disappearance of the Si–H maxima in the FTIR and
1 H NMR spectra of the reaction
mixtures.
1 H,
13 C,
29 Si, and
19 F NMR spectroscopies were applied to characterize
the products.
1 H combined with
13 C and
29
Si NMR spectra confirmed exactly the
eightfold substitution of hydrogen atoms in Q 8 M 8
H . Moreover, the
1
H NMR spectra
allowed to conclude that b adduct was the dominant one in most cases; only
incorporation of perfluoroaromatic units (Table 12.3, S23) resulted in ca. equal
amounts of b and a adducts. Blends of poly(methyl methacrylate) (PMMA) and
fluorinated POSS materials obtained in the studies showed increased hydrophobicity as compared to pure PMMA [107].
12.5.4 T 8
H and Q 8 M 8
H Modified by Nitrogen-Containing
Groups
Cage molecules with introduced nitrogen-containing substituents were obtained by
direct hydrosilylation of a nitrogen-containing alkene derivative or indirectly, by
successive chemical transformations in which hydrosilylation was the first step.
Direct hydrosilylation was applied to incorporate amine moieties originating
from N,N-dimethylallylamine (DMAA) (Table 12.3, S18) to Q 8 M 8
H (Karstedt’s
catalyst, THF, reflux [108, 109]), variously substituted azobenzene units (e.g.,
Table 12.3, S24) to T 8
H (dichlorodicyclopentadienyl)platinum(II) complex, dioxane, 80 °C [110]) or Q 8 M 8
H (Karstedt’s catalyst, toluene, 40–80 °C [111–113]),
carbazole groups (Table 12.3, S25) to Q 8 M 8
H via its reaction with 9-vinylcarbazole
(Karstedt’s catalyst, toluene, room temperature [114]), moieties-containing isocyanate groups (Table 12.3, S26) to Q 8 M 8
H by its treatment with m-isoprenyl-a,a′dimethylbenzyl isocyanate, m-TMI (Karstedt’s catalyst, 80 °C, solvent-free conditions [115]). In most cases,
1 H NMR and/or FTIR spectra of hydrosilylation
products showed complete functionalization of Q 8 M 8
H . Incomplete modification
was found for T 8
H [110] and Q 8 M 8
H in the work by Ledin et al. [112].
1 H NMR
spectra analysis allowed establishing that conducted hydrosilylation reactions were
exclusively b additions [111, 113, 115], but when T 8
H was functionalized, significant amounts of a addition product were formed [110].
29 Si NMR spectra
measured in several studies [110, 111, 113–115] confirmed that hydrosilylation
occurred and that the cage structure stayed intact during the performed processes.
FTIR (the band at 2243 cm
−1 of –N=C=O) and NMR (
1 H: multiplet at
d = *7.5 ppm of aromatic protons,
13 C: signals in the range of d = 121.8–
149.7 ppm—carbon atoms of phenyl rings, d = 25–35 ppm—aliphatic carbon
atoms) spectroscopies showed incorporation of the moieties originating from mTMI (Table 12.3, S26) to the spherosilicate [115].
Product of the reaction of Q 8 M 8
H and DMAA was subsequently converted to
QAS by treatment with alkyl iodides of various chain lengths [108] or long-chain
alkyl iodides, bromides, and chlorides [109]. Quaternization of amine groups
12 Application of Spectroscopic Methods in the Studies …
391
1 H NMR spectra of the reaction
mixtures.
1 H,
13 C,
29 Si, and
19 F NMR spectroscopies were applied to characterize
the products.
1 H combined with
13 C and
29
Si NMR spectra confirmed exactly the
eightfold substitution of hydrogen atoms in Q 8 M 8
H . Moreover, the
1
H NMR spectra
allowed to conclude that b adduct was the dominant one in most cases; only
incorporation of perfluoroaromatic units (Table 12.3, S23) resulted in ca. equal
amounts of b and a adducts. Blends of poly(methyl methacrylate) (PMMA) and
fluorinated POSS materials obtained in the studies showed increased hydrophobicity as compared to pure PMMA [107].
12.5.4 T 8
H and Q 8 M 8
H Modified by Nitrogen-Containing
Groups
Cage molecules with introduced nitrogen-containing substituents were obtained by
direct hydrosilylation of a nitrogen-containing alkene derivative or indirectly, by
successive chemical transformations in which hydrosilylation was the first step.
Direct hydrosilylation was applied to incorporate amine moieties originating
from N,N-dimethylallylamine (DMAA) (Table 12.3, S18) to Q 8 M 8
H (Karstedt’s
catalyst, THF, reflux [108, 109]), variously substituted azobenzene units (e.g.,
Table 12.3, S24) to T 8
H (dichlorodicyclopentadienyl)platinum(II) complex, dioxane, 80 °C [110]) or Q 8 M 8
H (Karstedt’s catalyst, toluene, 40–80 °C [111–113]),
carbazole groups (Table 12.3, S25) to Q 8 M 8
H via its reaction with 9-vinylcarbazole
(Karstedt’s catalyst, toluene, room temperature [114]), moieties-containing isocyanate groups (Table 12.3, S26) to Q 8 M 8
H by its treatment with m-isoprenyl-a,a′dimethylbenzyl isocyanate, m-TMI (Karstedt’s catalyst, 80 °C, solvent-free conditions [115]). In most cases,
1 H NMR and/or FTIR spectra of hydrosilylation
products showed complete functionalization of Q 8 M 8
H . Incomplete modification
was found for T 8
H [110] and Q 8 M 8
H in the work by Ledin et al. [112].
1 H NMR
spectra analysis allowed establishing that conducted hydrosilylation reactions were
exclusively b additions [111, 113, 115], but when T 8
H was functionalized, significant amounts of a addition product were formed [110].
29 Si NMR spectra
measured in several studies [110, 111, 113–115] confirmed that hydrosilylation
occurred and that the cage structure stayed intact during the performed processes.
FTIR (the band at 2243 cm
−1 of –N=C=O) and NMR (
1 H: multiplet at
d = *7.5 ppm of aromatic protons,
13 C: signals in the range of d = 121.8–
149.7 ppm—carbon atoms of phenyl rings, d = 25–35 ppm—aliphatic carbon
atoms) spectroscopies showed incorporation of the moieties originating from mTMI (Table 12.3, S26) to the spherosilicate [115].
Product of the reaction of Q 8 M 8
H and DMAA was subsequently converted to
QAS by treatment with alkyl iodides of various chain lengths [108] or long-chain
alkyl iodides, bromides, and chlorides [109]. Quaternization of amine groups
12 Application of Spectroscopic Methods in the Studies …
391