Article

Synthesis and Advanced NMR Characterization of Ordered 3D

Reticular Materials with PolySilicate Nodes and Hydrophobic
OrganoSilicone Linkers
Jelle Jamoul 1,† , Sambhu Radhakrishnan 1,2,† , Maarten Houlleberghs 1 , C. Vinod Chandran 1,2 , Aline Vits 1 ,
Pasquinel Weckx 1,2 , Sam Smet 1 , Daniel Arenas Esteban 3 , Sara Bals 3 , Johan A. Martens 1
and Eric Breynaert 1,2, *

1 Centre for Surface Chemistry and Catalysis—Characterization and Application Team (COK-KAT),
KU Leuven, Celestijnenlaan 200F Box 2461, 3001 Heverlee, Belgium
2 NMRCoRe—NMR/X-Ray Platform for Convergence Research, KU Leuven, Celestijnenlaan 200F Box 2461,
3001 Heverlee, Belgium
3 Electron Microscopy for Materials Science (EMAT), University of Antwerp, Groenenborgerlaan 171,
2020 Antwerp, Belgium
* Correspondence: [email protected]
† These authors contributed equally to this work.

Abstract: This work describes the synthesis of ordered 3D siloxane-silsesquioxane reticular

materials with silicate D4R cubes (Si8O208− ), harvested from a sacrificial tetrabutylammonium
cyclosilicate hydrate (TBA-CySH) precursor, interlinked with octyl and dicyclopentyl (Cp2)
hydrocarbon functionalities in a one-step synthesis with organodichlorosilanes. Advanced
solid-state NMR spectroscopy allowed us to unravel the molecular order of the nodes and their
interconnection by the silicone linkers. In the case of octyl-methyl silicone linkers, changing the
silane-to-silicate ratio in the synthesis allowed for tuning the length of the linker between the
nodes. With dicyclopentyl linkers, the addition of dimethyldichlorosilane was essential to enable
the formation of a reticular network. The resulting materials contained mixed, dimeric silicone
Academic Editors: Yan’an Gao and
Qi Chen
linkers, i.e., Si8-O-Si(Me2)-O-Si(Cp2)-O-Si8.
Received: 18 December 2024
Keywords: reticular material synthesis; silicate-silicone hybrids; POSiSils; cyclosilicate
Revised: 3 January 2025
Accepted: 6 January 2025
hydrate; siloxane-silsesquioxane; octyl-methyldichlorosilane; dicyclopentyldichlorosilane;
Published: 8 January 2025 advanced multidimensional NMR characterization; 29 Si NMR
Citation: Jamoul, J.; Radhakrishnan,
S.; Houlleberghs, M.; Chandran, C.V.;
Vits, A.; Weckx, P.; Smet, S.; Arenas
Esteban, D.; Bals, S.; Martens, J.A.; 1. Introduction
et al. Synthesis and Advanced NMR Siloxane-silsesquioxane resins incorporating cubic oligomeric silicate cage units (T8
Characterization of Ordered 3D
or Q8 ) are very popular for constructing covalently linked hybrid porous polymers with
Reticular Materials with PolySilicate
Nodes and Hydrophobic
tunable structures and multifunctional properties. The cubic symmetry of the Si8 O12 double
OrganoSilicone Linkers. Molecules 4-ring (D4R), its intrinsic structural rigidity, and nanosized dimensions (1.2–1.4 nm) render
2025, 30, 228. https://doi.org/ it an attractive supramolecular unit. Applications of hybrid polymers incorporating D4R
10.3390/molecules30020228 cage organosiloxanes include adsorption and storage of gasses, catalysis, water treatment,
Copyright: © 2025 by the authors. drug delivery, and sensing applications. Used as nanofillers of organic polymers, they serve
Licensee MDPI, Basel, Switzerland. to enhance the thermal, mechanical, and electrical properties of the final material [1–10].
This article is an open access article Depending on their peripheral chemical functionalities, D4R silicate units are identified
distributed under the terms and under different names (Figure 1). D4Rs terminated with organic groups ([R8 -Si8 O12 ]
conditions of the Creative Commons
units with R = H, alkyl, aryl, etc.) are typically referred to as polyhedral oligomeric
Attribution (CC BY) license
(https://creativecommons.org/
silsesquioxanes (POSS). When R is O− or OH, they are identified as cyclosilicates, and if R
licenses/by/4.0/). is a siloxy group, they are called spherosilicates. POSS D4R units are typically synthesized

Molecules 2025, 30, 228 https://doi.org/10.3390/molecules30020228

 Depending on their peripheral chemical functionalities, D4R silicate units are
identified under different names (Figure 1). D4Rs terminated with organic groups ([R8-
Molecules 2025, 30, 228 Si8O12] units with R = H, alkyl, aryl, etc.) are typically referred to as polyhedral oligomeric 2 of 14
silsesquioxanes (POSS). When R is O- or OH, they are identified as cyclosilicates, and if R
is a siloxy group, they are called spherosilicates. POSS D4R units are typically synthesized
by hydrolyzing
hydrolyzingand andcondensing
condensing alkoxy- or chlorosilanes.
alkoxy- This results
or chlorosilanes. This in inefficient
results synthesis
in inefficient
conditions and requires the implementation of lengthy purification to
synthesis conditions and requires the implementation of lengthy purification to eliminateeliminate silicate
byproducts, especially
silicate byproducts, when small
especially whenR-groups are targeted
small R-groups [11–13].[11–13].
are targeted Cyclosilicate D4Rs
Cyclosilicate
can be harvested from cyclosilicate hydrates (CySHs). CySHs are
D4Rs can be harvested from cyclosilicate hydrates (CySHs). CySHs are templated hydrate templated hydrate
crystals
crystals comprising
comprisingsilicate building
silicate blocks,
building i.e., D3R,
blocks, D4R, and
i.e., D3R, D4R,D6Randunits,
D6Rnext to template
units, next to
molecules and water [14–17]. Spherosilicate D4Rs can be obtained
template molecules and water [14–17]. Spherosilicate D4Rs can be obtained either fromeither from POSS or
from
POSScyclosilicate hydrates [13,17,18],
or from cyclosilicate with the latter
hydrates [13,17,18], withroute circumventing
the latter the drawbacks
route circumventing the
of POSS syntheses [7,8,17,19]. When synthesizing spherosilicates from
drawbacks of POSS syntheses [7,8,17,19]. When synthesizing spherosilicates from CySH CySH precursor
crystals,
precursorthe template
crystals, theused is extremely
template impactful impactful
used is extremely as it determines the crystalthe
as it determines structure
crystal
and, consequently, the amount of crystal water incorporated. Limited
structure and, consequently, the amount of crystal water incorporated. Limited water water contents are
preferred
contents areas they enable the
preferred selective
as they conversion
enable of cyclosilicates
the selective conversionintoofspherosilicate
cyclosilicatesunits
into
using chloro- or dichlorosilanes, which otherwise react with superfluous
spherosilicate units using chloro- or dichlorosilanes, which otherwise react with water to form
silicone polymers
superfluous waterrather
to form than spherosilicates
silicone polymers [7].
rather than spherosilicates [7].

