Reversible thermo-responsive luminescent metallo-supramolecular triblock copolymers based on platinum(II) terpyridyl chromophores with unusual aggregation behaviour and red-near-infrared (NIR) emission upon heating.
Reversible thermo-responsive luminescent metallo-supramolecular triblock copolymers based on platinum(II) terpyridyl chromophores with unusual aggregation behaviour and red-near-infrared (NIR) emission upon heating.
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DOI：
10.1039/c1dt10741k
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发表时间：
2011-11
影响因子：
4
通讯作者：
Yongchen Hu;K. Chan;C. Y. Chung;V. Yam
中科院分区：
文献类型：
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作者：
Yongchen Hu;K. Chan;C. Y. Chung;V. Yam
合成并表征了两种三吡啶基金属-超分子三嵌段共聚物[ClPt（tpy）PEO-PPO-PEO（tpy）PtCl]（OTf）（2）（1）和[（Ph-C）Pt（tpy）PEO-PPO-PEO（tpy）Pt（C）C-Ph）]（OTf）（2）（2）。通过UV/维斯吸收光谱、发射光谱和1H NMR研究发现，这两种配合物在高温下发生了PtPt和/或π-π相互作用的聚集。这是由于在高于临界胶束温度的温度下由PEO-PPO-PEO共聚物驱动的球形胶束的形成，这通过TEM和DLS证实。复合物的红色近红外（NIR）发射可以通过至少10次加热和冷却循环来打开和关闭，表明胶束化是高度可逆的。
Two platinum(II) terpyridyl-based metallo-supramolecular triblock copolymers, [ClPt(tpy)PEO-PPO-PEO(tpy)PtCl](OTf)(2) (1) and [(Ph-C≡C)Pt(tpy)PEO-PPO-PEO(tpy)Pt(C≡C-Ph)](OTf)(2) (2), have been synthesized and characterized. The two complexes were found to aggregate with PtPt and/or π-π interactions at high temperature, which have not been reported so far, as revealed by UV/Vis absorption, emission and (1)H NMR study. This is due to the formation of spherical micelles driven by the PEO-PPO-PEO copolymers at temperatures above the critical micelle temperature, which was confirmed by TEM and DLS. The red-near-infrared (NIR) emission of the complexes can be switched on and off by at least ten cycles of heating and cooling, suggesting that the micellization was highly reversible.