1983
DOI: 10.1002/pol.1983.130211008
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Organosilane high polymers: Electronic spectra and photodegradation

Abstract: Organosilane polymers have created widespread interest as precursors for &Sic fibers (1-S), as impregnating agents for strengthening ceramics (6,7), and as dopable semiconductors (4). In the preceding article we described a general synthesis for a variety of very high-molecular-weight organosilane homopolymers (8) :Me I I X t S i j n 1: X = P h 5 : X=n-butyl 2: x =p-tolyl 6: X=n-hexyl 3: X = 0-phenethyl 7 : X = n-dodecyl 4: X = n-propyl 8:We now report unusual ultraviolet (UV) absorption properties of the poly… Show more

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Cited by 157 publications
(67 citation statements)
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“…The UV spectra of the samples were also similar in shape but the lower molecular weight materials absorbed at slightly shorter wavelengths (332 Versus 340 nm), which is consistent with earlier observations made on related silicon polymers regarding the relationship of the Xmax and molecular weight. 16 As mentioned earlier, one of the most unusual features of polysilane derivatives is their remarkable electronic spectra. Not only is the UV-visible absorption dependent on molecular weight and on the substituents, but it also appears to depend on the conformation of the backbone.…”
Section: Resultsmentioning
confidence: 99%
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“…The UV spectra of the samples were also similar in shape but the lower molecular weight materials absorbed at slightly shorter wavelengths (332 Versus 340 nm), which is consistent with earlier observations made on related silicon polymers regarding the relationship of the Xmax and molecular weight. 16 As mentioned earlier, one of the most unusual features of polysilane derivatives is their remarkable electronic spectra. Not only is the UV-visible absorption dependent on molecular weight and on the substituents, but it also appears to depend on the conformation of the backbone.…”
Section: Resultsmentioning
confidence: 99%
“…It occurs between 305-325 nm for alkyl substituted materials, but is strongly red shifted to 335-350 nm when aromatic substituents are directly attached to the silicon backbone. 16 Very recently, we have demonstrated that the limiting values for the Xmax apply only to materials in solution or in the amorphous solid state. Films of materials which are symmetrically substituted with long chain alkyl 17% groups undergo a curious spectral red shift of 55-65 nm upon standing.…”
Section: Introductionmentioning
confidence: 99%
“…Since 1 is transparent at 365 nm, this 7 number overestimates the amount of exposure energy interacting with the film. The lack of significant ablation under these conditions is not surprising as polyarylsilanes are known to often crosslink upon exposure, presumably from attack of the silyl radical on the aromatic ring (9,24,25,26). Since only arylsilane monomers can be polymerized to a reasonable extent with metallocene catalysts, crosslinking is a concern with any polymer made by this method.…”
Section: Resultsmentioning
confidence: 99%
“…The one-photon allowed first excited states appear in the UV and have been studied previously [4]. In addition, the valence-band states of a polysilane have been studied using photoemission spectroscopy [5].…”
Section: Introductionmentioning
confidence: 99%