Figure 1. Chemical structure of the silicate cube (D4R) (left) and specification of peripheral chemical
Figure 1. Chemical structure of the silicate cube (D4R) (left) and specification of peripheral chemical
functionality (R) differentiating the material classes containing this building block (right).
functionality (R) differentiating the material classes containing this building block (right).
POSS D4Rs can be coupled into hybrid materials using a multitude of linkers. Purely
POSS
organic D4Rs can
linkages can bebe coupled
created by into hybrid materials
metal-catalyzed using a multitude
cross-coupling of linkers.
reactions Purely
(Sonogashiri
organic linkages can be created by metal-catalyzed cross-coupling reactions
and Friedel-Craft condensations), examples ranging from large aromatic to simple aliphatic (Sonogashiri
and Friedel-Craft
hydrocarbons condensations),
(ethyl). Such syntheses examples
typicallyranging fromoctahydrido-
start from large aromatic and to simple
octavinyl
aliphatic hydrocarbons (ethyl). Such syntheses typically start from
POSS units (R = H of C2 H3 , respectively) or their functionalized equivalents [10,20,21]. octahydrido- and
octavinyl
Using POSS units (R = Hasof
diethylhydroxylamine C2H3, respectively)
a catalyst, or their functionalized
H-POSS or spherosilicate equivalents
equivalent units can be
[10,20,21]. Using diethylhydroxylamine as a catalyst, H-POSS or spherosilicate
interlinked with silanol-terminated silanes (OH-(SiR2 -O)n -H with R = phenyl and methyl) equivalent
units
by can be interlinked
dehydrogenative with silanol-terminated
condensation silanes
[9,22]. This yields (OH-(SiR
materials 2-O)pure
with n-H with R = linkers.
silicone phenyl
and methyl) by dehydrogenative condensation [9,22]. This yields materials
Using organic diols, the same catalyst also enables the generation of Si-O-C bonds, yielding with pure
silicone linkers.
materials Usingorganic
with purely organiclinkers
diols, the same catalyst also enables the generation of Si-O-
[4,23].
C bonds, yielding materials with purely
CySHs can be obtained with a multitude organic linkers [4,23].
of quaternary ammonium species with at least
CySHssubstituent
one methyl can be obtained with a multitude of (TMA),
(e.g., tetramethylammonium quaternary ammonium
choline, species with at
1,1-dimethylpiperidinium,
phenyltrimethyl- and benzyltrimethylammonium, piperazinium derivatives, etc.),choline,
least one methyl substituent (e.g., tetramethylammonium (TMA), 1,1-
tetrabutylam-
dimethylpiperidinium,
monium phenyltrimethyl-(HMI)
(TBA), and hexamethyleneimine and benzyltrimethylammonium,
[14,17,19,24–26]. Using TMA piperazinium
as a template,
derivatives, etc.), tetrabutylammonium3 (TBA), and hexamethyleneimine
TMA-CySH nucleates as soon as Q 8 levels reach a threshold of ≈32 % of the total silicate (HMI)
[14,17,19,24–26].
species [27]. FurtherUsing
growthTMA as aTMA
yields template, TMA-CySH nucleates as soon as Q 8 levels
8Si8O20.65H2O, incorporating 65 water molecules per
3

reach a threshold of ≈32 % of the total silicate

D4R in the crystal structure. This high water content negatively species [27]. Further
affects the use growth
of TMA-CySHyields
TMA
for 8Si8O20.65H2O,with
functionalization incorporating
chlorosilanes 65due
water molecules per
to water-induced D4Rpolymerization,
silane in the crystalresulting
structure.
in
This high water content negatively affects the use of TMA-CySH for
lowered synthesis efficiency and uncontrollable network propagation [26]. HMI-CySH contains functionalization
with
12 chlorosilanes
water molecules per duecube
to water-induced
and can successfully silanebepolymerization, resulting in lowered
reacted with dimethyldichlorosilane to
yield a PolyOligoSiloxySilicone (POSiSil) material featuring monomeric dimethylsilicone-bridged
silicate cubes (PSS-1) [7]. Using TBA-CySH, with only 5.33 water molecules per D4R unit, selective
reaction with dimethyldichlorosilane converts the D4R units into octakis(dimethylsilyl chloride)
spherosilicates. The resulting terminal Si-Cl bonds, render these spherosilicates ideal as building
 bridged silicate cubes (PSS-1) [7]. Using TBA-CySH, with only 5.33 water molecules per
D4R unit, selective reaction with dimethyldichlorosilane converts the D4R units into
octakis(dimethylsilyl chloride) spherosilicates. The resulting terminal Si-Cl bonds, render
Molecules 2025, 30, 228 3 of 14
these spherosilicates ideal as building units for further reaction [17]. Self-polymerization
of this chlorinated precursor block in the presence of traces of water yields PSS-2, a 3D
POSiSil material [8]. The reaction of the chlorinated precursor with aliphatic alkanediols
units for further reaction [17]. Self-polymerization of this chlorinated precursor block in the
allows for the synthesis of a isoreticular family of PolySilicate Porous Organic Polymers
presence of traces of water yields PSS-2, a 3D POSiSil material [8]. The reaction of the chlorinated
(PSiPOPs), featuring Si-O-C connections between the polysilicate node and the linkers
precursor with aliphatic alkanediols allows for the synthesis of a isoreticular family of PolySilicate
[28].
Porous Organic Polymers (PSiPOPs), featuring Si-O-C connections between the polysilicate node
Hitherto, POSiSil materials only featured small (di)methyl silicone bridges.
and the linkers [28].
Consequently, in applications, they were no match for POSS-based hybrid siloxane-
Hitherto, POSiSil materials only featured small (di)methyl silicone bridges. Conse-
silsesquioxane resins incorporating long-chain organic groups. The literature has shown
quently, in applications, they were no match for POSS-based hybrid siloxane-silsesquioxane
that such hydrocarbon functionalities enable the adsorption of aromatic solutes, such as
resins incorporating long-chain organic groups. The literature has shown that such hy-
naproxen and bisphenol, from various media, including water and milk samples, and
drocarbon functionalities enable the adsorption of aromatic solutes, such as naproxen
enhance the conductivity of Li+ ions in solid-state battery applications [29–32]. When
and bisphenol, from various media, including water and milk samples, and enhance the
coordinated with +metal clusters, these siloxane-silsesquioxane hybrid materials function
conductivity of Li ions in solid-state battery applications [29–32]. When coordinated with
as catalysts for C-C cross-coupling reactions, facilitating the synthesis of complex and fine
metal clusters, these siloxane-silsesquioxane hybrid materials function as catalysts for C-C
chemicals [33,34].
cross-coupling reactions, facilitating the synthesis of complex and fine chemicals [33,34].
Recently, POSiSil-like octyl-methyl functionalized silicate-silicone hybrids were
Recently, POSiSil-like octyl-methyl functionalized silicate-silicone hybrids were syn-
synthesized by reacting TMA-CySH with dichloromethylsilane ((CH3)Si(H)Cl2). Grafting of
thesized by reacting TMA-CySH with dichloromethylsilane ((CH3 )Si(H)Cl2 ). Grafting of
the Si-H groups in the resulting spherosilicate with 1-octene yielded octyl-functionalized
the Si-H groups in the resulting spherosilicate with 1-octene yielded octyl-functionalized
silicone linkers [35]. Structurally incorporating similar siloxane-silsesquioxane resins into
silicone linkers [35]. Structurally incorporating similar siloxane-silsesquioxane resins into
polypropylene polymer blends was shown to improve their flame retardancy [36].
polypropylene polymer blends was shown to improve their flame retardancy [36]. However,
However, the unfavorable water content of TMA-CySH renders this synthesis route highly
the unfavorable water content of TMA-CySH renders this synthesis route highly inefficient
inefficient with respect to Si [35,37–40]. The present work presents new silicate-silicone
with respect to Si [35,37–40]. The present work presents new silicate-silicone hybrid ma-
hybrid materials with methyloctyldisiloxane and mixed dimethyl-dicyclopentyl disiloxane
terials with methyloctyldisiloxane and mixed dimethyl-dicyclopentyl disiloxane linkers,
linkers, synthesized in an efficient manner based on the reaction of TBA-CySH with long-
synthesized in an efficient manner based on the reaction of TBA-CySH with long-chain and
chain and bulky dichlorosilanes. Rather than anchoring octyl and cyclopentyl groups on
bulky dichlorosilanes. Rather than anchoring octyl and cyclopentyl groups on siloxane
siloxane linkages by post-synthetic grafting of a spherosilicate, the new synthesis strategy
linkages by post-synthetic grafting of a spherosilicate, the new synthesis strategy directly
directly incorporates the bulky organic groups during the initial reaction with cyclosilicate
incorporates the bulky organic groups during the initial reaction with cyclosilicate hydrate,
hydrate, while also avoiding extensive generation of side products. Implementing this
while also avoiding extensive generation of side products. Implementing this strategy
strategy with octylmethyldichlorosilane or a mixture of dimethyl- and
with octylmethyldichlorosilane or a mixture of dimethyl- and dicyclopentyldichlorosi-
dicyclopentyldichlorosilanes yielded reticular materials coined PSS-3 and PSS-4,
lanes yielded reticular materials coined PSS-3 and PSS-4, respectively (Figure 2). These
respectively (Figure 2). These new POSiSil materials were characterized1 extensively with
new POSiSil materials were characterized extensively with quantitative H and 29 Si NMR
quantitative 1H and 29Si NMR spectroscopy, TGA, SEM, and HAADF-STEM.
spectroscopy, TGA, SEM, and HAADF-STEM.

