoscale. The use of supraꢀmolecular
interactions to provide external templating for the
structuration of the porosity of silica13,14,1516 was extended to
the generation of ordered mesoporous organosilicas.17,18,19,20
The selfꢀassembly properties of organic substructures during
recently reported the construction of
a regular supraꢀ
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52
molecular assembly of cage siloxanes. The spherosilicate
building blocks assembled by hydrogen bonding owing to
the presence of silanol functional groups.38 We wanted to
sulphuric acid at 100°C
.
However, the obtained compound
was not soluble and solid state 29Si NMR indicated major T3
substructure with c.a. 2% of T2 substructure meaning that
explore the controlled assembly of the molecular 45 some ring opening of the POSS cube structure occurred to
5
silsesquioxane building blocks as an alternative route to
crystalline hybrid materials. Polyhedral oligomeric
give SiꢀOH groups. Moreover, the resulting solid was not
soluble in any solvent even at high temperature. It may be
indicative that some condensation of the SiꢀOH had occured
leading to oligomeric or polymeric materials. We therefore
silsesquioxanes (POSSs), (RSiO1.5
) with various organic
n
substituents were easily accessible and organic/inorganic
hybrid nanocomposites based on POSS derivatives have 50 looked for mild reaction conditions to generate pure and
10 attracted considerable interest.39,40,41,42,43,44,45 The POSS
substructure represented a wellꢀdefined silica substructure,
which upon functionnalisation by organic group with selfꢀ
assembly properties could form crystalline hybrid network.
soluble silsesquioxane cube derivatives. Various methods
have been reported to prepare functionalised silsesquioxane
cubes [RSiO3/2]8, particularly for those that are not
accessible by direct synthesis via hydrolytic condensation of
We thought that hydrogenꢀbonding interactions would be 55 RSiX3.39 The transformation reactions of simple
15 appropriate for directing the 3D structure arrangement of the
hybrid material.22,38 Here, we report the formation of
crystalline materials from cage T8 silsesquioxanes
functionalised with carboxylic acid groups. The supraꢀ
silsesquioxane cubes require the achievement of quantitative
reactions at the eight silicon atoms of the cube.
Hydrosilylation reactions of the simple hydridoꢀ
silsesquioxane [HSiO3/2
]
have been used. However, the
8
molecular assembly of an octaꢀacid resulted from the 60 vinyl silsesquioxane56,57 [CH2=CHSiO3/2]8 was interestingly
20 dimerization of the carboxylic acid groups, which acted as
hydrogen donors and hydrogen acceptors. In the solid state,
the linear arrangements of the silsesquioxane cubes seemed
to be directed by hydrogen bonding.
found to undergo easily crossꢀmetathesis reactions to
generate substituted derivatives of POSS58. The bulky vinyl
silsesquioxane cube did not undergo selfꢀmetathesis and
appeared to be an excellent substrate for crossꢀmetathesis
65 upon reaction with a variety of terminal alkenes. The
reaction was stereoꢀselective in most cases leading to the Eꢀ
alkenylene isomers as the major product.59 However, we
considered the hydrogenation of vinylidene metathesis
products into ethylidene derivatives in order to get a single
70 compound. Moreover, an ethylidene linker could introduce
some flexibility in the formation of supraꢀmolecular
assembly of the free acid.
The octa[2ꢀ(pꢀcarboxyphenyl)ethyl] silsesquioxane was
synthesized in two steps from the readily available octaꢀ
75 vinyl silsesquioxane as shown in Scheme 1. We first
protected the 4ꢀvinyl benzoic acid as the benzyl ester upon
reaction with benzyl alcohol in the presence of Nꢀ(3ꢀ
Results and discussion
25 Synthesis of POSS derivatives:
A readily available amino functionalised silsesquioxane
such as octa(3ꢀaminopropyl) silsesquioxane46,47,48 would be
of interest as a precursor capable of hydrogenꢀbonding.
However, whereas the compound was easily isolated as
30 ammonium salt, the free amine derivative was less stable
owing to the basicity of the functional group. The
neutralization of the salt to the free amine was difficult to
accomplish without compromising the silsesquioxane cage
structure. Carboxylic acid derivatives seemed more stable
35 and functionalised sperosilicates49 or silsesquioxanes50,51,52 53
,
dimethylaminopropyl)ꢀN′ꢀethylcarbodiimide hydrochloride
60
have been repoted. It led to luminescent material upon
complexation with terbium.54,55 We thus decided to explore
carboxylic acid derivatives that easily formed a dimer
structure even in solution. A straightforward synthesis of
40 carboxylic acid functionalised silsesquioxanes has been
reported by hydrolysis of cyano derivatives with 9ꢀmolar
and DMAP
. It was then reacted with octaꢀvinyl
80 silsesquioxane in CH2Cl2 in the presence of Grubbs’I
catalyst [RuCl2(=CHPh)(PCy3)2].61 The resulting octa[2ꢀ(pꢀ
benzyloxycarbonylphenyl)ethenyl]
isolated in 48 % yield.
