New Achiral and Chiral Multilayer 3D Polymers: Design, Synthesis, and Property Modulation using Anthracene and Ferrocene Bridges

This dissertation develops multilayer, $\pi$-conjugated polymers across three families: (i) compact naphthalene-derived architectures (including anthracene-naphthalene multilayers), (ii) ferrocene-naphthalene redox-photonic conjugates, and (iii) axially chiral binaphthyl frameworks. The polymers were constructed by Suzuki-Miyaura or CuI-assisted, Pd-catalyzed Sonogashira polycondensation and characterized by NMR and GPC, UV-Vis absorption/steady-state fluorescence, DLS, and electron microscopy. In dispersion, naphthalene-rich systems exhibit aggregation-induced emission (AIE)–like turn-on under mild aggregation, consistent with restriction of intramolecular motion in the condensed phase; by contrast, ferrocene-containing conjugates in our series show more pronounced aggregation-caused quenching (ACQ), in line with the general susceptibility of planar $\pi$-systems to excimeric or nonradiative decay pathways in the solid state. Axially chiral backbones present concentration-dependent optical switching, which we attribute to the evolving balance between short-range packing and conformational rigidity in aggregated states. In thin films, side-chain sterics and short-range $\pi$-$\pi$ contacts modulate brightness and color, while thermogravimetric analysis indicates stability above $250\,^\circ\mathrm{C}$, supporting use as durable optical coatings. Ferrocene units retain a reversible \ce{Fc/Fc+} redox couple without erasing essential photophysics, enabling electrochemically addressable sensing interfaces. Collectively, these results outline a practical design frame: deploy naphthalene-layered motifs to favor radiative channels (AIE regime), manage quenching in ferrocene-dense networks (ACQ regime), and tune axially chiral frameworks via concentration and packing control to obtain aggregation-responsive emitters and thermally robust photonic/sensing platforms.