Poly(dendrimers) with Phosphorescent Iridium(III) Complex-Based Side Chains Prepared via Ring-Opening Metathesis Polymerization
Poly(dendrimers) with Phosphorescent Iridium(III) Complex-Based Side Chains Prepared via Ring-Opening Metathesis Polymerization
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通过开环复分解聚合制备具有磷光铱（III）配合物侧链的聚（树枝状聚合物）
DOI：
10.1021/ma300306d
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发表时间：
2012-04-10
期刊：
影响因子：
5.5
通讯作者：
Samuel, Ifor D. W.
中科院分区：
文献类型：
--
作者：
Lai, Wen-Yong;Balfour, Michael N.;Samuel, Ifor D. W.
用Grubbs III催化剂进行开环易位聚合，合成了具有石墨烯衍生骨架的磷杂环丁烷聚（树枝状聚合物）。树枝状聚合物由具有两个2-苯基吡啶基配体和苯基三唑基配体的杂配铱（III）络合物核心、基于联苯的树枝状分子和2-乙基己氧基表面基团组成。苯基三唑基配体提供了与聚合物主链的连接点，并且两种聚（树枝状聚合物）在连接到2-苯基吡啶基配体的树枝化基元的数量上不同。每个配体具有一个和两个树枝状基元的聚（树枝状聚合物）被称为单树枝化和双树枝化。单和双树枝化的聚（树枝状聚合物）被发现具有相对较窄的多分散性，约1.4，接近喷墨印刷所需的粘度，并可以进行溶液处理，以形成薄膜。枝晶在控制材料的物理性能方面起着重要的作用。具有相同铱（III）络合物但没有连接到配体的树枝状分子的母体均聚物具有48%的溶液光致发光量子产率（PLQY）。发现溶液PLQY随着枝晶数目的增加而增加，单枝晶化材料和双枝晶化材料的溶液PLQY分别为65%和71%。PLQY的增加是由于链内发色团间相互作用的减少。在固态中观察到类似的趋势，其中母体、单树枝化聚合物和双树枝化聚合物的膜PLQY分别为2%、44%和58%，这表明链内和链间相互作用均受树枝化基元控制。© 2012美国化学学会。
Phosphorescent poly(dendrimers) with a norbornene-derived backbone have been synthesized using ring-opening metathesis polymerization with the Grubbs III catalyst. The dendrimers are comprised of a heteroleptic iridium(III) complex core with two 2-phenylpyridyl ligands and a phenyltriazolyl ligand, biphenyl-based dendrons, and 2-ethylhexyloxy surface groups. The phenyltriazolyl ligand provides the attachment point to the polymer backbone, and the two poly(dendrimers) differ in the number of dendrons attached to the 2-phenylpyridyl ligands. The poly(dendrimer) with one and two dendrons per ligand are termed mono- and doubly dendronized. The mono- and doubly dendronized poly(dendrimers) were found to have relatively narrow polydispersities, around 1.4, viscosities approaching those required for inkjet printing, and could be solution processed to form thin films. The dendrons played an important role in controlling the photophysical properties of the materials. The parent homopolymer with the same iridium(III) complex but no dendrons attached to the ligands had a solution photoluminescence quantum yield (PLQY) of 48%. The solution PLQY was found to increase with increasing number of dendrons with the mono- and doubly dendronized materials having solution PLQYs of 65% and 71%, respectively. The increase in PLQY is due to decreased intrachain interchromophore interactions. A similar trend was observed in the solid state with the parent, mono-, and doubly dendronized polymers having film PLQYs of 2%, 44%, and 58%, respectively, demonstrating that both intra- and interchain interactions are controlled by the dendrons. © 2012 American Chemical Society.