This review describes recent progress made in designing stimuli-responsive, functional, side-chain, end-on mesogen attached liquid crystalline polymers (LCPs). Developments in synthetic methodologies including controlled and living techniques provides an easy...

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The synthesis of a number of tailored architectures of rhodamine dye–norbornene conjugate monomers and corresponding homopolymers derived from them is described. The impact of the monomer architecture on the mechanochromic, photochromic, and thermochromic properties of rhodamine-modified polynorbornenes is reported. Color changes were caused by the reversible interconversion between the “open” and “closed” spirolactam form of the covalently attached dye. Monomers were synthesized in two principle architectures that varied on: (1) the number of polymerizable norbornene groups tethered to a bifunctional rhodamine dye; (2) the presence of flexible methylene spacers between the dye and the polymerizable norbornene groups. Introduction of norbornene groups on each of the two hydroxy groups of a bifunctional rhodamine resulted in a cross-linked polymer that exhibited better mechanochromic, photochromic, and thermochromic properties compared to the corresponding polymer without cross-links, derived from the derivatization of bifunctional rhodamine with only one norbornene. The introduction of flexible methylene spacers between the two polymerizable norbornenes and the dye molecule resulted in a polymeric framework with rapidly reversible color-changing properties upon mechanical or photostimulation. The ideal monomer molecular structure, whereby (1) attaching norbornene on both sides of the rhodamine dye and (2) methylene spacers between the dye and norbornenes on both sides afforded the nonpareil polymer structure that was capable of thermoreversible mechanochromic and photochromic features, and irreversible thermochromic features. These new materials may find utility as multi-stimuli-responsive soft materials.

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