Several new poly(alkylarylsilane)s, [Et 3 Si(CH 2 ) 2 Si(C 6 H 4 R)] n [R = H (1), p-Me (2), p-OMe (3), p-NMe 2 (4)] with M w = 2.9-4.6 Â 10 3 and PDI = 1.41-1.64, have been synthesized by dehalocondensation of appropriate dichlorodiorganosilanes using Na dispersion in refluxing toluene. The σ-σ* electronic transitions associated with the silicon backbone of 1-4 exhibit a progressive red shift (λ max : 320-342 nm) as a result of increasing electron donating ability of the substituent on the phenyl ring. This intrinsic optimization of band gap energy has been considered as a measure of oxidation potential of these polysilanes which varies in the following order: 1 > 2 > 3 > 4. The result obtained from electronic spectra is further confirmed by electrochemical studies using cyclic voltammetry which reveals a lowering of the oxidation potential (V peak ) from 0.95 to 0.49 V in the polysilanes 1-4. These polysilanes act as reducing agents of variable strengths toward Ag(I) and Pd(II) ions and afford the formation of metal nanoparticles with optimized size domains [21.0-4.8 nm for Ag; 31.6-16.6 nm for Pd], the smaller size nanoparticles being formed by the use of polysilanes with lower oxidation potential (or higher λ max ). The polymer-metal nanocomposites have been characterized by NMR and UV-vis spectroscopy as well as powder X-ray diffraction, TEM, and DLS studies.
Poly(hydrosilane)s, [R(H)Si]n [R = Ph, Si(CH2)3SiMe2Th, cy‐Hex], are investigated as sources of silyl radicals. The Si–H bonds in these oligomers exhibit good to excellent hydrogen donating properties which ensure the formation of reactive silyl radicals. For free radical photopolymerization, the polymerization initiating properties of these structures are checked. These polymers are found to be advantageous to overcome the classical oxygen inhibition of the FRP process. Their ability in FRPCP is also evaluated for an epoxy monomer. The mechanisms are investigated through ESR and laser flash photolysis experiments.
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