silsesquioxane
was
85 Scheme 1. Synthesis of the octa[2-(p-carboxyphenyl)ethyl] silsesquioxane
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The H NMR indicated doublets for the vinyl proton with a J
= 19 Hz coupling consistent with an Eꢀconfiguration of the
C=C bond ( Ha and Hb, Figure 1a). 29Si NMR showed a sharp
singlet at ꢀ78.8 ppm consistently with a T3 [Si(OSi)3Csp2
]
5
environment of the eight silicon atoms of the silsesquioxane
cube. (See SI, Figure S4) The ester was then treated by
hydrogen at atmospheric pressure in the presence of Pd/C. It
allowed both the hydrogenolysis of the benzyl ester functional
group and the hydrogenation of the vinylic C=C bonds to give
10 octa[2ꢀ(pꢀcarboxyphenyl)ethyl] silsesquioxane isolated in
80% yield. The octaꢀacid was obtained as a colourless solid
soluble in common organic solvents such as THF. Its IR
spectrum showed as expected highly broad νOH vibration
around 3000 cmꢀ1 and νC=O vibration at 1683 cmꢀ1.
30
1
Figure 2. 29Si NMR spectrum of octa[2ꢀ(pꢀcarboxyphenyl)ethyl]
15 Hydrogenation of the C=C double bond was established in H
NMR by the appearance of two new resonances at 0.88 ppm
(Ha) and 2.67 ppm (Hb) (Figure 1b). The sharp singlet at 12.79
ppm (He) was also consistent with the hydrogenolysis of the
ester group to the free acid.
silsesquioxane in DMSOꢀd6.
The octaꢀacid obtained under neutral reaction condition
35 appeared soluble and quite stable. In the solid state it was a
microcrystalline material as shown in the powder Xꢀray
diffraction diagram (Figure 3). The IR spectrum with a broad
νOꢀH band is consistent with the existence of interꢀmolecular
interactions by hydrogen bonding. This is indicative of the
40 formation of supramolecular network in the solid.
Additionaly, the octaꢀacid was easily converted into its
sodium carboxylate derivative upon treatment with an
equivalent amount of sodium bicarbonate in water.
20
30000
25000
20000
15000
10000
5000
0
a)
5
10
15
20
2θ (°)
25
30
35
45
Figure 3. PXRD pattern of the octa[2-(p-carboxyphenyl)ethyl]
silsesquioxane
We also prepared the biphenyl derivative in order to have
50 longer organic spacers possibly leading to
a different
arrangement in the porous hybrid network. The octa[2ꢀ(4ꢀ
carboxyꢀ1,1’ꢀbiphenyl)ethyl] silsesquioxane was obtained in a
similar way (scheme 2). The benzyl 4ꢀvinylꢀ[1,1'ꢀbiphenyl]ꢀ
4’ꢀcarboxylate was obtained from pꢀbromobenzoic acid upon
55 esterification with benzyl alcohol followed by Suzuki
coupling with pꢀstyrylboronic acid. It was then reacted as
aboveꢀmentionned with octaꢀvinyl silsesquioxane using
Grubbs’I catalyst to give octa[2ꢀ(4ꢀbenzyloxycarbonylꢀ1,1’ꢀ
biphenyl) ethenyl] silsesquioxane in 70% yield. Consistently,
b)
Figure 1. 1H NMR
benzyloxycarbonylphenyl)ethenyl] silsesquioxane in CDCl3 and
25 b) Octa[2ꢀ(pꢀcarboxyphenyl)ethyl] silsesquioxane in DMSOꢀd6.
ꢀDMSO, ꢁH2O
spectra of a) Octa[2ꢀ(pꢀ
The integrity of the silsesquioxane cube structure was shown by a
sharp resonance at ꢀ67,3 ppm in 29Si NMR in agreement with T3
[Si(OSi)3Csp3] environment of the eight silicon atoms (Figure 2).
1
60 the H NMR showed a doublet for the vinyl proton with a J =
19 Hz coupling (Ha and Hb, Figure 4a) and the 29Si NMR
with a sharp singlet at ꢀ78.3 ppm (See SI, Figure S12).
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Scheme 2. Synthesis of the octa[2-(4-carboxy-1,1’-biphenyl)ethyl] silsesquioxane.
10 As for the phenylene derivative, palladiumꢀcatalysed
hydrogenolysis of the biphenylene ester led to hydrogenation
of the vinylic C=C bond to yield the octa[2ꢀ(4ꢀcarboxyꢀ1,1’ꢀ
biphenyl)ethyl]
silsesquioxane.
(Figure
4b)
Again,
1
hydrogenation of the C=C double bond was established in H
15 NMR by the appearance of two new resonances at 0.90 ppm
(Ha) and 2.67 ppm (Hb). (Figure 1b) The sharp singlet at 12.79
ppm (Hg) was consistent with the hydrogenolysis of the ester
group to the free acid.
a)
5
b)
20 Figure 5. 29Si NMR spectrum of Octa[2ꢀ(4ꢀcarboxyꢀ1,1’ꢀ
biphenyl)ethyl] silsesquioxane octaꢀacid in DMSOꢀd6.
