Thesis advisor: Jia Niu / This dissertation discusses two main projects focusing on synthesizing degradable vinyl copolymers. The first project describes the development of a general approach to synthesizing degradable vinyl random copolymers through photocontrolled radical ring-opening cascade copolymerization (rROCCP). The rROCCP of a macrocyclic allylic sulfone with acrylates or acrylamides mediated by visible light at ambient temperature achieved near-unity comonomer reactivity ratios over the entire range of feed compositions. Such a powerful approach provides degradable vinyl random copolymers with comparable material properties to their non-degradable counterparts. Experimental and computational evidence also revealed an unusual reversible inhibition of chain propagation by in situ generated sulfur dioxide (SO2), which was successfully overcome by reducing the solubility of SO2 during polymerization. The second project depicts a general method for organocatalyzed photocontrolled radical copolymerization of a macrocyclic allylic sulfone and various types of vinyl monomers, including acrylates, acrylamides, styrene, and methacrylate. Catalyzed by Eosin Y under visible light irradiation, copolymerization of the macrocyclic allylic sulfone and acrylic monomers displayed near unity comonomer reactivity ratios by fitting the copolymer composition to the Beckingham-Sanoya-Lynd integrated model. The macrocyclic allylic sulfone was also successfully copolymerized with styrene or methyl methacrylate to generate degradable polystyrene and poly(methyl methacrylate). These degradable vinyl copolymers exhibited tunable thermal properties correlated with the incorporation of degradable main-chain diester motif. / Thesis (PhD) — Boston College, 2023. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Récemment, la chimie des phosphoramidites s’est montrée efficace et polyvalente en tant que plateforme pour accéder à des poly(phosphodiester)s à séquence définies abiotiques. Grâce à cette stratégie, les monomères peuvent être placés dans la chaîne à des positions choisies, ouvrant la voie à de nombreuses possibilités pour la préparation de macromolécules fonctionnelles. Ici, la méthode phosphoramidite a été explorée pour la synthèse de polymères dits numériques, qui contiennent des séquences de monomères encodées binairement. Des polymères dont les longueurs de chaînes et les séquences numériques sont contrôlées ont été préparés en utilisant une stratégie phosphoramidite classique impliquant des groupements protecteurs diméthoxytrityles, ou bien un procédé photocontrôlé faisant intervenir des groupements nitrophénylpropyloxycarbonyles clivables à la lumière. En outre, plusieurs stratégies pour modifier l’information contenue dans les chaînes latérales ont été étudiées dans cette thèse. Une modification binaire post-polymérisation à travers deux cycloadditions alcyne-azoture catalysées par le cuivre(I) consécutives a été examinée pour optimiser les chaînes latérales des poly(phosphodiester)s à séquences définies. De plus, la libération photocontrôlée de différents motifs éthers ortho-nitrobenzyliques latéraux a été étudiée. Ces fonctions ont permis la conception d’oligo(phosphodiester)s numériques dont les séquences d’information peuvent être effacées ou révélées grâce à la lumière. / Phosphoramidite chemistry has recently been evidenced to be an efficient and versatile platform to access sequence-defined abiotic poly(phosphodiester)s. Using this strategy, monomers can be placed at defined positions positions in a chain, thus opening up wide possibilities for the preparation of functional macromolecules.Here, the phosphoramidite platform was explored to synthesize so-called digital polymers, which contain monomer-coded binary sequences. Polymers with controlled chain lengths and digital sequences were prepared using either a standard phosphoramidite strategy involving dimethoxytrityl protective groups or a photo-controlled process involving light-cleavable nitrophenylpropyloxycarbonyl protective groups. Additionally, several strategies to modify the side chain information were investigated in this thesis. A binary post-polymerization modification by means of sequential copper(I)-catalyzed alkyne-azide cycloadditions was investigated for tuning the side chain functionality of sequence-defined poly(phosphodiester)s. Moreover, the photo-controlled release of several ortho-nitrobenzylic ether side chain motifs was studied. These moieties allowed the design of digital oligo(phosphodiester)s whose sequence information can be erased or revealed with light as a trigger.