02416nas a2200229 4500008004100000022001400041245013400055210006900189260006800258300001400326490000700340520153300347653002401880653001701904653003001921653002401951653003601975100001402011700002002025700001902045856012202064 2009 eng d a0887-624X00aControl of molecular aggregation in symmetrically substituted pi-conjugated bulky poly(p-phenylenevinylene)s and their copolymers0 aControl of molecular aggregation in symmetrically substituted pi a111 RIVER ST, HOBOKEN, NJ 07030 USAbJOHN WILEY & SONS INCcMAY a2631-26460 v473 a
A new series of symmetrically substituted bulky PPV-copolymers based on poly(bis-2,5-(2-ethylhexyloxy)-1,4-phenylenevinylene) (BEH-PPV) bearing tricyclodecane (TCD) pendants were synthesized to study the effect of chain aggregation in the pi-conjugated polymer backbone. The composition of the copolymers was varied up to 100 mol % and the structures of the copolymer were confirmed by NMR and FTIR. The molecular weights of the copolymers were obtained as M(w) = 11,500-1,78,800 depending on the TCD-incorporation in BEH-PPV. The origin of the pi-aggregation was investigated using mixture of solvents (polar or nonpolar) or temperature as external stimuli. Absorption, photoluminescence, and time-resolved fluorescence decay techniques were employed as tools to trace molecular aggregation in solution and solid state. The TCD-substituted bulky copolymers showed almost twice the enhancement in photoluminescence compared with that of BEH-PPV Solvent-induced aggregation studies of copolymers revealed the existence of strong molecular aggregation in BEH-PPV compared with that of bulky copolymers. Variable temperature studies further evidence for the reversibility of molecular aggregation on beating/cooling cycles and showed isosbetic points with respect to free and aggregated polymer chains. Time-resolved fluorescent studies confirmed the existence of free and aggregated pi-conjugated species with a life time of 0.1 to 1.0 ns. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2631-2646, 2009
10aconjugated polymers10afluorescence10apoly(p-phenylenevinylene)10asolution properties10aStructure-property relationship1 aResmi, R.1 aAmrutha, S., R.1 aJayakannan, M. uhttp://library.ncl.res.in/content/control-molecular-aggregation-symmetrically-substituted-pi-conjugated-bulky-polyp-0