Overview of
Figure 2. Overview of new
new POSiSil
POSiSil materials
materials presented
presented in
in this
this work,
work, PSS-3
PSS-3 and PSS-4, with their
respective silicate and silicone composition. Silicate cubes are sourced from aa TBA-CySH
respective silicate and silicone composition. Silicate cubes are sourced from TBA-CySH crystal.
crystal.

2. Results and Discussion

2.1. Synthesis and Structure Elucidation of PSS-3
Octyl-methyl POSiSil samples (PSS-3) were synthesized using different concentrations
of n-octyl(methyl)dichlorosilane, by adding liquid silane to vacuum-dried TBA-CySH
suspended in dry THF. Based on the PSS-2 synthesis protocol, 10 silane molecules are
needed per silicate cube for the complete conversion of CySH to PSS. Hereafter, this ratio is
referred to as a stoichiometric amount of silane [8]. Three concentrations, i.e., 50% deficit,
Molecules 2025, 30, 228 4 of 14

stoichiometric, and 50% excess of n-octyl(methyl)dichlorosilane were added. After evapora-

tion of the high-boiling silane and THF at 90 ◦ C and vacuum, intermediate spherosilicates
were resuspended in THF and converted to octyl-methyl POSiSils by hydrolysis with water
vapor. X-ray diffraction of PSS-3 identified the material as amorphous (Figure S1). As
the reaction of chlorosilanes with silicate cubes of CySH in THF progresses, the hydrogen
bonding network of the initial CySH crystals is disrupted. This liberates individual silicate
cubes from the LTA-like topology of the starting CySH crystals [17]. While the material is
reticular, the intrinsic flexibility of the silicone linkers bridging the silicate cubes renders
the final POSiSil materials amorphous [8]. Consequently, NMR spectroscopy is required
to elucidate the local chemical order and structure of PSS-3 (Figure 3). Previous reports
on silicate-silicone hybrid materials with octyl-methyl functionalities synthesized from
TMA-CySH, limited their characterization to qualitative trends observed with infrared
spectroscopy and direct excitation 29 Si NMR. The length of silicone linkers was estimated
from the initial silane concentration, but given the high water content of TMA-CySH,
promoting random polymerization of the silane, a more accurate quantification of the linker
length is recommended [35,37].
29 Si NMR spectroscopy allows for differentiation between Si atoms of silicate cubes (Q3

and Q4 ) and silicone linkers (D2 ), resonating around −100 to −110 ppm and between −15
and −23 ppm, respectively (Figure 3a). The relative concentrations of these different 29 Si
species can be derived from the spectral decomposition of the 29 Si NMR spectra (Figure S3
and Table S1) [41,42]. The results are summarized in Figure 3e. Efficient silylation of the
silicate cubes with octyl-methyl silicone moieties is confirmed by the strong Q4 Si signal
(Figure 3d). Since Si D4R cubes cannot directly fuse, the Q4 /Q3 ratio represents an efficiency
factor for the conversion of Q3 Si in CySH to Q4 Si by reaction with silane. Based on the
structure of PSS-2, exhibiting disiloxane linkers between the D4Rs, adding a 50% deficit of
silane theoretically can only functionalize five out of eight corners. An 87.5% conversion
was nevertheless observed, implying that 7 out of 8 corners were functionalized. This
implies that in contrast with the synthesis of PSS-2, where dichlorosilane was added in
the gas phase, the present synthesis route using dichlorosilane in THF also allows for the
linking of D4R units using a monomeric siloxane bridge.
Silyl chloride groups attached to a D4R can thus react with a free silanol of another
silicate cube. Only when monomeric silicone linkers occupy two corners of different silicate
cubes, can the observed degree of conversion be achieved under silane-deficient conditions.
Dimeric silicone linkers, in contrast, are formed when the terminal Si-Cl bonds of two
functionalized silicate cubes are hydrolyzed and condensed.
Examining the D2 Si atoms, multiple signals are observed in the −15 to −23 ppm
range of the 1D 29 Si NMR spectra (Figures 3b and S3). These signals indicate the presence
of silicone species bridging the silicate D4R cubes, as well as a polymer phase formed due
to the self-polymerization of dichlorosilane upon reaction with water, introduced in the
synthesis as crystal water in the CySH precursor [7,43].
29 Si NMR resonances of D2 Si species from pure octyl-methyl silicone polymers (OM