Figure 4. 1H NMR spectrum of a) Octa[2ꢀ(4ꢀbenzyloxycarbonylꢀ
1,1’ꢀbiphenyl) ethenyl] silsesquioxane in CDCl3 and b) Octa[2ꢀ
(4ꢀcarboxyꢀ1,1’ꢀbiphenyl)ethyl] silsesquioxane in DMSOꢀ
d6. ꢀDMSO, ꢁH2O
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It showed a sharp singlet at ꢀ67.2 ppm in 29Si NMR, as expected
for the T3 [Si(OSi)3Csp3] environment of the eight silicon atoms
of the silsesquioxane cube. (Figure 5)
On the one hand, the rigidity of the vinylene linker in the ester
derivative and its trans configuration guided the organic pods
into a cubic symmetry with the organic substituents radiating
30 diagonally from the Si atoms around the inorganic core
(Figure 6a). This threeꢀdimensional molecular structure was
also encountered in the octaꢀstyryl silsesquioxane described
by Marciniec et al.59 On the other hand, in the case of the acid
derivative, the flexibility of the ethylene linker and, more
35 importantly, the orientation given by the hydrogen bond
network resulted in a rodꢀlike biꢀdimensional conformation of
the whole molecule with two groups of four podes oriented
into two opposite directions (Figure 6b).
In both cases, the SiꢀO bond lengths fell in the range 1.60-
40 1.63 Å, as found in other siloxanes (Table 2).39 However, the
SiꢀOꢀSi angles in the POSS core varied significantly within a
single molecule (ester or acid). As already observed in the
literature, the SiꢀOꢀSi angle fell in the range 138° ꢀ 165°
(Table 2) and the nonbonded SiꢂꢂꢂSi distances in the range 3.0
45 Å ꢀ 3.2 Å, (Table 3). These wide ranging angles are due to the
propensity of many of the structures to deform and adopt
conformations that minimize the spaces that would occur in
the lattice if they were to point ideally toward the vertices of a
cube.
X-Ray crystal structure of POSS derivatives and solid-state
assembly through hydrogen bonding
5
We were interested in studying the selfꢀassembly properties of
the octa[2ꢀ(pꢀcarboxyphenyl)ethyl] silsesquioxane. The
presence of eight carboxylic acid functions could lead to a 3D
network upon formation of intermolecular dimer structures by
10 hydrogen
bonding.
Both
the
octa[2ꢀ(pꢀ
benzyloxycarbonylphenyl)ethenyl] silsesquioxane and the
octa acid formed crystal from THF solutions. We studied the
solidꢀstate structure of the two new POSS derivatives for
comparison. The ester derivative without selfꢀassembly
15 properties had
a
rigid vinylene linker between the
silsesquioxane cube and the organic; whereas in the acid
derivative capable of selfꢀassociation the ethylene linker was
much more flexible and could adapt different conformations.
Recrystallization of both the ester and the acid derivatives
20 furnished single crystals suitable for XꢀRay diffraction. (Table
1).
Table 1. Crystallographic data
50 Table 2. Bond lengths (Å) and bond angles (deg) in octa[2ꢀ(pꢀ
octa[2-(p-
octa[2-(p-
benzyloxycarbonylphenyl)ethenyl] silsesquioxane
carboxyphenyl)ethyl] silsesquioxane (mean values).
and octa[2ꢀ(pꢀ
benzyloxycarbonylphenyl)ethenyl] carboxyphenyl)ethyl]
silsesquioxane
silsesquioxane
C76H80O29Si8, 0.6753
C4H8O
formula
C
128H104O28Si8
2314.84
octa[2-(p-
octa[2-(p-
benzyloxycarbonylphenyl)ethenyl] carboxyphenyl)ethyl]
formula
weight
crystal
system
space group
a (Å)
1754.22
triclinic
silsesquioxane
silsesquioxane
SiꢀO
1.614
1.625
triclinic
SiꢀOꢀSi
158.8
163.5
149.2
138.3
142.7
141.1
Pꢀ1
Pꢀ1
13.7763(12)
16.0926(12)
17.8036(10)
82.048(5)
72.999(6)
68.508(8)
3509.9(2)
1
10.894(3)
12.114(3)
15.800(3)
85.936(10)
76.182(9)
78.08(2)
1980.6(8)
1
b (Å)
c (Å)
Table 3. Nonbonded SiꢂꢂꢂSi distances (Å) in a) octa[2ꢀ(pꢀ
55 benzyloxycarbonylphenyl)ethenyl]
carboxyphenyl)ethyl] silsesquioxane.
(°)
(°)
silsesquioxane and
octa[2ꢀ(pꢀ
γ
(°)
volume (Å3)
Z
octa[2-(p-
benzyloxycarbonylphenyl)ethenyl]
silsesquioxane
octa[2-(p-carboxyphenyl)ethyl]
silsesquioxane
Cell
measurement
temperature
D (g/cm3)
R1
175
100
SI1ꢀSI5 = 3.172
SI3ꢀSI8 = 3.174
SI1ꢀSI8 = 3.028
SI3ꢀSI5 = 3.028
SI1ꢀSI3 = 3.095
SI8ꢀSI5 = 3.093
SI2ꢀSI1 = 3.210
SI3ꢀSI4 = 3.209
SI2ꢀSI4 = 3.085
SI3ꢀSI1 = 3.077
SI2ꢀSI3 = 3.069
SI4ꢀSI1 = 3.074
1.095
0.0989
1.471
0.0586
The compounds crystallised on an inversion center in the
25 same Pꢀ1 space group and their elemental unit exhibited
different geometries (Figure 6).
