-Conjugated Polyphenylenes with Diazaborole Side Chains Synthesized via 1,2-Phenylenediamine Polymer

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• 作者：Isao Yamaguchi ; Bong-Jin Choi ; Take-aki Koizumi ; Kenji Kubota ; Takakazu Yamamoto
• 刊名：Macromolecules
• 出版年：2007
• 出版时间：February 6, 2007
• 年：2007
• 卷：40
• 期：3
• 页码：438 - 443
• 全文大小：138K
• 年卷期：v.40,no.3(February 6, 2007)
• ISSN：1520-5835

文摘

Pd-complex-catalyzed polycondensation of 3,6-dibromo-1,2-phenylenediamine (1) with 2,7-bis(1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene (2) gave polymer 1a which consisted of 1,2-phenylenediamine-3,6-diyl and 9,9-dioctylfluorene-2,7-diyl units in 99% yield. Polymer 1a showed a weight-average molecularweight (M_w) of 78 000 in the light scattering analysis and gave an intrinsic viscosity of 0.74 dL g^-1. Reaction ofpolymer 1a with aromatic boronic acids, Ar-B(OH)₂ (Ar = C₆H₅, C₆H₄-p-Bu, and C₆H₄-p-OMe), providedpolymers 2a-2c with a diazaborole ring in the side chain. A model compound of polymer 1a, [1,4';1',1' ';4' ',1' '';4' '',1' '' ']quinquephenyl-2' ',3' '-diamine (model compound 1), was also prepared by Pd-complex-catalyzed reactionof 1 with biphenyl-4-boronic acid. Structures of the polymers and the model compound were determinedby ¹H NMR and IR spectroscopy as well as by elemental analyses. All the polymers and the modelcompound were photoluminescent in solution, and introduction of the diazaborole ring enhanced intensity ofphotoluminescence (PL). Cyclic voltammetry revealed that all the polymers and the model compound wereelectrochemically active in solutions, and the phenylenediamine and benzodiazaborole units behave as an electron-donating group. Thermal stability of polymer 1a was improved by transformation of the diamino group to thediazaborole side chain.