polymers) were identified using the 1D 29 Si NMR spectra of such a phase, obtained by
self-polymerization of n-octyl(methyl)dichlorosilane in the presence of water (Figure 3b).
The OM polymer exhibited signals around −20.3 ppm and in the range of −22 to −23 ppm.
The narrow signals suggest that the polymer species are relatively mobile. Signals assigned
to the POSiSil phase appear between −15 and −19 ppm and at −21.6 ppm, and are also
broader. The incorporation of the octyl-methyl silicone linkers between the rigid silicate
cubes reduces the mobility of the silicone linkers, causing broader signals. Based on these
assignments, the D2 /Q4 ratio in the PSS-3 siloxane-silsesquioxane phase is 0.69 for the
sample synthesized with a 50% deficit silane. This implies that monomeric and dimeric
Molecules 2025, 30, 228 5 of 14

silicone linkers are present in a ratio of 4 to 3. The length of silicone linkers can also be
rationalized from the chemical shift of D2 Si atoms. In structurally related PSS-2 materials,
monomeric and dimeric linkers resonated at −14.5 and −16.5 ppm, and −18.7 ppm and
Molecules 2025, 30, x FOR PEER REVIEW
−19.7 ppm, respectively. D2 Si atoms shift to more negative chemical shift values5 with of 15

increasing length of the silicone linkers [44].

Figure 3. (a) The

Figure 3. The chemical
chemical structure model of of different
different silicon
silicon species
species present
present in
in an
an octyl-methyl
octyl-methyl
POSiSil 1 H decoupled2929 Si single-pulse MAS NMR spectra of
POSiSil with
with their NMR chemical
their NMR chemical shift.
shift. (b)
(b)1H decoupled Si single-pulse MAS NMR spectra of an
an octyl-methyl
octyl-methyl POSiSil
POSiSil (50%
(50% excess,top)
excess, top)and
andthe
thesilicone
silicone polymer
polymer of of n-octyl(methyl)dichlorosilane
n-octyl(methyl)dichlorosilane
(OM polymer, bottom), focusing on D-coordinated Si atoms.
(OM polymer, bo om), focusing on D-coordinated Si atoms. The decompositionThe decomposition of PSS
of the the PSS spec-
spectrum
trum is given, and the colors are ascribed to the phase they occur, i.e., the PSS-3 network (green),
is given, and the colors are ascribed to the phase they occur, i.e., the PSS-3 network (green), silicone
silicone polymer fraction (gray), and silicone grease (purple). (c) The chemical structure model of
polymer fraction (gray), and silicone grease (purple). (c) The chemical structure model of spherosil-
spherosilicate with monomeric octyl-methyl silyl moieties. (d) 1 H decoupled 29 Si direct excitation
icate with monomeric octyl-methyl silyl moieties. (d) 1H decoupled 29Si direct excitation MAS NMR
MAS NMR spectra of PSS-3 materials with different concentrations of n-octyl(methyl)dichlorosilane.
spectra
The of resonance
sharp PSS-3 materials
(‡) at with
−22.4different concentrations
ppm is assigned of n-octyl(methyl)dichlorosilane.
to contamination The sharp
with silicone grease, which was
resonance
applied (‡) at
to the −22.4 glass
ground ppm joints
is assigned
of the to contamination
reaction with
set-up, also siliconesome
covering grease, whichpolymer
silicone was applied to
signals.
the ground
Better glass joints
visualization of the reaction
is provided set-up,
in (b). (e) also covering
Quantitative numberssome 4 , Q3 , and
of Qsilicone D2 -coordinated
polymer signals. Be29 Si
er
visualization
atoms is provided
per silicate in (b). based
cube of PSS-3, (e) Quantitative numbers
on Figure S3, of Qto, the
according 4 Q , different
3 and D -coordinated
2 29 Si atoms
silane concentrations
applied in the
per silicate synthesis
cube protocol.
of PSS-3, based D on2 Figure
Si atomsS3,were differentiated,
according belonging
to the different to either
silane the PSS or the
concentrations ap-
polymer phase.
plied in the synthesis protocol. D Si atoms were differentiated, belonging to either the PSS or the
2

polymer phase.
The D2 /Q4 ratio increases to 1 with stoichiometric amounts of silane or higher, corre-
sponding to dimeric silicone 2 Si atoms resonating at −18.6 and −19.7 ppm.
29Si NMR resonances of linkers with Dfrom
D2 Si species pure octyl-methyl silicone polymers (OM
The same ratio
polymers) werewould also be
identified obtained
using the 1Dby29Si
theNMR
presence of equal
spectra fractions
of such a phase,ofobtained
monomeric and
by self-
trimeric silicone of
polymerization linkers. Since only a minor fraction
n-octyl(methyl)dichlorosilane of Si
in the atoms exhibited
presence a chemical
of water (Figure 3b).shift
The
at − 21.6 ppm, i.e., more negative than those attributed to dimeric linkers,
OM polymer exhibited signals around −20.3 ppm and in the range of −22 to −23 ppm. The the presence of
equal
narrow fractions
signalsofsuggest
monomeric andpolymer
that the trimeric species
linkers can
are be excluded.
relatively BasedSignals
mobile. on the assignment
assigned to
of these chemical shift ranges to D 2 Si atoms present in, respectively, monomeric, dimeric,
the POSiSil phase appear between −15 and −19 ppm and at −21.6 ppm, and are also
and trimeric
broader. Thelinkers, the maximum
incorporation of the octyl-methyl D2 Si atoms
of 10% of thesilicone linkersinbetween
the PSS phase is present
the rigid silicate
cubes reduces the mobility of the silicone linkers, causing broader signals. Based on these
assignments, the D2/Q4 ratio in the PSS-3 siloxane-silsesquioxane phase is 0.69 for the sam-
ple synthesized with a 50% deficit silane. This implies that monomeric and dimeric sili-
cone linkers are present in a ratio of 4 to 3. The length of silicone linkers can also be ra-
2
Molecules 2025, 30, 228 6 of 14

in trimeric linkers. The length variation of silicone linkers also explains the presence of
multiple Q4 Si signals of the silicate cubes in the 29 Si NMR spectrum, ranging from −108.4
to −109.8 ppm [45,46].
When the silane concentration beyond the stoichiometric ratio is increased, the D2 /Q4
ratio no longer increases. This can be explained as follows. The CySH crystal liberates
individual silicate cubes in an acidified solvent (THF). The acidification results from the
release of HCl upon the reaction of dichlorosilane with hydroxyl groups on the corners of
the silicate D4R. TBA-CySH crystals readily dissolve in acidified THF [17]. This releases
silicate D4R into the solution, where they immediately react with octylmethyldichlorosilane
to form octakis(n-octylmethylsilyl chloride) spherosilicates (Figure 3c). Since the silane is
added all at once in liquid form, the disintegration of the CySH crystal structure occurs
fast, and octakis(n-octylmethylsilyl chloride) spherosilicates are formed simultaneously.
Increasing the silane concentration beyond the stoichiometric amount, the D2 /Q4 ratio
of the system remained constant. The transition of spherosilicates to POSiSils involves
a condensation reaction with water (vapor) and two peripheral Si-Cl bonds from the
n-octylmethyl silyl moieties.

