From N,N-diphenyl-N-naphtho[2,1-b]thieno[2,3-b:3′,2′-d] dithiophene-5-yl-amine to propeller-shaped N,N,N-tri(naphtho[2,1-b]thieno[2,3-b:3′,2′-d]dithiophene-5-yl)-amine: syntheses and structures

Three unique propeller-shaped helicenyl amines compounds: N,N-diphenyl-N-naphtho[2,1-b]thieno[2,3b:3 ',2 '-c]Iclithiophene-5-yl-amine (1), N-phenyl-N,N-di(naphtho[2,1-b]thieno[2,3-6:3 ',2 '-d]dithiophene5-yl)amine (2), and N,N,N-tri(naphtho[2,1-b]thieno[2,3-b:3 ',2 '-d]dithiophene-5-yl)amine (3) were efficiently synthesized by Wittig reaction and oxidative photocyclization. The crystal structures of 1, 2 and molecular configuration optimization (DFT-B3LYP/6-3 +G(d)) of 3 reveal that the steric hindrance from the moiety of trithia[5]helicene effectively forces the nitrogen atom and the three bonded carbon atoms to coplanar and the interplanar angles of the facing terminal thiophene ring and benzene ring becoming larger when the helical arm increased from 1 to 3. Electrochemical properties and UV-vis absorption behaviors of 1, 2, 3 were primarily determined by the moiety of trithia[5]helicene. (C) 2014 Elsevier Ltd. All rights reserved.