Hyperbranched poly(silylenephenylenes) from polycyclotrimerization of A-type diyne monomers: Synthesis, characterization, structural modeling, thermal stability, and fluorescent patterning
Macromolecules, ISSN: 0024-9297, Vol: 40, Issue: 21, Page: 7473-7486
2007
- 53Citations
- 12Captures
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Article Description
A group of hyperbranched poly(silylenephenylenes) (hb-PSPs) were synthesized in high yields (up to 100%) by TaBr-catalyzed polycyclotrimerization of A-type monomers of silylenediynes [HC≡C-CHSi(CH) -CH-C≡CH, n = 2, 4, 6]. The hb-PSPs are completely soluble in common organic solvents such as chloroform, toluene, and THF. Spectroscopic and modeling studies confirmed that the polymers had formed via a [2 + 2 + 2] cyclotrimerization mechanism. Analysis of the triple-bond conversion processes led to the establishment of a relationship between the degree of branching and the fraction of dendritic unit. Computational simulation shed light on the real topological structures of the hb-PSPs. The polymers lost little weights when heated up to 480 °C and carbonize in high yields (up to 71%) after pyrolysis at 800 °C. The hb-PSPs possess a unique σ-π conjugated electronic structure and emit strong violet-blue light upon photoexcitation. The triple bonds on the peripheries allowed the thin films of the polymers to be readily photo-cross-linked, generating fluorescent photoimages in high resolutions. © 2007 American Chemical Society.
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