Synthesis and Charge/Discharge Properties of Polyacetylenes Carrying 2,2,6,6‐Tetramethyl‐1‐piperidinoxy Radicals

The 2,2,6,6‐tetramethyl‐1‐piperidinoxy (TEMPO)‐containing acetylenic monomers HCCC 6 H 3 ‐p , m‐ (CONH‐4‐TEMPO) 2 ( 1 ), HCCC 6 H 3 ‐p , m‐ (COO‐4‐TEMPO) 2 ( 2 ), ( S , S , S , S )‐HCCC 6 H 3 ‐p , m‐ [CO‐NHCH{COO‐(4‐TEMPO)}CH 2 COO‐(4‐TEMPO)] 2 ( 3 ), ( S , S )‐HCCC 6 H 4 CO‐NHCH{COO‐(4‐TEMPO)}CH 2 COO‐(4‐TEMPO) ( 4 ), HCCC 6 H 4 ‐ p ‐OCO‐4‐TEMPO ( 5 ), HCCCH 2 C(CH 3 )(CH 2 OCO‐4‐TEMPO) 2 ( 6 ), HCCCH 2 NHCO‐4‐TEMPO ( 7 ), and HCCCH 2 OCO‐4‐TEMPO ( 8 ) were polymerized to afford novel polymers containing the TEMPO radical at high densities. Monomers 1 , 3 – 6 , and 8 provided polymers with average molecular weights of 10 000–136 500 in 62–99 % yield in the presence of a rhodium catalyst, whereas monomers 2 and 7 gave insoluble polymers in 100 % yield. The formed polymers were thermally stable up to approximately 274 °C according to thermogravimetric analysis (TGA). All the TEMPO‐containing polymers demonstrated reversible charge/discharge processes, whose discharge capacities were 21.3–108 A h kg −1 . In particular, the capacity of poly( 1 )‐, poly( 4 )‐, and poly( 5 )‐based cells reached 108, 96.3, and 89.3 A h kg −1 , respectively, which practically coincided with their theoretical values.