Synthesis of new poly(arylamine)s (aryl = oligo-p-phenyl or pyridyl) by organometallic polycondensation and chemical properties of the polymers
Synthesis of new poly(arylamine)s (aryl = oligo-p-phenyl or pyridyl) by organometallic polycondensation and chemical properties of the polymers
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DOI：
10.1021/ma0611265
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发表时间：
2006-10-31
期刊：
影响因子：
5.5
通讯作者：
Yamamoto, Takakazu
中科院分区：
文献类型：
--
作者：
Horie, Masaki;Yamaguchi, Isao;Yamamoto, Takakazu
合成了[-(Ar)(M)Nr-](N)(Ar=对苯基或吡啶-2，5-二基；m=2-4；R=H或烷基)的一系列聚芳胺S。在镍或钯的促进下，相应的BOC-(叔丁氧羰基)取代的二溴单体进行脱卤化缩聚，得到了聚对苯胺S，[-(p-C6H4)(M)N(BOC)-](N)(m=2-4)。聚合物的BOC基团在200℃下脱保护得到[-(p-C6H4)MNH-](N)(m=2-4)。该聚合物作为聚苯胺和聚对苯撑PPP之间的中间聚合物。例如，[-(p-C6H4)(2)NH-](N)，P(DPA)在其循环伏安图上与PAN相似，在0.3和0.65V处出现两个等强度的氧化峰，与PAN相似；而[-(p-C6H4)(4)NH-](N)的循环伏安图在0.60V处出现一个主氧化峰，与PPP相似。掺碘聚合物的ESR数据支持聚合物氧化过程中自由基物种的形成。聚合物是光致发光的，量子产率为12-46%。含有吡啶单元的聚合物与金属络合物MX2(M=铜、镍、钴)形成金属络合物，具有手性侧链的吡啶聚合物金属络合物的圆二色谱表明金属络合形成了螺旋结构。
A series of poly(arylamine)s formulated as [-(Ar)(m)NR-](n) (Ar = p-phenylene or pyridine-2,5-diyl; m = 2-4; R = H or alkyl) were prepared. Ni- or Pd-promoted dehalogenative polycondensation of the corresponding BOC- (tert-butoxycarbonyl-) substituted dibromo monomers afforded poly(oligo-p-phenyleneamine) s, [-(p-C6H4)(m)N(BOC)-](n) (m = 2-4). Deprotection of the BOC group of the polymer at 200 degrees C gave [-(p-C6H4)mNH-](n) (m = 2-4). The polymer behaved as an intermediate polymer between poly(aniline) PAn and poly(p-phenylene) PPP. For example, [-(p-C6H4)(2)NH-](n), P(DPA), showed two oxidation peaks at around 0.3 and 0.65 V vs Ag+/Ag with equal intensity in its CV (cyclic voltammetry) chart, similar to PAn; in contrast, the CV chart of[-(p-C6H4)(4)NH-](n) exhibited a main oxidation peak at 0.60 V vs Ag+/Ag, similar to PPP. ESR data of iodine-doped polymers supported the formation of radical species in oxidation of the polymer. The polymers were photoluminescent and gave quantum yields of 12-46%. Polymers with the pyridine unit formed metal complexes with MX2 (M = Cu, Ni, Co), and CD (circular dichroism) spectra of the metal complexes of the pyridine polymer having chiral side chains suggested formation of a helical structure by the metal complexation.