π-Conjugated Poly(aryleneethynylene)s Consisting of Salophen and Ni-Salophen Units in the π-Conjugated Main Chain: Preparation and Chemical Properties
π-Conjugated Poly(aryleneethynylene)s Consisting of Salophen and Ni-Salophen Units in the π-Conjugated Main Chain: Preparation and Chemical Properties
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DOI：
10.1021/ma101800f
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发表时间：
2010-12
期刊：
影响因子：
5.5
通讯作者：
Hiroki Fukumoto;Kazuto Yamane;Y. Kase;Takakazu Yamamoto
中科院分区：
文献类型：
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作者：
Hiroki Fukumoto;Kazuto Yamane;Y. Kase;Takakazu Yamamoto
通过钯催化的H-Salophen-Ar-H-Salophen（Ar =芴或2，5-二烷氧基对苯撑）与Salophen的二溴化合物（Br 2-Salophen）及其镍配合物（Br 2-Salophen-Ni）的缩聚反应，高产率地制备了由N，N′-双（亚水杨基）-1，2-苯二胺（Salophen）单元（Poly-1-Poly-3）和Salophen-镍配合物单元（Poly-1-Ni）组成的π共轭聚芳撑乙炔。不含Ni的聚合物（Poly-1−Poly-3）在CHCl 3和THF中显示出良好的溶解性，具有高的热稳定性，并且在GPC分析中显示出9200−14000的数均分子量（Mn）。聚合物的紫外-维斯光谱在约420 nm处显示出π-π* 跃迁峰，这与聚（对苯乙炔）的那些相当。Poly-1-Ni的紫外-维斯光谱在480和600 nm处显示出额外的中间峰和小峰，分别归属于电荷转移（CT）电子跃迁和d-d跃迁。Poly-1与Ni ~（2+）的络合过程清晰、定量。
π-Conjugated poly(aryleneethynylene)s consisting of N,N′-bis(salicylidene)-1,2-phenylenediamine (salophen) units (Poly-1−Poly-3) and salophen−nickel complex units (Poly-1−Ni) were prepared in high yields by the palladium-catalyzed polycondensation of H−≡−Ar−≡−H (Ar = fluorene or 2,5-dialkoxy-p-phenylene) with dibromo compounds of salophen (Br2−Salophen) and its nickel complex (Br2−Salophen−Ni), respectively. The Ni-free polymers (Poly-1−Poly-3) showed good solubility in CHCl3 and THF, had high thermal stability, and exhibited number-average molecular weights (Mn) of 9200−14000 in GPC analysis. The UV−vis spectra of the polymers showed π−π* transition peaks at about 420 nm, which was comparable to those of poly(p-phenyleneethynylene)s. The UV−vis spectrum of Poly-1−Ni exhibited additional intermediate and small peaks at about 480 and 600 nm, which were assigned to a charge-transfer (CT) electronic transition and a d−d transition, respectively. The complexation of Poly-1 with Ni2+ proceeded clearly and quan...