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a)
b)
Figure 6. Asymmetric units of the crystal structures of a) octa[2ꢀ(pꢀbenzyloxycarbonylphenyl)ethenyl] silsesquioxane and b)
octa[2ꢀ(pꢀcarboxyphenyl)ethyl] silsesquioxane
The different molecular architectures resulted in the distorsion
15 of the molecules (Table 3). In particular, the inorganic core of
the acid derivative was compressed in the direction of the
formation of hydrogenꢀbonded ribbons along the c axis. This
was attested by the increase of the SiꢂꢂꢂSi distances along the
a and b axises and a diminutions along the c axis compared to
20 the ester. The two different molecular conformations resulted
in two different types of supramolecular organization (Figure
7). The threeꢀdimensional conformation of the ester provided
an interpenetrated compact packing of the molecular building
blocks without any specific supramolecular interaction.
25 (Figure 7a) The shortest carbonꢀcarbon distances could be
observed (C32ꢂꢂꢂC35 = 3.777 Å and C33ꢂꢂꢂC36 = 3.760 Å on
Figure 8a) between two phenyl rings of two different styryl
functions. These were higher than the sum of the van der
Waals radius of the carbon atoms (3.54 Å) and the distance
30 expected for π−π stacking interaction.62
5
a)
The bidimensional character of the acid and the directionality
of the hydrogen bond pattern of a dimer of acid led to the
formation of hydrogenꢀbonded ribbons. (Figure 7b, Figure 8b)
b)
35 Indeed, the octaꢀacid selfꢀorganised through R2 (8) hydrogen
2
bond motif according to Etter et al. classification63. The
distance between the different oxygen atoms engaged as
hydrogen bond donors and acceptors were in the range of
hydrogenꢀbonded acid dimers (d(DꢀH…A) = d(O10ꢂꢂꢂO11) =
40 2.57(2); d(O12ꢂꢂꢂO9) = 2.63(2); d(O13ꢂꢂꢂO8) = 2.64(2);
d(O7ꢂꢂꢂO14) = 2.65 (2)). The ribbons (red and blue on Figure
5b) are aligned and the whole structured was stabilised by the
inclusion of a molecule of THF (yellow on figure 8b).
The presence of eight carboxylic acid functional groups
45 allowed to obtain ordered silicaꢀbased hybrid materials by
hydrogen bondꢀdirected assembly of the silsesquioxanes
cubes. It provided a softꢀchemical approach to crystalline
hybrid silica materials.
Figure
7.
Crystal
packing
of
a)
octa[2ꢀ(pꢀ
50
10 benzyloxycarbonylphenyl)ethenyl] silsesquioxane and b)
octa[2ꢀ(pꢀcarboxyphenyl)ethyl] silsesquioxane.
6
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a)
b)
Figure 8. Different contacts present in the structures of a) octa[2ꢀ(pꢀbenzyloxycarbonylphenyl)ethenyl] silsesquioxane and b)
octa[2ꢀ(pꢀcarboxyphenyl)ethyl] silsesquioxane (Hydrogen atoms have been omitted for clarity)
5
45 the organic layer was dried over magnesium sulfate. The solvent
was then evaporated and the crude product was purified over a
column of silica gel (eluent cyclohexane/ diethylether 95/5) to
yield a colourless oil (yield 80 %). 1H NMR (400 MHz, CDCl3) δ
(ppm) 8.09 (d, 2 H, J = 8,4 Hz) ; 7.47 (m, 4H) ; 7.40 (m, 3 H) ;
50 6.77 (m, 1H) ; 5.88 (d, 1H, J = 17.6 Hz) ; 5, 41 (d, 1 H, J = 11.2
Hz) ; 5.40 (s, 2 H). 13C NMR (100 MHz, CDCl3) δ (ppm) : 166.2
(1C) ; 142.1 (1C) ; 136.2 (1C) ; 136.1 (1C) ; 130.1 (2C) ; 129.3
(1C) ; 128.7 (2C) ; 128.3 (1C) ; 128.2 (2C) ; 126.2 (2C) 116.6
(1C) ; 66.7 (1C).
Conclusions
In conclusion, we have demonstrated the formation of a
crystalline organosilica by associating molecularly designed
precursors. Silsesquioxane cubes are useful building blocks of
10 hybrid silica based nanomaterials because of the rigid silica
framework and their easy functionalisation. We reported the
synthesis and regular arrangement of silsesquioxane cages
through hydrogen bonding. This approach should be quite
general and various supramolecular assemblies could be
15 constructed by hydrogen bonding between designed
functionalized silsesquioxane cages. It should allow the
formation of stable molecular crystals stabilized by hydrogen
bonding networks. The use of carboxylic acid groups is
interesting because of their ability to form hydrogen bonds
20 and also because of their ability to form metal carboxylate
derivatives. It may lead to hybrid metal organic silica
frameworks. Moreover the structure and properties of the
organic linkers can be varied to reach new organized
materials.
