Polyacetylene and polynorbornene derivatives carrying TEMPO. Synthesis and properties as organic radical battery materials

2,2,6,6-Tetramethylpiperidine 1-oxyl (TEMPO)containing N-propargylamide HC=CCH2NHCO-4-TEMPO (1), propargyl ester HC=CCH2OCO-4-TEMPO (2), phenylacetylene derivative HC=CC6H3-3,4-(CO2-4-TEMPO)(2) (3), and norbornene diester monomers, NB-2,3-exo,exo-(CH(2)OCO4-TEMPO)(2) (4), NB-2,3-endo,exo-(COO-4-TEMPO)(2) (5a), NB-2,3-endo,endo-(COO-4-TEMPO)(2) (5b) (NB = norbornorbornene, TEMPO= 2,2,6,6-tetramethyl-1-piperidinyloxyl) were synthesized and polymerized with rhodium and ruthenium catalysts. Monomers 2, 5a, and 5b gave polymers with number-average molecular weights of 47000-185000 in 59-100% yields, while 1, 3, and 4 gave polymers insoluble in common organic solvents in 88-100% yields. The capacities of cells fabricated with poly(l), poly(2), and poly(3) were 67, 82, and 23 Ah . kg(-1) based on the weight, respectively. The capacity of poly(5a)-based cell reached the theoretical value (109 Ah . kg(-1)) of the polymer.