Polysilane derivatives

Another fertile area of current interest is the synthesis of stable homocyclic polysilane derivatives.Typical examples are cyclo-(SiMe2)7, > (cyclo-Si5Me9)-(SiMe2) -(cyclo-SisMeg), n = 2-5, and several new permethy-lated polycylic silanes such as the colourless crystalline compounds bicyclo[3.2.1]-Si8Mei4 (mp 245°), bicyclo[3.3.1]-Si9Mei6 (mp >330°) and... 

In a continuing study of substituent effects on the spectra of polysilane derivatives, we have succeeded in the preparation of the first soluble poly(diarylsilane) homopolymers. Materials of this type have traditionally proved to be insoluble and intractable. Very recently, West and co-workers have reported the preparation of some soluble copolymers which contain diphenylsilylene units (48,49). 

Contrast enhancement lithography is a clever procedure which uses a bleachable contrast enhancing layer to restore the distorted aerial image of the mask which has been blurred by diffraction effects into a sharp image at the underlying photoresist surface. The process is too complicated to explain in detail here and the interested reader is referred to the cited literature (60,61). Suffice it to say that the large extinction coefficients of most polysilane derivatives coupled with their ready bleachability make them ideally suited for such purposes and we have demonstrated this application at 313 nm (16,18). 

A few synthetic helical polymers are known to act as chiral selectors.7a,918d l8k i9d i9h ancj are widely used as chiral stationary phases (CSP) in gas or liquid chromatography.73,53 Recently, it has been reported that the preference of one helical sense in isotropic solution can be induced by some interaction between optically inactive polymers and chiral solvents/additives. Examples of this include poly(n-hexyl isocyanate)18d l8k and poly(phenylacetylene)s bearing functional group.19d 19h The polysilane derivatives also show chiral recognition ability in solution at room temperature. Poly(methyl-ft-pinanylsilane) includes two chiral centers per bulky hydrophobic pinanyl side group28 and... 

Soluble polysilane derivatives (I) represent a new class of radiation sensitive materials for which a number of new applications have recently appeared. In this regard, they have been utilized as (i) thermal precursors to ceramic materials (2,3) ... 

Table I. Trapping. products from the exhaustive irradiation of some polysilane derivatives [ (SiR R2 ) ] at 254 nm in the presence of triethylsilane (a) yields were less than 2% ...

Other polymers containing Si in the main chain are the polysilanes. The discovery that polysilane derivatives were radiation sensitive(20), coupled with their stability in an oxygen plasma, has led to a number of microlithographic applications(14, 21-24). For the... 

The chemical modification of fullerenes has received considerable attention in the last decade in order to achieve new applications to material sciences [27]. Fuller-ene-bonded polysilane derivatives might be expected to show high conductivity since Ceo-doped polysilane is found to be a good photoconductor [28]. Therefore, a variety of silylated derivatives have been obtained to date, although the available methods are limited to the photoinduced addition of various silanes to Ceo-... 

The observation that more soluble, less crystalline materials containing larger alkyl substituents (6) or aromatic groups (7,8) could be synthesized suggested additional applications for polysilane derivatives. In this regard, West and co-workers have reported that a soluble copolymer 1 produced by the... 

The key intermediates in the process are the silylenes and the radical fragments, both of which should be amenable to trapping experiments. With this in mind, two representative, polysilane derivatives 6 and 9, were irradiated (254 nm) in the presence of excess triethylsilane, and the results of this experiment are shown in Figure 6. Since the polysilane 9 was not soluble in the trapping reagent, it was dissolved in cyclohexane which contained a 100 fold molar excess of triethylsilane. In each case, the major isolable volatile products... 

Figure 5. Mechanistic hypothesis for the photodegradation of high molecular weight polysilane derivatives.

In an effort to increase the efficiency of scission, particularly in the solid-state where chain repair is most competitive, a number of external additives were auditioned. Since both the Xmax and the absorptivity of polysilane derivatives are functions of molecular weight, splitting the main polymer chain results in a rapid bleaching of the original absorption. This unusual feature can be used as a qualitative, diagnostic test of scission efficiency which greatly facilitates the testing of additives. 

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