55 Benzyl 4-Bromobenzoate65. As shown above, benzyl alcohol (7.9
mmol., 1.4 eq) was added dropwise to a solution containing paraꢀ
bromobenzoic
acid
(5.5
mmol.,
1
eq),
Nꢀ(3ꢀ
dimethylaminopropyl)ꢀN′ꢀethylcarbodiimide
hydrochloride
(EDC.HCl) (7.2 mmol., 1,3 eq) and N,Nꢀdiméthylꢀ4ꢀ
60 aminopyridine (DMAP) (0.7 mmol., 0.1 eq) in dichloromethane
(60 mL). After addition, it was refluxed for 12hrs, cooled to r.t.
and washed with water (3x20 mL). The organic layer was dried
over magnesium sulphate and the solvent was removed under
vacuum. The crude product was chromatographed on a silica
65 column (eluent cyclohexane/ diethylether 9/1) to give a colourless
solid (yield 70%). 1H NMR(400 MHz, CDCl3) δ (ppm) : 7.92 (d,
2H, J = 8.8 Hz) ; 7.75 (d, 2H, J = 8.8 Hz) ; 7.47 (d, 2H, J = 8.4
Hz) ; 7. 40 (m, 3H) ; 5.35 (s, 1H). 13C NMR (100 MHz, CDCl3) δ
(ppm) : 164.9(1C) ; 131.9 (2C) ; 131.2 (2C) ; 128.7 (1C) ; 128.5
70 (2C) ; 128.2 (1C) ; 128.1 (2C) ; 127.5 (1C) ; 66.5 (1C).
Benzyl 4'-vinyl-[1,1'-biphenyl]-4-carboxylate: As shown above,
a solution of 4ꢀvinylphenylboronic acid (4.3 mmol.), benzyl 4ꢀ
bromobenzoate (4.1 mmol.) in dimethoxyethane (30 mL) was
placed in a 100 mL round bottom flask under nitrogen. After
75 20mn, an aqueous solution of potassium carbonate (3 mol. eq in
25 Experimental section
General:
All chemicals and solvents were of reagent grade. N,Nꢀ
dimethylformamide, (DMF), and tetrahydrofuran (THF) were
dried under 4Å molecular sieves. Octaꢀvinyl silsesquioxane was
30 prepared as described in the literature (ref 56). Samples were also
purchased from SigmaꢀAldrich. Nuclear magnetic resonance
spectra (NMR) were recorded on a Bruker 400 MHz in deuterated
chloroform or dimethylsulfoxyde. IR spectra were performed
with a Spectrum 100 FTꢀIR spectrometer from Perkin Elmer.
34
mL
of
water)
was
added,
followed
by
tetrakis(triphenylphosphine)palladium(0) (0.07 mmol). The
mixture was refluxed for 12hrs. The solvent was then removed
under vacuum and the remaining aqueous phase was extracted
80 with ethyl acetate. The organic layer was dried over anhydrous
magnesium sulphate. After removal of the solvent, the crude
35
Synthetic procedures:
Benzyl-4(vinylbenzoate)64 . In a 100 mL round bottom flask
under nitrogen, paraꢀvinylbenzoic acid (7 mmol., 1 eq), Nꢀ(3ꢀ
product was purified over
a
silica column (eluent
dimethylaminopropyl)ꢀN′ꢀethylcarbodiimide
hydroꢀchloride
cyclohexane/dichloromethane: 6/4). The pure product was
obtained as a colourless solid (yield 70%). H NMR (400 MHz,
85 DMSO d-6)) δ (ppm) : 8.06 (d, 2H, J = 8.4 Hz) ; 7.85 (d, 2H, J =
8.4 Hz) ; 7.73 (d, 2H, J = 8.4 Hz) ; 7.60 (d, 2H, J = 8.4 Hz) ; 7.48
(d, 2H, J = 7.2 Hz) ; 7.40 (m, 3H) ; 6.79 (m, 1H), 5.92 (d, 1H, J =
17.6 Hz) ; 5.38 (s, 2H) ; 5.32 (d, 1H, J = 10.8 Hz). 13C NMR (100
1
40 (EDC.HCl) (8,5 mmol. 1,2 eq) and N,Nꢀdiméthylꢀ4ꢀ
aminopyridine (DMAP) (0,7 mmol. 0,1 eq) were dissolved in
dichloromethane (60 mL). Benzyl alcohol (8.5 mmol., 1.2 eq)
was then added dropwise. The mixture was stirred and refluxed
for 3hrs. After cooling, it was washed with water (3x20 mL) and
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DOI: 10.1039/C6CE02369J
MHz, DMSO d-6)) δ (ppm) : 165.9 (1C) ; 144.8 (1C) ; 138.6
and stirred for 48h. The advancement of the reaction was
(1C) ; 137.7 (2C) ; 136.7 (1C) ; 136.5 (1C) ; 130.4 (2C) ; 129.0 60 followed by 1H NMR. The catalyst was then removed by
(2C) ; 128.9 (1C) ; 128.6 (1C) ; 128.4 (2C) ; 127.7 (2C) ; 127.3
(2C) ; 115.6 (1C)
filtration and the solvent was removed. The crude product was
obtained as highly viscous colourless oil. It was soluble in THF
and recrystallized from a THF/heptane mixture.