2.2. Synthesis and Structure Elucidation of PSS-4

Dicyclopentyldichlorosilane is used in the production of silicones with improved ther-
mal and chemical resistance, rendering it an obvious choice for incorporation into siloxane-
silsesquioxane hybrids. Replacing octyl-methyldichlorosilane with dicyclopentyldichlorosi-
lane in the deficit synthesis protocol for PSS-3 did, however, not allow the formation of a
fully connected POSiSil material. Exclusively using dichlorodicyclopentylsilane yielded a
material exhibiting high fractions of defects. They are observed as silanols at the non-linked
corners of the silicate cube, Q3 Si, and interrupted silicone linkers, (sharp) D1 Si atoms,
appearing, respectively, at −100 and −10 ppm in the 29 Si NMR spectrum of the material
(Figure S4). The highly defective nature of the material was attributed to the steric hin-
drance induced by the cyclopentyl moieties, preventing the efficient formation of silicone
linkers between silicate cubes. To achieve sufficient silicone network propagation, along
with the incorporation of dicyclopentyl functionalities (Cp2 ), dicyclopentyldichlorosilane
was used in combination with dimethyldichlorosilane in a ratio of 8 to 3. As shown by the
increase of D2 Si atoms (-Si-O-Si(R2 )-O-Si-) in the 1D 29 Si NMR spectrum (Figure 4c), this
facilitated silicone bond formation between spherosilicate units [7,8]. The 1D 29 Si NMR fur-
ther revealed mainly Q4 Si (Q4 :Q3 = 7.7:0.3), demonstrating an efficient functionalization of
the silicate D4R. Multiple D2 Si species were observed in the chemical shift range between
−16 and −25 ppm (i.e., −16, −19.1, −21.9, and −24.8 ppm; D2 :Q4 = 10.2:7.7). The relative
concentrations of these 29 Si resonances, derived by decomposing the 1D 29 Si MAS NMR
spectrum (Figure S5), are provided in the Supplementary Materials (Table S2). Since the
previously reported PSS-2, incorporating exclusively dimethylsilicone linkers, only showed
D2 29 Si resonances between −16 and −21 ppm, the resonance at −24.8 ppm was assigned
to a D2 Si atom of a dicyclopentylsilicone moiety (-Si-O-Si(Cp)2 -O-Si-). The assignment
of the resonance at −24.8 ppm as Si(Cp)2 was confirmed from the decomposition of the
1D 29 Si and 1 H MAS NMR spectra (Figures S5–S7, and Discussion S2.1). In the 1 H-29 Si
HETCOR spectrum, both the cyclopentyl protons and the methyl protons correlate with
the Q4 Si atoms of the silicate D4R, thus demonstrating the successful incorporation of
both silanes into the PSS-4 structure (Figure 4e). Further structure elucidation was based
on 1 H-1 H double quantum-single quantum (DQ-SQ) MAS NMR spectroscopy, showing
self-correlation of all protons in the methyl and cyclopentyl groups, consistent with their
chemical structure and in agreement with the 1 H-13 C HETCOR (Figure 4b,d). DQ cross-
correlations between methyl and cyclopentyl protons reveal their close proximity and are
 structure (Figure 4e). Further structure elucidation was based on 1H‐1H double quantum‐
single quantum (DQ‐SQ) MAS NMR spectroscopy, showing self‐correlation of all protons in
Molecules 2025, 30, 228 the methyl and cyclopentyl groups, consistent with their chemical structure and in agreement 7 of 14
with the 1H‐13C HETCOR (Figure 4b,d). DQ cross‐correlations between methyl and
cyclopentyl protons reveal their close proximity and are consistent with the formation of
mixed silicone
consistent with linkers, i.e., ‐O‐Si(Me
the formation of mixed 2)‐O‐Si(Cp
silicone2)‐O‐. This
linkers, i.e.,is-O-Si(Me
further confirmed
2 )-O-Si(Cp2by
1H‐
)-O-. 29Si
This
HETCOR,
is further confirmed by 1 H-29 Si HETCOR,
showing cyclopentyl proton correlations with D2 Si(Me
showing cyclopentyl 2) atoms
proton (Figurewith
correlations D2
4b,e,f).
Overall, this confirms
Si(Me2 ) atoms the assignment
(Figure 4b,e,f). Overall, thisof the Si resonances
confirms
29 the assignment at −16of and 29
the −24.8 ppm to,
Si resonances
at −16 and −
respectively, 24.8 2ppm
Si(Me ) andto, respectively,
Si(Cp 2) contained Si(Me
in the
2 ) and
mixedSi(Cp
silicone
2 ) contained
linkers. in
The the mixed
resonances sili-
at
cone linkers.
−19.1 and −21.9 Theppmresonances
are ascribedat −to19.1 andand
outer −21.9 ppmSiare
central atomsascribed to outer
in trimeric and central Si
dimethylsilicone
atoms inrespectively
linkers, trimeric dimethylsilicone
(Figure 4c,f). The linkers, respectively
formation (Figure
of such trimeric 4c,f). The formation of
dimethylsilicone such
linkers
trimericpartial
implies dimethylsilicone
oligomerization linkersof implies partial oligomerization
dimethyldichlorosilane of dimethyldichlorosilane
via the reaction of the silane with
via thewater
crystal reaction
fromofthe
theTBA‐CySH
silane withprecursor.
crystal water from the TBA-CySH precursor.

CH3
(CH2)4∆
a CH

b -3 d -5 f
-2 0
-1
5
0
10
 (1H) / ppm

 (13C) / ppm

2 15

3 Si 20

4
25
5
Si 30
6

7 35
3 2 1 0 -1 3 2 1 0 -1
 (1H) / ppm  (1H) / ppm

c e
-120 -120
Q4
-100 -100

-80 -80
 (29Si) / ppm

 (29Si) / ppm

-60 -60

-40 -40

D2
-20 -20 D2

0 0
0 -20 -40 -60 -80 -100 -120 3 2 1 0 -1
 (29Si) / ppm  (1H) / ppm

Figure
Figure 4.4.Solid‐state
Solid-state NMR
NMR crystallography
crystallographyanalysis of PSS‐4.
analysis (a) 1D
of PSS-4. (a)direct excitation
1D direct 1H MAS
excitation 1 H NMR
MAS
NMR spectrum; (b) 2D 1 H-1 H dipolar DQ-SQ correlation spectrum. Cross-correlations between the
spectrum; (b) 2D H‐ H dipolar DQ‐SQ correlation spectrum. Cross‐correlations between the
1 1

protons of the dimethylsilyl

protons dimethylsilyl and
and dicyclopentyl
dicyclopentyl groups
groups areare marked
marked withwith full
full lines
lines in
in the
the colors
colors used
used
to mark the respective protons in the structure model in (f); (c) 1D 1 H decoupled 29 Si single-pulse
to mark the respective protons in the structure model in (f); (c) 1D H decoupled Si single‐pulse
1 29

