High Molecular Weight Phosphazene Copolymers Having Chemical Functions Inside Chiral Pockets Formed by (R)‐(1,1′‐Binaphthyl‐2,2′‐dioxy)phosphazene Units

The polyphosphazene {[NPCl2]x[NP(O2C20H12)]1−x}n (O2C20H12 = 1,1′-binaphthyl-2,2′-dioxy) reacted in refluxing THF in the presence of Cs2CO3 with HOC5H4N or para-substituted phenols HOC6H4R to give the random copolymers {[NP(OC5H4N)2]x[NP(O2C20H12)]1−x}n (1) or {[NP(OC6H4R)2]x[NP(O2C20H12)]1−x}n [R = CN (2), COMe (3), CO2nPr (4), PPh2 (5)] and with H2NnBu to give {[NP(NHnBu)2]x[NP(O2C20H12)]1−x}n (6). The reaction of the polymer {[NPCl2]x[NP(O2C20H10Br2)]1−x}n (O2C20H10Br2 = 6,6′-dibromo-1,1′-binaphthyl-2,2′-dioxy) with HOC6H4PPh2 and Cs2CO3 gave {[NP(OC6H4PPh2)2]x[NP(O2C20H10Br2)]1−x}n (7). Those polymers have a very high glass-transition temperature (Tg) and a chemical function or ligand that is in the interior of a chiral pocket. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)