5
Metathesis reactions:
Octa[2-(p-carboxyphenyl)ethyl] silsesquioxane. The compound
In a round bottom flask under nitrogen, octaꢀvinyl T8 POSS (0.8 65 was obtained as a colourless powder (yield 80%). Mp: 280°C
mmol., 1 eq), the functionalized styrene derivative (7.2 mmol., 9
eq) and the Grubbs’I catalyst: benzylideneꢀbis(tricyclohexylꢀ
(decomposition); IR spectrum (ATR) ѵ (cmꢀ1): 3200ꢀ2600
(broad band), 1683, 1610, 1603, 1514, 1420, 1297, 1288, 1081,
1017, 939, 837, 803, 797, 751, 695. 1H NMR (400 MHz, DMSO
d-6) δ (ppm): 12.79 (s, 1H); 7.85 (d, 2 H, J = 8.2 Hz) ; 7.31 (d, 2
10 phosphine), dichlororuthenium [RuCl2(=CHPh)(PCy3)2] (0.18
mmol., 0.15 eq) were placed in solution with 60 mL of
dichloromethane. The mixture was stirred at 55 °C for 12hrs. The 70 H, J = 8.2 Hz); 2.67 (m, 2 H); 0.88 (m, 2 H). 13C NMR (100
advancement of the reaction was followed by 1H NMR.
MHz, DMSO d-6) δ (ppm) : 167.7 (1C), 148.9 (1C), 129.8 (2C) ;
128.9 (1C), 128.5 (2C) ; 28.8 (1C) ; 12.9 (1C). 29Si NMR (79.5
MHz, DMSO d-6) δ (ppm) : ꢀ 67.3. MS (Maldy-Tof in positive
ionisation) m/z (M+Na) = m/z 1631.2, calc 1631.23. ; MS
Octa[2-(p-benzyloxycarbonylphenyl)ethenyl]
silsesquioxane.
15 The crude mixture was poured into 150 mL of methanol. The
white precipitate was dissolved in the minimum quantity of
dichloromethane. It was chromatographed on a silica gel column 75 (Maldy-Tof in negative ionisation): (MꢀH) = obsd 1607.1, calc
(eluent cyclohexane / dichloromethane (2/8). A colourless solid
was isolated and recrystallized from mixture of
1607.21; Analysis: calc. : % C : 53.71 ; % H : 4.51 ; found : %
C : 53.56 ; % H : 4.57.
a
Sodium octa[2-(p-carboxylatephenyl)ethyl] silsesquioxane. 0.66
mmol. of sodium bicarbonate was added to a suspension of the
80 octaꢀacid (0.08 mmol.) in 50 ml of water. After heating at 60°C
for 12hrs, 30ml of toluene were added to the homogeneous
solution. The solid that formed (yield 80%) was isolated after
evaporation of the solvents. IR spectrum (ATR) ѵ (cmꢀ1):
2962,1674,1590, 1567, 1397, 1213, 1111, 997, 852, 781, 763,
20 dichloromethane/cyclohexane to yield octa[2ꢀ(pꢀcarboxyphenyl)
ethenyl] silsesquioxane octaꢀbenzyl ester (yield 48 %). Mp:
115°C; IR spetrum (ATR) ѵ (cmꢀ1) : 3066, 3034, 2998, 2936,
2851, 1714, 1605, 1567, 1498, 1455, 1410, 1375, 1269, 1221,
1202, 1159, 1076, 1015, 990, 913, 836, 830, 829, 748, 695, 654;
25 1H NMR (400 MHz, CDCl3) δ (ppm) : 8.07 (d, 2 H, J = 8 Hz) ;
7.55 (d, 2 H, J = 8.4 Hz) ; 7.40 (m, 6 H) ; 6.43 (d, 1 H, J = 19.2
Hz) ; 5.38 (s, 2H); 13C NMR (100 MHz, CDCl3) δ (ppm) : 166.0
(1C) ; 148.4 (1C) ; 141.3 (1C) ; 136.0 (1C) ; 130.5 (1C) ; 130.2
(2C) ; 128.7 (2C) ; 128.4 (1C) ; 128.3 (2C) ; 126.9 (2C) ; 120.0
30 (1C) ; 66.9 (1C). 29Si NMR (79.5 MHz, CDCl3) δ (ppm) : ꢀ 78.8.
MS (Maldy-Tof in positive ionisation) m/z (M+Na) = obsd
2335.4, calc 2335,48; Analysis : calc. : % C : 66.41 % H : 4.53 ;
% ; found: % C : 66.26 ; % H : 4.54.
1
85 702; H NMR (400 MHz, D2O) δ (ppm): 7.81 (d, 2 H, J = 8,.4
Hz) ; 7.37 (d, 2 H, J = 8.2 Hz); 2.81 (m, 2 H); 1.03 (m, 2 H). MS
(Maldy-Tof in positive ionisation) m/z (M+Na) = obsd 1807
calc 1807.08; M = 1785; MꢀNa = 1763.3; Mꢀ2Na = 1741.3; Mꢀ
3Na = 1720.3; Mꢀ4Na = 1697.3; Mꢀ5Na = 1675.3; Mꢀ6Na =
90 1653.3; Mꢀ7Na = 1631.3
Octa[2-(4-carboxy-1,1’-biphenyl)ethyl] silsesquioxane.
IR spectrum (ATR) ѵ (cmꢀ1): 3200ꢀ2600 (broad band), 1681,
1607, 1578, 1527, 1498, 1447, 1427, 1302, 1289, 1083, 1005,
822, 814, 769, 694. 1H NMR (400 MHz, DMSO d-6) δ (ppm) :
95 12.96 (s, 1H) ; 7.95 (d, 2H, J = 8.4 Hz) ; 7.64 (d, 2H, J = 8 Hz);
7.51 (d, 2H, J = 8.4 Hz) ; 7.22 (d, 2H, J = 8 Hz) ; 2.66 (m, 2H);
0.91 (m, 2H). 29Si NMR (79.50 MHz, CDCl3) δ (ppm): ꢀ 67.2
MS (Maldy-Tof in negative ionisation) m/z (MꢀH) = obsd
2215.5, calc 2215.48.
