Organocatalyzed Controlled Radical Copolymerization toward Hybrid Functional Fluoropolymers Driven by Light

Abstract

Photo-controlled polymerizations are attractive to tailor macromolecules of complex compositions with spatiotemporal regulation. In this work, with a convenient synthesis for trifluorovinyl boronic ester (TFVB), we report a light-driven organocatalyzed copolymerization of vinyl monomers and TFVB for the first time, which enabled the controlled synthesis of a variety of hybrid fluorine/boron polymers with low dispersities and good chain-end fidelity. The good behaviors of "ON/OFF" switch, chain-extension polymerizations and post-modifications further highlight the versatility and reliability of this copolymerization. Furthermore, we demonstrate that the combination of fluorine and boron could furnish copolymer electrolytes of high lithium-ion transference number (up to 0.83), bringing new opportunities of engineering high-performance materials for energy storage purposes.

Neutral and Anionic Diboron Compounds Bearing Electron‐Precise B−B Bond

“…[30][31][32] Following a very similar strategy, the Yamashita group reported the synthesis of the tetra(o-tolyl)diborane(4) 7 through the reaction of B 2 cat 2 and o-tolMgBr (Scheme 3). [33][34] Compound 7 showed a broad signal at 89 ppm in the 11 B NMR spectra, indicating the high electrophilicity of the boron centers. The BÀ B bond of compound 7 could facilitate dihydrogen activation, leading to the formation of di(otolyl)hydroborane 8 (Scheme 4).…”

“…The cleavage of the B−B single bond can be utilized for the construction of B−E (E=O, N, C) bonds to give boryl products [1] . This approach is a very effective strategy to obtain functionalized organoboranes (such as boronic acids and their derivatives), which are essential building blocks for pharmaceutical production, [2–4] total synthesis, [5–9] and functional materials [10–14] . Common diborane(4) reagents, such as bis(pinacolato)diborane(4) B 2 pin 2 and bis(catecholato)diboron B 2 cat 2 (Figure 1), have been extensively used in organic synthesis to facilitate borylation reactions.…”

“…[1] This approach is a very effective strategy to obtain functionalized organoboranes (such as boronic acids and their derivatives), which are essential building blocks for pharmaceutical production, [2][3][4] total synthesis, [5][6][7][8][9] and functional materials. [10][11][12][13][14] Common diborane(4) reagents, such as bis(pinacolato)diborane(4) B 2 pin 2 and bis(catecholato)diboron B 2 cat 2 (Figure 1), have been extensively used in organic synthesis to facilitate borylation reactions. However, the reactivity of the BÀ B bond in these compounds is limited as a result of p-π interactions between the boron and heteroatoms.…”

Controlled Radical Copolymerization toward Well‐Defined Fluoropolymers

“…reported the introduction of trifluoromethacrylic acid units in diblock terpolymers to render pH responsiveness in water. The design of trifluorovinyl boronic esters as comonomers allowed convenient access to post‐modifiable copolymers and block copolymers via combining with boron chemistry [56] . The merging of boron and fluorine elements in copolymer matrixes enhances lithium transferring by limiting the counter‐anion movement.…”

Carborane based chalcogen-fused phenazines for visible light induced ATRP

“…After a long period of research, controlled radical polymerizations (CRPs) have provided polymers with diverse structures and stable properties. CRP methods mainly include nitroxide-mediated polymerization (NMP), 1 atom transfer radical polymerization (ATRP), 2 and reversible addition-fragmentation chain transfer (RAFT) polymerization. 3 Among these, ATRP can often provide polymers with a more controllable molecular weight (MW) and dispersity ( Đ ), and has received more widespread attention.…”