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

The polyphosphazene {[NPCl 2 ] x [NP(O 2 C 20 H 12 )] 1− x } n (O 2 C 20 H 12 = 1,1′‐binaphthyl‐2,2′‐dioxy) reacted in refluxing THF in the presence of Cs 2 CO 3 with HOC 5 H 4 N or para ‐substituted phenols HOC 6 H 4 R to give the random copolymers {[NP(OC 5 H 4 N) 2 ] x [NP(O 2 C 20 H 12 )] 1− x } n ( 1 ) or {[NP(OC 6 H 4 R) 2 ] x [NP(O 2 C 20 H 12 )] 1− x } n [R = CN ( 2 ), COMe ( 3 ), CO 2 n Pr ( 4 ), PPh 2 ( 5 )] and with H 2 N n Bu to give {[NP(NH n Bu) 2 ] x [NP(O 2 C 20 H 12 )] 1− x } n ( 6 ). The reaction of the polymer {[NPCl 2 ] x [NP(O 2 C 20 H 10 Br 2 )] 1− x } n (O 2 C 20 H 10 Br 2 = 6,6′‐dibromo‐1,1′‐binaphthyl‐2,2′‐dioxy) with HOC 6 H 4 PPh 2 and Cs 2 CO 3 gave {[NP(OC 6 H 4 PPh 2 ) 2 ] x [NP(O 2 C 20 H 10 Br 2 )] 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)