Polymer chains electronic properties

This tendency is related to the polarization properties of the monomer substituents (42). Monomers that are dissimilar in polarity tend to form alternating monomer sequences in the polymer chain. An example is the monomer pair acrylonitrile—styrene. Styrene, with its pendent phenyl group, has a relatively electronegative double bond whereas acrylonitrile, with its electron-withdrawing nitrile group, tends to be electropositive. 

Another important factor affecting the electronic properties is the steric barrier to planarity along the polymer chain. Since polyheterocycles and polyarylenes must adopt a planar geometry in the ionized state to form quinoid-like segments, steric factors that limit the ability of the polymer to adopt geometries which are planar with respect to adjacent rings have a detrimental effect on the electronic properties (181). 

Another possible modification of poly(sulfur nitride) that is expected to produce conducting polymers is the replacement of alternating sulfur in the thiazyl chain by an RC unit, i.e., [(R)CNSN]x. This type of polymer would have five r-electrons per four atoms in the repeating unit and, consequently, would have a partially occupied conducting band. The prospect of tuning the electronic properties of this polymer by... 

Finally, we would like to point that one of the easiest ways to influence the electronic properties of conjugated oligomers and polymers is to vary the chain... 

The results presented up to here concern only one-dimensional oligomers and polymers of the PPP-lype. This section is mainly focussed on the electronic properties of extended re-chains and on the morphology of solid PPPs using chain-stiffness as a structure-forming principle for supramolecular architectures. 

The recent interest in substituted silane polymers has resulted in a number of theoretical (15-19) and spectroscopic (19-21) studies. Most of the theoretical studies have assumed an all-trans planar zig-zag backbone conformation for computational simplicity. However, early PES studies of a number of short chain silicon catenates strongly suggested that the electronic properties may also depend on the conformation of the silicon backbone (22). This was recently confirmed by spectroscopic studies of poly(di-n-hexylsilane) in the solid state (23-26). Complementary studies in solution have suggested that conformational changes in the polysilane backbone may also be responsible for the unusual thermochromic behavior of many derivatives (27,28). In order to avoid the additional complexities associated with this thermochromism and possible aggregation effects at low temperatures, we have limited this report to polymer solutions at room temperature. 

The conformational mobility of a chromophoric main-chain polymer is often connected to its electronic structure. Therefore, changes in the UV-visible absorption spectra and/or chiroptical properties are spectroscopically observable as thermo-, solvato-, piezo-, or electrochromisms. It is widely reported that o-conjugating polysilanes exhibit these phenomena remarkably clearly.34 However, their structural origins were controversial until recently, since limited information was available on the correlation between the conformational properties of the main chain, electronic state, and (chir)optical characteristics. In 1996, we reported that in various polysilanes in tetrahydrofuran (THF) at 30°C, the main-chain peak intensity per silicon repeat unit, e (Si repeat unit)-1 dm3 cm-1, increases exponentially as the viscosity index, a, increases.41 Although conventional viscometric measurements often requires a wide range of low-dispersity molecular-weight polymer samples, a size exclusion chromatography (SEC) machine equipped with a viscometric detector can afford... 

The chemistry of compounds containing Si-Si bond(s) is an intriguing subject in the field of organosilicon chemistry because Si-Si bonds have unique physical and chemical properties. The reactivities of Si-Si bonds is often compared with those of carbon-carbon double bonds. The current interest in polysilanes in material science stems from the fact that they exhibit unusual properties implying considerable electron delocalization in the polymer chain [62]. This section concerns with the unique elecrochemical properties of compounds containing Si-Si bonds (Sect. 2.4). 

Apart from the tunable color emission covering the full visible range, there are several other aspects supporting the interest in PTs for PLEDs. PTs are examples of classical conjugated polymers with intrinsic one-dimensionality of the polymer chain. Alignment can induce anisotropy in macroscopic properties such as electron transport or optical properties. Polarized... 

The electronic properties of germanium have led to an interest in incorporating the element into extended polymeric chains due to the intrinsic properties of the polymers themselves or in their use as precursors for material synth-esis. Catalytic co-polymerization of the germylene Ge[N(SiMe3)2]2 with various substituted acetylenes leads to... 

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