indolyl (Table 12.1, S30 and S31) or benzo-/dibenzocarbazolyl (Table 12.1, S32
and S33) side groups. Those with incorporated exclusively carbazolyl units were
further functionalized by azo chromophores containing p-sulfonyl or p-nitrophenyl
electron acceptors [79]. Indolyl side groups in the hydrosilylation products were
subsequently modified by azo chromophores with introduced p-sulfonylphenyl
moieties [80]. Products of the hydrosilylation reactions and the final functionalized
compounds were characterized by FTIR and
1 H NMR spectroscopies which corroborated their expected chemical structures. Based on
1 H NMR spectra, degrees of
polymer functionalization and the amounts of chromophores in carbazolyl/indolyl
moieties were calculated [79, 80]. Additionally, their UV/Vis absorption [80, 81]
and photoluminescence [81] spectra were measured. Polysiloxanes functionalized
by the proposed carbazolyl or indolyl side groups were found to be good candidates
for photorefractive [79, 81] or nonlinear optical [80] applications.
Polysiloxane with phthalocyanine side groups (Table 12.1, S34) was prepared in
the reaction between PHMS and a phthalocyanine derivative containing alkoxy
groups and a single terminal alkenyloxy substituent in the molecule (Karstedt’s
catalyst, toluene, 60 °C [82]). Progress of the PHMS functionalization process was
monitored by IR spectroscopy (disappearance of the Si–H absorption band at
2150 cm
−1 ). As determined by the spectra, the maximum conversion of Si–H
groups equal to 94.4% could be attained in the adopted experimental conditions.
Modification of the polymer by the phthalocyanine group was evidenced by
1 H and
13 C NMR spectroscopies which also showed that the b hydrosilylation product was
formed. From thermo-optical measurements, it was concluded that attachment of
phthalocyanine moieties to polysiloxane chain causes slower crystallization of the
compound as compared with the corresponding free phthalocyanine [82].
Chemical membrane sensors for detection of Fe
3+ ions in water based on cyclam
(1,4,8,11-tetraazacyclotetradecane)-functionalized polysiloxanes were investigated
by Mefteh et al. [83]. One of the materials studied was prepared by hydrosilylating
N-10-undecenylcyclam (synthesized in the work) with PHMS in a chloroform
solution, at 60 °C using Karstedt’s catalyst. FTIR,
1 H, and
13
C NMR spectroscopies
proved formation of the expected product (Table 12.1, polymer A-S35). The
presence of azamacrocycles attached to Si atoms was manifested by the IR bands at
1127 cm
−1 (stretching C–N vibrations in secondary amines), 1573 and 3185 cm
−1
(deformational and stretching, respectively, N–H vibrations in secondary amines),
1 H NMR signals at d = 1.25, 1.4, 1.7, 2.5, 2.55, 2.75, and 2.85 ppm from the
protons of the CH 2 groups of azamacrocycle and the undecamethylene spacer, and
at d = 0.5, 1.95, 1.13 ppm assigned to methylene protons in the linker formed upon
hydrosilylation (b adduct),
13 C NMR lines at d = 14.57, 18.8, and 31.7 ppm from
carbon atoms of methylene groups. No spectral signatures of the preserved vinyl or
Si–H groups were observed.
Our group performed the reactions of PHMS with N-allylmorpholine (NAM,
Karstedt’s catalyst, solvent-free conditions, room temperature, 24 h) and 4vinylpyridine (4VP, Karstedt’s catalyst, toluene, or solvent-free conditions, 60 or
110 °C, 72 h) with the aim to obtain new catalysts or catalytic supports containing
NAM or 4VP moieties (Table 12.1, S36 and S37). Products were solid materials
382
A. Chechelska-Noworyta et al.
and S33) side groups. Those with incorporated exclusively carbazolyl units were
further functionalized by azo chromophores containing p-sulfonyl or p-nitrophenyl
electron acceptors [79]. Indolyl side groups in the hydrosilylation products were
subsequently modified by azo chromophores with introduced p-sulfonylphenyl
moieties [80]. Products of the hydrosilylation reactions and the final functionalized
compounds were characterized by FTIR and
1 H NMR spectroscopies which corroborated their expected chemical structures. Based on
1 H NMR spectra, degrees of
polymer functionalization and the amounts of chromophores in carbazolyl/indolyl
moieties were calculated [79, 80]. Additionally, their UV/Vis absorption [80, 81]
and photoluminescence [81] spectra were measured. Polysiloxanes functionalized
by the proposed carbazolyl or indolyl side groups were found to be good candidates
for photorefractive [79, 81] or nonlinear optical [80] applications.
Polysiloxane with phthalocyanine side groups (Table 12.1, S34) was prepared in
the reaction between PHMS and a phthalocyanine derivative containing alkoxy
groups and a single terminal alkenyloxy substituent in the molecule (Karstedt’s
catalyst, toluene, 60 °C [82]). Progress of the PHMS functionalization process was
monitored by IR spectroscopy (disappearance of the Si–H absorption band at
2150 cm
−1 ). As determined by the spectra, the maximum conversion of Si–H
groups equal to 94.4% could be attained in the adopted experimental conditions.
Modification of the polymer by the phthalocyanine group was evidenced by
1 H and
13 C NMR spectroscopies which also showed that the b hydrosilylation product was
formed. From thermo-optical measurements, it was concluded that attachment of
phthalocyanine moieties to polysiloxane chain causes slower crystallization of the
compound as compared with the corresponding free phthalocyanine [82].
Chemical membrane sensors for detection of Fe
3+ ions in water based on cyclam
(1,4,8,11-tetraazacyclotetradecane)-functionalized polysiloxanes were investigated
by Mefteh et al. [83]. One of the materials studied was prepared by hydrosilylating
N-10-undecenylcyclam (synthesized in the work) with PHMS in a chloroform
solution, at 60 °C using Karstedt’s catalyst. FTIR,
1 H, and
13
C NMR spectroscopies
proved formation of the expected product (Table 12.1, polymer A-S35). The
presence of azamacrocycles attached to Si atoms was manifested by the IR bands at
1127 cm
−1 (stretching C–N vibrations in secondary amines), 1573 and 3185 cm
−1
(deformational and stretching, respectively, N–H vibrations in secondary amines),
1 H NMR signals at d = 1.25, 1.4, 1.7, 2.5, 2.55, 2.75, and 2.85 ppm from the
protons of the CH 2 groups of azamacrocycle and the undecamethylene spacer, and
at d = 0.5, 1.95, 1.13 ppm assigned to methylene protons in the linker formed upon
hydrosilylation (b adduct),
13 C NMR lines at d = 14.57, 18.8, and 31.7 ppm from
carbon atoms of methylene groups. No spectral signatures of the preserved vinyl or
Si–H groups were observed.
Our group performed the reactions of PHMS with N-allylmorpholine (NAM,
Karstedt’s catalyst, solvent-free conditions, room temperature, 24 h) and 4vinylpyridine (4VP, Karstedt’s catalyst, toluene, or solvent-free conditions, 60 or
110 °C, 72 h) with the aim to obtain new catalysts or catalytic supports containing
NAM or 4VP moieties (Table 12.1, S36 and S37). Products were solid materials
382
A. Chechelska-Noworyta et al.