Polyacetylene and Polynorbornene Derivatives Carrying TEMPO. Synthesis and Properties as Organic Radical Battery Materials

Summary: 2,2,6,6‐Tetramethylpiperidine 1‐oxyl (TEMPO)‐containing N ‐propargylamide HCCCH 2 NHCO‐4‐TEMPO ( 1 ), propargyl ester HCCCH 2 OCO‐4‐TEMPO ( 2 ), phenylacetylene derivative HCCC 6 H 3 ‐3,4‐(CO 2 ‐4‐TEMPO) 2 ( 3 ), and norbornene diester monomers, NB‐2,3‐ exo,exo ‐(CH 2 OCO‐4‐TEMPO) 2 ( 4 ), NB‐2,3‐ endo,exo ‐(COO‐4‐TEMPO) 2 ( 5a ), NB‐2,3‐ endo,endo ‐(COO‐4‐TEMPO) 2 ( 5b ) (NB = norbornene, 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 47 000–185 000 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( 1 ), 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.Charge–discharge curves of poly( 5a ) at a current density of 0.13 mA · cm −2 (100 mA · g −1 ‐cathode active material ) in the voltage range of 2.5–4.2 V.