Octa[2-(4-benzyloxycarbonyl-1,1’-biphenyl)
ethenyl]
35 silsesquioxane. As described above, the crude product was
obtained as a white precipitate upon pouring the crude reaction
mixture in 150 mL of methanol. It was purified by column
chromatography (silica column, eluent cyclohexane
dichloromethane (2/8). The colourless solid collected, was
40 recrystallized from mixture of solvents
/
a
(dichloromethane/cyclohexane), in a 75 % yield. Mp: 180°C ; IR
spectrum (ATR) ѵ (cmꢀ1) : 3031, 2926, 2851, 1714, 1606, 1575,
1555, 1523, 1495, 1455, 1421, 1379, 1376, 1266, 1203, 1158,
1076, 989, 988, 912, 831, 830, 798, 765, 700, 695. 1H NMR (400
45 MHz, CDCl3) δ (ppm) : 8.16 (d, 2 H, J = 8.4 Hz) ; 7.65 (m, 6 H) ;
7.40 (m, 6 H) ; 6.35 (d, 1 H, J = 19.2 Hz) ; 5.42 (s, 2H). 13C
NMR (100 MHz, CDCl3) δ (ppm) : 166.3 (1C) ; 148.6 (1C) ;
144.9 (1C) ; 140.5 (1C) ; 137.2 (1C) ; 136.1 (1C) ; 130.3 (2C) ;
129.2 (1C) ; 128.7 (4C) ; 128.3 (1C) ; 128.2 (2C) ; 127.6 (2C) ;
50 126.9 (2C) ; 118.0 (1C) ; 66.9 (1C). 29Si NMR (79.5 MHz,
CDCl3) δ (ppm) : ꢀ 78.3. Analysis : calc. : % C : 72.30 % H :
4.69 ; % ; found : % C : 70.63 % H : 4.64.
100 Crystal preparation and X-ray diffraction:
a) Octa[2-(p-benzyloxycarbonylphenyl)ethenyl]
silsesquioxane
The octaꢀester was dissolved in a minimum of tetrahydrofuran in
a testꢀtube and placed in a Schlenk tube containing another testꢀ
105 tube filed with hexane. Crystals were grown by slow diffusion of
hexane vapours at room temperature. X-ray structure
determination. Crystal evaluation and data collection were
performed on
a
Rigaku OxfordꢀDiffraction GeminiꢀS
diffractometer with sealedꢀtube MoꢀK radiation using the
110 CrysAlis Pro programme66. The same programme was used for
the integration of the data using default parameters, for the
empirical absorption correction using spherical harmonics
employing symmetryꢀequivalent and redundant data, and the
correction for Lorentz and polarization effects. The crystal
115 structure was solved using the ab-initio iterative charge flipping
method with parameters described elsewhere67 using the
Hydrogenation reactions:
55 The above POSS benzyl ester derivatives (0.18 mmol., 1 eq) were
dissolved in 150 mL of THF. The catalyst 10% Pd/C (0.02
mmol., 0.10 eq) was added and the solution was stirred
vigorously. The flask was then connected to a hydrogen balloon
8
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Superflip programme68,69 and it was refined using fullꢀmatrix
60 Therefore, due to the small scattering volume of the crystal,
absorption effects due to the crystal itself were expected to be
very weak.
leastꢀsquares procedures as implemented in CRYSTALS70 on all
independent reflections with I>2 (I).
Although of reasonable size, the diffracting power of this crystal
was rather low. Beyond 0.9 Å there was no significant diffraction
spots and it was therefore decided to cut the data at 0.9 Å for
refinement. In order to regularize the geometry of some phenyl
rings distance restraints were used and one phenyl ring was
refined as a rigid body. The solvent molecules, probably two,
5
10 were heavily disordered and the Squeeze procedure, as
implemented in PLATON,71 was used to take into account their
contribution to the diffracted signal. The squeezed volume was
902 Å3 and the number of solvent electrons 196 per unit cell.
Figure 9. Crystal of octa[2-(p-carboxyphenyl)ethyl]
65 silsesquioxane mounted on a nylon loop embedded with Paratone
oil from Hampton Research.
The H atoms were all located in a difference map, but
15 repositioned geometrically. They were initially refined with soft
restraints on the bond lengths and angles to regularise their
geometry (CꢀꢀꢀH in the range 0.93ꢀ0.98 Å) and Uiso(H) (in the
range 1.2ꢀ1.5 times Ueq of the parent atom). Then their positions
were refined with riding constraints72. Crystal data ꢀ formula:
20 C128H104O28Si8, moiety: C128H104O28Si8, T = 175 K, Mr = 2314.84
The crystal structure of the nonꢀhydrogen atoms was determined
by direct methods using SHELXS97.75 Refinement was carried
out with SHELXL97. After
a few leastꢀsquared cycles,
70 anisotropic displacement parameters were employed on all Si, O
and C atoms. The hydrogen atoms were placed in idealised
positions with CꢀH = 0.95 Å during the refinement. Rings were
refined without any constraints. SHELXS97 and SHELXL97
were used through the WinGX Graphical User Interface.76
75 Crystal data for octa-acid: C76H80O29Si8, 0.6753 C4H8O
triclinic, Pꢀ1 (no.2), a = 10.894(3) Å, b = 12.114(3) Å, c =
15.800(3) Å, α = 85.936(10)°, β = 76.182(9)°, γ = 78.08(2)°, V =
1980.6 (8) Å3, T = 100(2) K, R1 = 0.0586 for 4132 independent
observed reflections [F > 4σ(Fo)], S = 1.026. Data collection: ϕ
80 scans, 0.3° oscillation range, 1 pass of 0.04 s exposure time per
image, 1200 images, λ = 0.8729 Å, 7/8 multibunch mode.
