TY - JOUR
T1 - Triarylamine-bearing poly(1,4-phenylenevinylene)
T2 - Facile preparation and its durable aminium polyradical
AU - Kurata, Takashi
AU - Pu, Yong Jin
AU - Nishide, Hiroyuki
PY - 2007
Y1 - 2007
N2 - Poly[2-{bis(4-methoxyphenyl)amino}phenyl-5-(2-ethylhexyloxy)-1, 4-phenylenevinylene] 1 was prepared via the Gilch reaction of the p-bis(chloromethyl)benzene monomer, 2-{bis(4-methoxyphenyl)aminophenyl}-α, α′-dichloro-p-xylene. The Gilch reaction facilitated the preparation of the polyphenylenevinylene with a triarylamine pendant group when compared to that via the Heck polycondensation. The molecular weight of the polymer was approximately 4.0 × 105, and it was soluble in common solvents and was reversibly redoxed due to the pendant arylamine moiety. Chemical oxidation of 1 afforded the corresponding aminium polyradical 1+ with the half life-time of ca. 2 weeks under ambient conditions. ESR and magnetization measurements of 1+ revealed a forbidden multiplet signal and an average spin quantum number (S) of 3/2 at low temperature, respectively. The polyradical 1+ was the first example of a high molecular weight, high-spin organic polymer with solvent-solubility and film formability. 2,3-Bis[N,N-bis(4-methoxyphenyl)aminophenyl]stilbene 2 and its aminium diradical 2+ were also prepared as the model dimer compounds; 2+ was a triplet molecule at low temperature. The effect of the π-conjugated poly(1,4-phenylene-vinylene) backbone on the high-spin alignment was also discussed.
AB - Poly[2-{bis(4-methoxyphenyl)amino}phenyl-5-(2-ethylhexyloxy)-1, 4-phenylenevinylene] 1 was prepared via the Gilch reaction of the p-bis(chloromethyl)benzene monomer, 2-{bis(4-methoxyphenyl)aminophenyl}-α, α′-dichloro-p-xylene. The Gilch reaction facilitated the preparation of the polyphenylenevinylene with a triarylamine pendant group when compared to that via the Heck polycondensation. The molecular weight of the polymer was approximately 4.0 × 105, and it was soluble in common solvents and was reversibly redoxed due to the pendant arylamine moiety. Chemical oxidation of 1 afforded the corresponding aminium polyradical 1+ with the half life-time of ca. 2 weeks under ambient conditions. ESR and magnetization measurements of 1+ revealed a forbidden multiplet signal and an average spin quantum number (S) of 3/2 at low temperature, respectively. The polyradical 1+ was the first example of a high molecular weight, high-spin organic polymer with solvent-solubility and film formability. 2,3-Bis[N,N-bis(4-methoxyphenyl)aminophenyl]stilbene 2 and its aminium diradical 2+ were also prepared as the model dimer compounds; 2+ was a triplet molecule at low temperature. The effect of the π-conjugated poly(1,4-phenylene-vinylene) backbone on the high-spin alignment was also discussed.
KW - π-Conjugated polymer
KW - Aminium radical
KW - Gilch reaction
KW - High-spin molecule
KW - Poly(phenylenevinylene)
KW - Radical polymer
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U2 - 10.1295/polymj.PJ2006226
DO - 10.1295/polymj.PJ2006226
M3 - Article
AN - SCOPUS:34548335103
VL - 39
SP - 675
EP - 683
JO - Polymer Journal
JF - Polymer Journal
SN - 0032-3896
IS - 7
ER -