기능성 다이벤조실올의 합성.

Abstract

CHAPTER 1 Polysiloles have recently received much attention because of their unusual electronic properties. These unusual optical and electrical properties can be useful in electronic devices, such as electron transporting materials, light-emitting diodes (LEDs), and chemical sensors. Poly(2,3,4,5-tetraphenyl)siloles (1, so called polysilole,PTPS) shown in Scheme 1 possess both 2,3,4,5-tetraphenyl-1-silacyclopenta- 2,4-diene and Si-Si backbone but the unsaturated five-membered ring of the silole shifts their optical absorption and emission spectra into the visible spectral region. Polysilanes are well known as thermally stable polymers and they exhibit efficient emission in the UV region, high hole mobility, and high nonlinear optical susceptibility. These novel properties arise from σ-σ* delocalization of electrons along the Si-Si backbones. Siloles (2) has a low reduction potential and a low-lying LUMO due to σ*-π* conjugation arising from the interaction between the σ* orbital of the silicon atom and the π* orbital of the butadiene moiety of the five membered ring. Water-soluble polymers encompass a wide variety of macromolecules, from biopolymers to synthetic polymers, that are of great industrial and commercial importance.1 Although water-soluble organic polymers have been widely studied, their inorganic counterparts have been largely left unexplored.2 Poly[bis(methoxyethoxyethoxy) phosphazene] represents the most wellknown polymer of this class.3 Several examples of watersoluble poly(silanes) and poly(siloxanes) have also been reported.4 However, water-soluble polymers with transition elements in the main chain are rare. To our knowledge, the only previous report of a water-soluble ferrocene-based polymer is that from Neuse et al., in which low molecular weight (ca. Mn ) 2400) poly(ferrocenium) salts were studied.5 Thermal ring-opening polymerization (ROP) of siliconbridged [1]ferrocenophanes 1 provides a convenient route to high molecular weight (Mn > 105) poly(ferrocenes) 2 (Scheme 1).6 Ambient temperature transitionmetal catalyzed and anionic ROP routes to these materials have subsequently been reported.7,8 Initially, the substituents attached to silicon were limited to aryl and alkyl groups. More recently, we described a general route to polymerizable silicon-bridged [1]ferrocenophanes with amino, alkoxy, and aryloxy substituents at silicon.9 The resulting poly(ferrocenylsilanes) are redox-active and possess interacting metal atoms in the main chain. Interest has also focused on their pyrolytic conversion to magnetic ceramic materials (including nanostructures) and their semiconductive properties.6 To further diversify the properties accessible with poly(ferrocenylsilanes), in this paper we report the introduction of polyether or ionic substituents that can impart hydrophilicity or water solubility to the resultant organometallic polymer. These poly(ferrocenylsilanes) are of potential interest as electrode materials and as redox-active polymeric electrolytes, in which the ionic conductivity might be switched by oxidation of the iron centers.10 Such materials are also of interest for multilayer self-assembly applications and for the preparation of micellar aggregates as preliminary results indicate that ferrocene-based surfactants could potentially be used as redox-active drug delivery agents.11 Moreover, various water-soluble ferrocenium salts have been shown to display anticancer activity.12 CHAPTER 2 Polysiloles have recently received much attention because of their unusual electronic properties. These unusual optical and electrical properties can be useful in electronic devices, such as electron transporting materials, light-emitting diodes (LEDs), and chemical sensors. Poly(2,3,4,5-tetraphenyl)siloles (1, so called polysilole,PTPS) shown in Scheme 1 possess both 2,3,4,5-tetraphenyl-1-silacyclopenta- 2,4-diene and Si-Si backbone but the unsaturated five-membered ring of the silole shifts their optical absorption and emission spectra into the visible spectral region. Polysilanes are well known as thermally stable polymers and they exhibit efficient emission in the UV region, high hole mobility, and high nonlinear optical susceptibility. These novel properties arise from σ-σ* delocalization of electrons along the Si-Si backbones. Siloles (2) has a low reduction potential and a low-lying LUMO due to σ*-π* conjugation arising from the interaction between the σ* orbital of the silicon atom and the π* orbital of the butadiene moiety of the five membered ring.