1
gmol , crystal size = 0.15x0.23x0.31 mm3, triclinic, spacegroup
P-1, a = 13.7763(12) Å, b = 16.0926(12) Å, c = 17.8036(10) Å,
α
= 82.048(5)º,
β
= 72.999(6)º,
γ
= 68.508(8)º, V = 3509.9(2) Å3, Z
3
1
= 1, ρcalcd = 1.095 gcm ,
ꢀ
= 0.140 mm , Θmax = 27.861º,
25 experimental resolution = 0.88 Å, 13712 reflections measured,
13712 unique, 7005 with I>2 (I), Rint = 0.041, < (I)/I> = 0.0587,
697 refined parameters, R1(I>2 (I)) = 0.0989, wR2(I>2 (I)) =
0.1254, R1(all data) = 0.1262, wR2(all data) = 0.1518, GOF =
σ
σ
σ
σ
3
1.1368, ꢁρ(min/max) = ꢀ0.63/1.10 eÅ .
30
b) Octa[2-(p-carboxyphenyl)ethyl] silsesquioxane
The crystals of the octaꢀacid were grown by slow evaporation of
a tetrahydrofuran solution. X-ray structure determination Data
Acknowledgment. This study was funded by ANR "Projet
blanc ANRꢀ13ꢀBS07ꢀ0004 ꢀ CrystOS". The authors gratefully
acknowledge financial support from the “Ministère de la
85 Recherche” and the CNRS. We acknowledge the allocation of
beam time for the experiment at the ID23ꢀ2 beamline at the
European Synchrotron Radiation Facility–ESRF, Grenoble.
35 collection. Because of the small crystal volume and small
scattering power, synchrotron radiation was required for structure
determination. Microdiffraction patterns were recorded at the
ID23ꢀ2 structural biology microfocus beamline (European
Synchrotron Radiation Facility – ESRF, Grenoble) where the
40 beam was focused down to approximately 8 µm in diameter.73
Each sample was mounted on a nylon loop embedded with
Paratone oil from Hampton Research (Figure 9). Several crystals
were tested to select a single crystal of suitable quality for data
collection. The best acid crystal was approximately 60x20x5 µm3.
45 Data were collected by the oscillation technique using a twoꢀ
dimensional pixel detector (DECTRIS Pilatus3 2M;
~253.7x288.8 mm2, 1475 x 1679 pixels and a pixel size of 0.172
x 0.172 µm2). The measurements were carried out at a fixed
temperature of 100 (2) K using an Oxford 700 Cryostream
50 device. X-ray diffraction. Structure Solution and Refinement.
The frames were indexed and the reflections integrated using the
XDS software suite.74 Each reflection intensity was corrected
from the action of intensity loss due to air absorption. XDS (in
the CORRECT step) applied Lorentz and polarization factors as
55 well as factors that partially compensate from damage and
absorption effects to intensities and standard deviations of all
reflections. These factors were determined from many symmetryꢀ
equivalent reflections usually found in the data images so that
their integrated intensities become as similar as possible.
Notes and references
a
Institut Charles Gerhardt de Montpellier, Laboratoire AM2N, UMR
90 CNRS 5253, ENSCM 8 rue de l’Ecole Normale, 34296 Montpellier Cedex
5 (France)
joel.moreau@enscm.fr, olivier.dautel@enscm.fr
b
ESRF—The European Synchrotron 71, Avenue des Martyrs Grenoble
(France)
c
95 Institut Européen des Membranes, CNRS UMR 5635, Université de
Montpellier, Place E. Bataillon 34095 Montpellier Cedex 5 (France)
† CCDC 1508340 and CCDC 1509522 contain the supplementary
crystallographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
100 www.ccdc.cam.ac.uk/data_request/cif.
Electronic
Supplementary
Information (ESI) available: [Experimental Details, 1H, 13C, 29Si NMR
spectra and Maldy spectra].
1 J. Livage. Chemica Scripta, 1988, 28, 9ꢀ13.
2 J. Rouxel, Chemica Scripta, 1988, 28, 33ꢀ40
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DOI: 10.1039/C6CE02369J
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CrystEngComm
View Article Online
DOI: 10.1039/C6CE02369J
Hydrogen Bond-Directed Assembly of Silsesquioxanes Cubes:
Synthesis of Carboxylic Acid POSS Derivatives and the Solid
State Structure of Octa[2-(p-carboxyphenyl)ethyl] Silsesquioxane†
Voisin Doria, Flot David, Van der Lee Arie, Dautel Olivier and Moreau Joel J. E.
Table of Contents Entry
A crystalline organo-silica network was constructed through a self-organization process by
assembling organic functionalised silsesquioxane cages capable of hydrogen bonding.