MAS NMR
NMR spectrum
spectrum with 29 29 Si CP RFDR spectrum. 29 Si atoms of pure
MAS with their
their corresponding
corresponding 2D 2D 29Si-
Si‐29Si CP RFDR spectrum. 29Si atoms of pure
dimethylsilicone linkers correlate with the silicate cube, represented by the cross-correlations (off-
dimethylsilicone linkers correlate with the silicate cube, represented by the cross‐correlations (off‐
diagonal); (d) 2D 1 H-13 C HETCOR spectrum; (e) 2D 1 H-29 Si HETCOR spectrum. The correlations
diagonal); (d) 2D 1H‐13C HETCOR spectrum; (e) 2D 1H‐29Si HETCOR spectrum. The correlations are
are indicated with dashed lines corresponding to the colors of the 1 H and 13 C atoms in the structure
indicated with dashed lines corresponding to the colors of the H and 13C atoms in the structure
1
model in (f). (f) The chemical structure model with a mixed silicone linker (-O-SiMe2 -O-SiCp2 -O-)
model in (f).dimethylsilicone
and a pure (f) The chemicallinker
structure model-O)
(-O-(SiMe with a mixed silicone linker (‐O‐SiMe2‐O‐SiCp2‐O‐)
2 3 -).
and a pure dimethylsilicone linker (‐O‐(SiMe2‐O)3‐).
Overall, PSS-4 contains a combination of dimeric, mixed Me2 -Cp2 silicone linkers, and
trimeric dimethylsilicone linkers, present in equal amounts. This results in a D2 /Q4 ratio
of 1.33, similar to what was observed for PSS-2, synthesized from the same TBA-CySH
precursor with exclusive dimethyldichlorosilane to generate the linkers [8].
Molecules 2025, 30, 228 8 of 14

2.3. Thermal Stability of PSS-3 and PSS-4

The thermal stability of these new PSS materials was probed with thermogravimetric
analysis in an inert (N2 ) atmosphere after the selective removal of TBA-Cl by initial calcina-
tion at 250 (PSS-3) and 200 ◦ C (PSS-4) in an inert atmosphere (Figures S8 and S10). From
previous literature reports, it is known that the TBA template, as a chloride salt, decomposes
around 190 ◦ C [8,28,47]. This is observed in both PSS-3 and PSS-4 (Figures S8 and S10). For
PSS-4, the calcination temperature was lowered to 200 ◦ C due to the lower thermal stability
of the cyclopentyl functional groups (Figure S10).
The PSS-3 material remains thermally stable up to 400 ◦ C, as indicated by its T5% . From
that temperature onward, the organic octyl and methyl functionalities start to decompose,
consistent with what has previously been reported for similar siloxane-silsesquioxane
resins [36]. The decomposition proceeds via a multistage weight loss, only visible after
fitting the DTG curve, with a main decomposition peak at 482 ◦ C (Figure S9). The weight
loss observed upon decomposition of the organic functional groups (45.4 wt%) is consistent
with the composition of the silicone linkers derived from NMR spectroscopy. The theoretical
weight fraction of the octyl and methyl groups, as calculated from the chemical composition
(Figure 3e), is 46.5 wt%.
For PSS-4, T5% is 255 ◦ C. The DTG curve shows a multistage decomposition of the
dicyclopentyl and dimethyl functional groups, with maxima of decomposition peaks
occurring at 354 ◦ C, 460 ◦ C, 514 ◦ C, and 670 ◦ C (Figure S11). The total weight fraction of
the dicyclopentyl and dimethyl groups, as estimated from the NMR-derived composition
(35.9 wt%) is in good agreement with the experimental weight loss measured by TGA
(34.4 wt%) (Discussion S2.2).

2.4. Morphological and Porosity Analysis of PSS-3 and PSS-4

The morphology of PSS materials was evaluated by means of scanning electron mi-
croscopy (SEM). Large particles with random morphology were observed for PSS-3 as
well as PSS-4 (Figure 5). Some superficial porosity, in the form of macropores, might be
observed but are rather rare. As expected, PSS-3 nor PSS-4 could not be characterized by
N2 physisorption. N2 physisorption typically fails for PSS materials because the tempera-
Molecules 2025, 30, x FOR PEER REVIEW 9 of 15
ture conditions at which N2 physisorption occurs cause the flexible matrix to collapse, a
phenomenon also observed in other silicate hybrid materials with flexible linkers [8,28,30].

Figure5.5. SEM
Figure SEM images
images of
of PSS‐3
PSS-3 with
with aa 50%
50% deficit
deficit of
of silane
silane (a)
(a) and
andPSS‐4
PSS-4(b).
(b).HAADF‐STEM
HAADF-STEM
tomography and
tomography and data
data analysis
analysis of
of PSS‐4.
PSS-4. (c)
(c)The
Thedata
dataillustrate
illustratethe
the3D3Dvolume,
volume, showing thethe
showing pore
pore
volume(blue),
volume (blue),material
material (yellow)
(yellow) (left), and pore
pore size
sizedistribution
distribution(right).
(right).

3. Materials and
To gain some Methods
insight into the presence or absence of porosity, HAADF-STEM tomogra-
phy was performed on PSS-4
3.1. Chemical and Reagents (Figure 5c). This analysis indicated a porosity of 28%, mainly
caused by a broad pore size distribution comprising meso- and macropores.
TEOS (Acros organics, Geel, Belgium, 98%), ammonium hydroxide (Chem‐lab,
Zedelgem, Belgium, 29wt% in water), tetrabutylammonium hydroxide (TBA‐OH) (Acros
organics, 40 wt% in water), tetrahydrofuran (THF) (Acros organics, 99.8%, extra dry over
molecular sieve, stabilized, acrosealTM), dimethyldichlorosilane (Acros organics, >99%,
acroseal), octylmethyldichlorosilane (Alfa Aesar, Ward Hill, MA, USA 98%),
dicyclopentyldichlorosilane (Gelest, Morrisville, PA, USA, 97%), and potassium sulfate
(Acros organics, ≥ 99%) were used as purchased, without any further purification.
Molecules 2025, 30, 228 9 of 14

3. Materials and Methods

3.1. Chemical and Reagents
TEOS (Acros organics, Geel, Belgium, 98%), ammonium hydroxide (Chem-lab, Zedel-
gem, Belgium, 29wt% in water), tetrabutylammonium hydroxide (TBA-OH) (Acros organ-
ics, 40 wt% in water), tetrahydrofuran (THF) (Acros organics, 99.8%, extra dry over molecu-
lar sieve, stabilized, acrosealTM), dimethyldichlorosilane (Acros organics, >99%, acroseal),
octylmethyldichlorosilane (Alfa Aesar, Ward Hill, MA, USA 98%), dicyclopentyldichlorosi-
lane (Gelest, Morrisville, PA, USA, 97%), and potassium sulfate (Acros organics, ≥ 99%)
were used as purchased, without any further purification.

