Turn-on Phosphorescence by Metal Coordination to a Multivalent Terpyridine Ligand: A New Paradigm for Luminescent Sensors
Turn-on Phosphorescence by Metal Coordination to a Multivalent Terpyridine Ligand: A New Paradigm for Luminescent Sensors
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DOI：
10.1021/ja501458s
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发表时间：
2014-04-30
影响因子：
15
通讯作者：
Ceroni, Paola
中科院分区：
文献类型：
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作者：
Fermi, Andrea;Bergamini, Giacomo;Ceroni, Paola
设计了一种在外围带有六个三联吡啶 (tpy) 单元的六硫苯分子，将固态核心显示的聚集诱导磷光与 tpy 单元的金属结合特性耦合起来。当 Mg2+ 在 THF 溶液中络合时，六硫苯核心的磷光被打开。金属离子配位形成超分子聚合物，阻碍核心发色团的分子内旋转和运动，从而有利于发光激发态的辐射失活。当激发聚合结构的[Mg(tpy)(2)](2+)单元时，核心磷光发生敏化，效率>90%。添加氟离子后，光捕获聚合物天线可以被拆卸，从而关闭发光并为氟离子传感提供一种新工具。因此，这个独特的系统可以用作阳离子或阴离子传感器。
A hexathiobenzene molecule carrying six terpyridine (tpy) units at the periphery has been designed to couple the aggregation induced phosphorescence, displayed by the core in the solid state, to the metal binding properties of the tpy units. Upon Mg2+ complexation in THF solution, phosphorescence of the hexathiobenzene core is turned on. Metal ion coordination yields the formation of a supramolecular polymer which hinders intramolecular rotations and motions of the core chromophore, thus favoring radiative deactivation of the luminescent excited state. Upon excitation of the [Mg(tpy)(2)](2+) units of the polymeric structure, sensitization of the core phosphorescence takes place with >90% efficiency. The light-harvesting polymeric antenna can be disassembled upon fluoride ion addition, thereby switching off luminescence and offering a new tool for fluoride ion sensing. This unique system can, thus, serve as cation or anion sensor.