Acetylenic monomers are a group of versatile building blocks for the construction of π-conjugated polymers and acetylenic polymerizations have emerged as useful techniques for the syntheses of advanced specialty polymers with novel molecular structures and unique functional properties. In this thesis work, I have launched a program for the exploration of new triple-bond polymerization reactions for synthesizing new opto-electronically active acetylenic polymers. Four types of acetylenic polymerization reactions have been successfully developed: (1) rhodium (Rh)-catalyzed thio-click polymerization of dithiols and diynes to linear poly(vinylene sulfide)s, (2) Rh-catalyzed decarbonylative polyaddition of aroyl chlorides and alkynes to linear and hyperbranched poly(arylene chlorovinylene)s,...[ Read more ]

Acetylenic monomers are a group of versatile building blocks for the construction of π-conjugated polymers and acetylenic polymerizations have emerged as useful techniques for the syntheses of advanced specialty polymers with novel molecular structures and unique functional properties. In this thesis work, I have launched a program for the exploration of new triple-bond polymerization reactions for synthesizing new opto-electronically active acetylenic polymers. Four types of acetylenic polymerization reactions have been successfully developed: (1) rhodium (Rh)-catalyzed thio-click polymerization of dithiols and diynes to linear poly(vinylene sulfide)s, (2) Rh-catalyzed decarbonylative polyaddition of aroyl chlorides and alkynes to linear and hyperbranched poly(arylene chlorovinylene)s, (3) tantalum- and ruthenium-catalyzed homopolycyclotrimerizations of A₂-type diynes to functional hyperbranched poly(arylene)s, and (4) copper-catalyzed azide−alkyne click reaction to large luminogenic molecules with self-assembled capability and high fluorescence quantum efficiency in the aggregate state.

Main research efforts were devoted to the synthesis of new functional monomers, catalyst screening, systematic study of polymerization behaviors, characterization of different orders of structures, and explorations of functional properties of the polymers and their practical applications. The acetylenic polymers were synthesized in high yields (up to 100%) with high molecular weights (M_w up to ~5.3 × 10⁵). The structures and properties of the polymers were carefully characterized and evaluated by standard spectroscopic techniques such as IR, NMR, TGA, DSC, UV, PL, CD, XRD, SEM, TEM, and VSM analyses. The structure−property relationship was established. Apart from the excellent solubility and thermal stability, an array of novel functional properties was discovered, such as high light refractivity (refractive index up to ~1.9), novel aggregation-induced/enhanced emission (fluorescence quantum efficiency up to unity in the solid state), fluorescent chemosensors for superamplified detection of explosives, molecular containers for potential drug delivery, fluorescent patterning, supramolecular assembly, ceramization and magnetization, and so on.