Synthesis of miktoarm star copolymer Ru(II) complexes by click-to-chelate approach
Synthesis of miktoarm star copolymer Ru(II) complexes by click-to-chelate approach
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DOI：
10.1038/pj.2012.100
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发表时间：
2013-02
期刊：
影响因子：
2.8
通讯作者：
Nao Xiao;Yougen Chen;Xiande Shen;Chunhong Zhang;S. Yano;M. Gottschaldt;U. Schubert;T. Kakuchi;T. Satoh
中科院分区：
文献类型：
--
作者：
Nao Xiao;Yougen Chen;Xiande Shen;Chunhong Zhang;S. Yano;M. Gottschaldt;U. Schubert;T. Kakuchi;T. Satoh
用一步法合成了一系列AB2-、ABC-、(AB)2-、A2B2-和ABCD型杂臂共聚物Ru(II)的配合物。该方法包括Ru(II)(DMSO)4Cl2与聚合物取代的2-(1H-1，2，3-三氮唑-4-基)吡啶(Tapy)或2，6-双(1H-1，2，3-三唑-4-基)吡啶(双)配体的第一步螯合反应，得到了稳定的聚合物Ru(II)单配体。以及聚合物Ru(II)与另一个Tapy或Bitapy配体的第二步螯合反应，得到杂臂共聚物Ru(II)配合物。为了合成它们，首先通过叠氮末端聚合物分别与2-乙炔基吡啶和2，6-二乙炔基吡啶的点击反应合成了聚合物取代的tapy和bitapy配体。以2-溴异丁酸乙酯为引发剂，通过原子转移自由基聚合法合成了叠氮基封端的聚苯乙烯(PS)和聚丙烯酸丁酯(PBA)。以6-叠氮基-1-己醇和三氯环戊二烯基钛为原料，采用活性配位聚合的方法，以异氰酸正己酯为原料，合成了叠氮化端基聚异氰酸酯。以6-叠氮基-1-己醇为引发剂，以磷酸二苯酯为催化剂，ɛ-己内酯为原料，t-Bu-P4磷腈为催化剂，通过控制/活性开环聚合合成了ɛ-己内酯的叠氮基封端聚环氧苯乙烯和聚己内酯。
A series of AB 2-, ABC-,(AB) 2-, A 2 B 2-and ABCD-type miktoarm copolymer Ru (II) complexes was synthesized by a stepwise chelating method, which involved the first-step chelating reaction of Ru (II)(DMSO) 4 Cl 2 with a polymer-substituted 2-(1H-1, 2, 3-triazol-4-yl) pyridine (tapy) or 2, 6-bis (1H-1, 2, 3-triazol-4-yl) pyridine (bitapy) ligand to produce a stable polymer Ru (II) mono-complex, and a second-step chelating reaction of the polymer Ru (II) mono-complex with another tapy or bitapy ligand to afford the miktoarm copolymer Ru (II) complexes. In order to synthesize them, the polymer-substituted tapy and bitapy ligands were first prepared by the click reaction of azido-terminated polymers with 2-ethynylpyridine and 2, 6-diethynylpyridine, respectively. The azido-terminated polystyrene (PS) and poly (n-butyl acrylate)(PBA) were prepared by the atom-transfer radical polymerizations of styrene and n-butyl acrylate using ethyl 2-bromoisobutyrate as the initiator, followed by the substitutions of their end bromines with an azido group, respectively. The azido-terminated poly (n-hexyl isocyanate) was prepared by the living coordination polymerization of n-hexyl isocyanate using dichloro (cyclopentadienyl)(6-azidohexyloxy) titanium that was prepared by mixing 6-azido-1-hexanol with trichloro (cyclopentadienyl) titanium before the polymerization. The azido-terminated poly (styrene oxide) and poly (ɛ-caprolactone) were synthesized by the controlled/living ring-opening polymerizations of ɛ-caprolactone using diphenyl phosphate as the catalyst and of styrene oxide using the phosphazene base of t-Bu-P 4 as the catalyst, respectively, in which 6-azido-1-hexanol was used as the initiator.