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Synthesis and chemical properties of electrochromic π-conjugated polyphenylenes with pendant viologen-TCNQ salts

机译:含侧链紫精-TCNQ盐的电致变色π共轭聚苯撑的合成及化学性质

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Polyphenylene (PP) with NH2 side groups, namely, PFluNH _2, was synthesized by the Pd-catalyzed reaction of 2,5-dibromoaniline with 9,9-dihexylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester. The reaction of PFluNH2 with 1-hexyl-1′-(2,4-dinitrophenyl)-4, 4′-bipyridinium diiodide (SaltBPy(I-)) eliminated 2,4-dinitroaniline to yield PPs with viologen (1,1′-disubstituted 4,4′-bipyridinium dications), PFluBPy(I~-). The reaction of PFluBPy(I~-) with Li~+TCNQ~- resulted in anion exchange between Cl~- and TCNQ~-, and yielded PFluBPy(TCNQ~-). The reaction of PFluBPy(TCNQ~-) with the neutral TCNQ~0 resulted in an interaction between TCNQ~- and TCNQ~0, and yielded PFluBPy(TCNQ~--TCNQ~0). Cyclic voltammetry measurements suggested that an electrochemical reduction of the viologen moiety and oxidation of the polymer backbone within PFluBPy(TCNQ~-) and PFluBPy(TCNQ~--TCNQ~0). Furthermore, this reaction was accompanied by electrochromism. The electric conductivities (σ) of the pellets molded from PFluBPy(TCNQ~-) to PFluBPy(TCNQ~--TCNQ~0) were 2.7 × 10~(- 4) and 4.2 × 10~(-4) Scm~(- 1), respectively; these σ values were higher than that observed for PFluNH_2 (σ < 10~(-8) Scm ~(-1)) due to the self-doping in the polymers.
机译:通过2,5-二溴苯胺与9,9-二己基芴-2,7-二硼酸双(1,3-丙二醇)酯的Pd催化合成具有NH2侧基的聚苯撑(PPluNH _2) 。 PFluNH2与1-己基-1'-(2,4-二硝基苯基)-4,4'-联吡啶二碘化物(SaltBPy(I-))的反应消除了2,4-二硝基苯胺,生成具有紫精(1,1'的PPs -双取代的4,4'-联吡啶鎓),PFluBPy(1-)。 PFluBPy(I〜-)与Li〜+ TCNQ〜-的反应导致Cl〜-与TCNQ〜-之间发生阴离子交换,生成PFluBPy(TCNQ〜-)。 PFluBPy(TCNQ〜-)与中性TCNQ〜0的反应导致TCNQ〜-和TCNQ〜0之间发生相互作用,并产生PFluBPy(TCNQ〜--TCNQ〜0)。循环伏安法测量表明,PFluBPy(TCNQ〜-)和PFluBPy(TCNQ〜-TCNQ〜0)中紫精部分的电化学还原和聚合物主链的氧化。此外,该反应伴随有电致变色。由PFluBPy(TCNQ〜-)成型为PFluBPy(TCNQ〜-TCNQ〜0)的颗粒的电导率(σ)为2.7×10〜(-4)和4.2×10〜(-4)Scm〜(- 1);由于聚合物中的自掺杂,这些σ值高于PFluNH_2(σ<10〜(-8)Scm〜(-1))。

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