3.2. Tetrabutylammonium Cyclosilicate Hydrate (TBA-CySH) Synthesis

Tetrabutylammonium cyclosilicate hydrate synthesis is based on the work by
Smet et al. (2017) [17]. TEOS (139 mL) was added dropwise to a stirred solu-
tion of tetrabutylammonium—(140.52 mL) and ammonium hydroxide (222.47 mL)
[1TBAOH:7.8NH4 OH:59H2 O on a molar basis], to prevent gelation. After 48 h, a white
suspension was filtered (Whatman™ qualitative filter paper grade 5; 90 mm diameter, Cy-
tiva, Marlborough, MA, USA) and washed with water. After drying in ambient conditions,
TBA-CySH crystals were recovered.

3.3. PSS-3 Synthesis

TBA-CySH (1 g) was dried under a vacuum (1 mbar) at room temperature for 72 h in
a 100 mL, 2-neck round-bottom flask, sealed with rubber stoppers, and a high-vacuum sili-
cone grease connected to a standard Schlenk line. THF (12 mL) and octylmethyldichlorosi-
lane were added to the pre-dried TBA-CySH crystals. Respectively, 1.3 mL, 2.6 mL, or
3.9 mL of octylmethyldichlorosilane were added to achieve a 50% deficit, stoichiometric
ratio, and 50% excess PSS-3. After 6 h of reaction, THF and excessive silane were evaporated
under a vacuum (1 mbar) at 90 ◦ C for 16 h to yield an intermediate spherosilicate powder.
To generate PSS-3, these spherosilicates were dissolved in THF (14 mL) and subsequently
reacted with water vapor in a desiccator at 98% relative humidity. After 24 h, PSS-3 powders
were collected and dried at 60 ◦ C at ambient pressure.

3.4. PSS-4 Synthesis

PSS-4 was synthesized via a similar procedure as PSS-3, but other silanes were added.
Dicyclopentyl- (0.74 mL) and dimethyldichlorosilane (1.1 mL) were mixed together in a
glass vial under an inert atmosphere prior to the addition to pre-dried TBA-CySH dissolved
in THF (12 mL). The molar ratio of CySH, dicyclopentyl- and dimethyldichlorosilane was
1/3/8. After 6 h of reaction, THF and excessive silane were evaporated at vacuum and
room temperature for 16 h to yield an intermediate spherosilicate powder. To yield to PSS-4,
these spherosilicates were redissolved in THF (14 mL) and reacted to with water vapor in a
desiccator at 98% relative humidity. After 24 h, PSS-4 powders were collected and dried at
60 ◦ C at an ambient pressure.

3.5. Calcination of PSS Materials

PSS-3 was calcined in a U-tube flow oven under an N2 atmosphere at 250 ◦ C with a rate
of 1◦ C/min. The calcination temperature was kept for 2 h before gradually being cooled to
room temperature. PSS-4 was calcined via a similar procedure but at 200 ◦ C for 4 h.

3.6. Characterization of PSS Materials

Powder XRD patterns were recorded in transmission mode on a high-throughput
STOE stadi P diffractometer (STOE & Cie GmbH, Darmstadt, Germany) equipped with
Molecules 2025, 30, 228 10 of 14

an image plate detector. Thermogravimetric analyses under the N2 atmosphere were

performed using a TGA/DSC3+ apparatus (Mettler Toledo, Greifensee, Switzerland). At
a rate of 10 ◦ C/min, each sample was heated from room temperature to 900 ◦ C before
gradually being cooled back to ambient conditions. The temperature at which a weight
loss of 5 wt% was observed is denoted as T5% and is referred to as the thermal stability
temperature of the POSiSil materials. Scanning electron microscopy images were taken
with a Nova NanoSEM 450 (FEI, Eindhoven, The Netherlands) at a voltage of 2 kV. The
powders obtained upon crushing the materials were dispersed on carbon tape and imaged
as such, without additional coating. High-Angle Annular Dark-Field Scanning Transmis-
sion Electron Microscopy (HAADF-STEM) of images at room temperature (RT) has been
performed on an aberration-corrected cubed Thermo Fisher Titan microscope (Thermo
Fischer Scientific, Waltham, MA, USA) operating at 300 kV. Electron tomography tilt series
were acquired using a Fischione 2020 tomography holder (E.A. Fischione Instruments,
Inc., Export, PA, USA). A high-resolution HAADF-STEM tilt series was acquired over a
tilt range between ±75◦ with a tilt increment of 3◦ . To obtain a reliable reconstruction
of the pore structure, a recently developed approach was used for which a time series of
images was acquired for every tilt angle at a short dwell time [48]. The projection images
were acquired using 5 frames at 1 µs dwell time, while the image resolution was set to
1024 × 1024 pixels. Next, these images were used as inputs for a non-rigid registration
method in combination with a convolutional neural network (CNN) [48]. The obtained
series were aligned using cross-correlation, and 3D reconstructions were obtained using
the Expectation Maximization (EM) algorithm implemented in Astra Toolbox (v2.1) [49,50].
All solid-state NMR experiments were carried out in Bruker 300 Avance III (7.4 T)
and Bruker 500 Avance III (11.4 T) spectrometers (Bruker BioSpin, Ettlingen, Germany)
with respective 29 Si Larmor frequencies of 59.63 MHz and 99.36 MHz, with 4 mm triple
resonance MAS probes. For PSS-3, the octyl-methyl silicone polymer and the stoichiometric
PSS-3 sample were recorded at 300 MHz with a 1 H decoupled direct excitation sequence
with 320 and 304 transients, respectively, and a recycle delay of 150 and 240 s, respectively,
using a π/2 pulse of radiofrequency strength of 66 kHz and a 1 H decoupling (strength of
~55 kHz) achieved using the SWf -SPINAL sequence [51]. For the 50% deficit and excess
PSS-3 samples, 1 H decoupled 29 Si MAS spectra were recorded at 500 MHz with 240 and
128 transients, respectively, and a recycle delay of 300 s, using a π/2 pulse of radiofrequency
strength of 60 kHz and 1 H decoupling (strength of ~55 kHz) achieved using a SWf -SPINAL
sequence [51]. For PSS-4, all measurements were performed at 500 MHz using the above
sequence and parameters. In total, 136 transients were recorded with a recycle delay of
400 s. The 1 H NMR experiments were performed with 8 scans and a 15 s recycle delay.
The 29 Si chemical shifts were referenced against the resonances of Q8 M8 , a secondary
reference of tetramethylsilane (TMS). The 1 H-1 H double quantum-single quantum (DQ-SQ)
experiments were performed with BABA pulses of 50 kHz strength [52]. In total, 256 slices
were collected with an increment of 66.67 µs (rotor synchronized). The 29 Si CP-RFDR
experiment was conducted at 20 kHz MAS using a CP contact of 6.5 ms and 29 Si pulses
of 70 kHz strength. In total, 700 slices were collected with an increment of 66.67 µs (rotor
synchronized), with 416 transients recorded for each slice at an RFDR mixing time of
90 ms. The 2D 1 H-13 C CP-HETCOR experiment was carried out using a CP contact time of
0.5 ms. A recycle delay of 4 s was used for 32 scans per slice of the 2D experiment. With an
increment of 19 µs, 640 slices were recorded. The 2D 1 H-29 Si CP-HETCOR experiment was
carried out using a CP contact time of 2 ms. A recycle delay of 5 s was used for 176 scans
per slice of the 2D experiment. With an increment of 25 µs, 256 slices were recorded. All
NMR spectra fittings were performed by using the Dmfit software (v. #20200306) [53].
Molecules 2025, 30, 228 11 of 14

