Spray coatable electrochromic dioxythiophene polymers with high coloration efficiencies

被引:319
作者
Reeves, BD
Grenier, CRG
Argun, AA
Cirpan, A
McCarley, TD
Reynolds, JR [1 ]
机构
[1] Univ Florida, Dept Chem, Ctr Macromol Sci & Engn, Gainesville, FL 32611 USA
[2] Louisiana State Univ, Dept Chem, Baton Rouge, LA 70803 USA
关键词
D O I
10.1021/ma049222y
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Four new disubstituted propylenedioxythiophene polymers have been synthesized by Grignard metathesis on the 1-5 g scale. All polymers were found to be soluble in chloroform, methylene chloride, toluene, and tetrahydrofuran and were fully structurally characterized having GPC determined number-average molecular weights ranging from 33000 to 47000 g mol(-1). Dilute polymer solutions in toluene exhibited strong red fluorescence with moderate quantum efficiencies from 0.38 to 0.50. Homogeneous thin films were formed by electropolymerization and spray casting polymer solutions onto ITO coated glass slides at thicknesses of ca. 150 nm. The films were electroactive, switching from a dark blue-purple to a transmissive sky blue upon p-doping, often with subsecond switching times, and high electrochromic contrast luminance changes (% DeltaY) of 40-70%. These studies revealed that the branched derivatives, [poly(3,3-bis(2-ethylhexyl)-3,4-dihydro-2H-thieno[3,4-b] [1,4] dioxepine)] and [poly(6,8-dibromo-3,3-bis(2-ethylhexyloxymethyl)-3,4-dihydro-2H-thieno[3,4-b] [1,4]dioxepine)], gave an electrochemical response and associated color change over a much smaller voltage range in comparison to the linear chain substituted derivatives, [poly(3,3-dihexyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine)] and [poly(3,3-bis(octadecyloxymethyl)-3,4-dihydro-2H-thieno[3,4-b] [1,4]dioxepine)]. Composite coloration efficiency values were found up to 1365 cm(2)/C; this was considerably larger than values obtained from previously studied alkylenedioxythiophene based polymers (similar to375 cm(2)/C).
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页码:7559 / 7569
页数:11
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