Light- and Heat-Triggered Reversible Linear-Cyclic Topological Conversion of Telechelic Polymers with Anthryl End Groups.

This study demonstrates the comprehensive investigation on the reversible linear-cyclic topological conversion of hydrophilic and hydrophobic polymers with various molecular weights. The reactions were triggered by light or heat, which reversibly dimerize and cleave the anthryl or coumarinyl end groups of the telechelics. Poly(ethylene oxide) telechelics with anthryl end groups attached through electron-donating (Ant-O-PEO and Ant-CH2-PEO) and electron-withdrawing (Ant-CO2-PEO) linking groups were synthesized. While Ant-O-PEO and Ant-CH2-PEO decomposed upon photoirradiation at 365 nm, Ant-CO2-PEO efficiently cyclized through the photodimerization of the anthryl end groups both in water and in organic solvents shown by NMR, SEC, and MALDI-TOF MS. The lower the molecular weight, the faster the cyclization proceeded. When cyclized Ant-CO2-PEO was heated at 150 °C in bulk, the polymers quantitatively converted back into the original linear topology. Furthermore, repeatable linear-cyclic topological conversion was confirmed. The reversible topological conversion of hydrophobic poly(tetrahydrofuran) telechelics with anthryl end groups (Ant-PTHF) was also successful. In addition, poly(ethylene oxide) telechelics with coumarinyl end groups (Cou-PEO) were also cyclized by irradiation at 365 nm in water. However, the cyclization hardly occurred when performed in methanol likely due to the lack of sufficient hydrophobic interaction of the coumarinyl end groups. Cyclized Cou-PEO was irradiated at 254 nm to test for linearization, finding the linear product and cyclic precursor were likely photoequilibrated.