4. Conclusions
In summary, this research demonstrated the successful incorporation of long and bulky
hydrocarbon functionalities in novel silicate-silicone hybrid materials, belonging to the
PolyOligoSiloxySilicone (POSiSil) material class. Both PSS-3 and PSS-4 syntheses started
from zero-dimensional hydrogen-bonded tetrabutylammonium cyclosilicate hydrate crys-
tals constituted of silicate cubes [Si8 O20 ], a silicate precursor enclosing a low amount of
crystal water that allows using organodichlorosilane reagents as linkers. Octyl-methyl and
a mix of dimethyl—and dicyclopentylsilicone moieties were incorporated in PSS-3 and PSS-
4, respectively, through silylation of silicate cubes with the corresponding dichlorosilanes,
followed by subsequent hydrolysis with water (vapor). The linear, aliphatic octyl hydro-
carbon in PSS-3 induced a maximum average length of the silicone linkers of two. Steric
hindrance was experienced with dicyclopentyl functionalities, which was bypassed using
an additional, “smaller” dimethyldichlorosilane reagent. A mixed dimethyl-dicyclopentyl
silicone linker, (Si8 -O-Si(Me2 )-O-Si(Cp2 )-O-Si8 ), was identified. Multidimensional 1 H, 13 C,
and 29 Si NMR spectroscopy were employed for the quantitative characterization of silicone
linkers in PSS-3 and PSS-4, addressing a scientific gap in previous studies on similar mate-
rials with large hydrocarbon functionalities. Physical properties like thermal stability up to
400 ◦ C were observed for amorphous PSS particles. Looking at the overall porosity with
HAADF-STEM, PSS-4 with the bulkier cyclopentyl functionalities showed a porosity of
28%. A detailed characterization of the porosity of PSS-3 and PSS-4 is necessary, but the
collapse of the sample’s flexible network at 77 K renders conventional N2 physisorption
unsuitable. Water intrusion-extrusion cycles could be a potential alternative.
The controlled incorporation of large hydrocarbon functionalities could facilitate
a mesostructured or hierarchical pore network due to their compatibility with reverse
micelles. Hydrophobic interactions between reverse micelle tails and, for example, the
linear octyl moieties of PSS-3 could organize the silicate-silicone hybrid material around
the micellar shape or even self-assembly into an ordered mesoscopic fashion, a feature
only achieved by few other reports, albeit suffering from a low synthesis efficiency starting
from POSS precursors [54–56]. The unique set of properties of silicate-silicone hybrid
materials, combined with in situ chemical functionalization, offer potential applications
such as high-pressure gas storage, catalysis, and adsorption and separation processes.

Supplementary Materials: The following supporting information can be downloaded at: https:
//www.mdpi.com/article/10.3390/molecules30020228/s1, Figure S1: Diffraction patterns of PSS-
3 (50% deficit silane) before and after calcination; Figure S2: Diffraction patterns of PSS-4 before
and after calcination; Figure S3: Decomposition of 1D 29 Si MAS NMR spectra of PSS-3; Figure
S4: 1D 1 H decoupled 29 Si MAS NMR spectra of PSS materials synthesized with a 50% deficit of
dicyclopentylsilane only and a mix of dimethyl- and dicyclopentylsilane; Figure S5: Decomposition of
the 1D 1 H decoupled 29 Si MAS NMR spectrum of PSS-4; Figure S6: Decomposition of the 1D 1 H MAS
NMR spectrum of PSS-4 measured at 15 kHz in a 500 MHz spectrometer; Figure S7: Decomposition
of the 1D 1 H MAS NMR spectrum of PSS-4 measured at 40 kHz in a 800 MHz spectrometer; Figure S8:
Thermogravimetric analysis of PSS-3 in inert (N2 ) atmosphere before and after calcination; Figure S9:
Decomposition of the DTG curve of a calcined PSS-3 sample; Figure S10: Thermogravimetric analysis
of PSS-4 in inert (N2 ) atmosphere before and after calcination; Figure S11: Decomposition of the DTG
curve of a calcined PSS-4 sample; Table S1. Chemical shift, signal intensity, and Si atom designation
of all individual signals from Figure S3; Table S2: Si speciation, chemical shift, and relative intensities
per cube of all individual components fitted in the decomposition of the 29 Si NMR of PSS-4; Table S3.
Details of individual proton components according to Figure S6; Table S4. Molecular weight of all
individual components of PSS-3 and PSS-4; Section S1.1. Diffraction patterns describing PSS materials
before and after calcination (Figures S1 and S2); Section S1.2. NMR spectra unravelling the chemical
structure of PSS materials (Figures S3–S7 & Tables S1 and S2); Section S1.3. Investigation of thermal
Molecules 2025, 30, 228 12 of 14

properties of PSS materials (Figures S8–S11); Discussion S2.1.: Assignment of resolved D-coordinated
Si atoms in 1D 29 Si MAS NMR of PSS-4; Discussion S2.2.: Calculations of the theoretical weight of
PSS-3 and PSS-4.

Author Contributions: Conceptualization, S.S., J.A.M., and E.B.; methodology, J.J., S.S., and M.H.;
validation, J.J., A.V., and P.W.; formal analysis, J.J., S.R., and C.V.C. under the supervision of S.S. and
E.B., and D.A.E.; writing—original draft preparation, J.J., S.S., and M.H.; writing—review and editing,
J.J., M.H., S.R., C.V.C., S.B., and E.B.; supervision, J.A.M., and E.B.; funding acquisition, M.H., J.A.M.,
and E.B. All authors have read and agreed to the published version of the manuscript.

Funding: J.A.M. acknowledges the European Research Council (ERC) for an Advanced Research
Grant under the European Union’s Horizon 2020 research and innovation program under grant
agreement No. 834134 (WATUSO). NMRCoRe acknowledges the Flemish government, department
EWI for infrastructure investment via the Hermes Fund (AH.2016.134) and for financial support as
International Research Infrastructure (I001321N: Nuclear Magnetic Resonance Spectroscopy Platform
for Molecular Water Research). The authors acknowledge VLAIO for Moonshot funding (ARCLATH,
No. HBC.2019.0110).

Institutional Review Board Statement: Not applicable.

Information Consent Statement: Not applicable.

Data Availability Statement: Data are contained within the article and Supplementary Materials.

Acknowledgments: The authors acknowledge Gina Vanbutsele, Sreeprasanth Pulinthanathu Sree,

Anke Snauwaert, Frea Van Steenweghen, Dirk Dom, Karel Duerinckx, Dries Vandenabeele, Loes
Verheyden, and Wauter Wangermez for assistance with material characterization.

Conflicts of Interest: The authors declare no conflicts of interest.

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