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首页> 外文期刊>Chemistry: A European journal >Tuning the decay time of lanthanide-based near infrared luminescence from micro- to milliseconds through d -> f energy transfer in discrete heterobimetallic complexes
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Tuning the decay time of lanthanide-based near infrared luminescence from micro- to milliseconds through d -> f energy transfer in discrete heterobimetallic complexes

机译：通过离散异质双金属配合物中的d-> f能量转移，将基于镧系元素的近红外发光的衰减时间从微秒调整到毫秒

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Inert and optically active pseudo-octahedral (CrN6)-N-III and (RuN6)-N-II chromophores have been incorporated by self-assembly into heterobimetallic triple-stranded helicates HHH-[CrLnL(3)](6+) and HHH-[RuLnL(3)](5+). The crystal structures of [CrLnL(3)](CF3SO3)(6) (Ln = Nd, Eu, Yb, Lu) and [RuLn(3)]- (CF3SO3)(5) (Ln = Eu, Lu) demonstrate that the helical structure can accommodate metal ions of different sizes, without sizeable change in the intermetallic M(...)Ln distances. These systems are ideally suited for unravelling the molecular factors affecting the intermetallic nd -> 4f communication. Visible irradiation of the (CrN6)-N-III and (RuN6)-N-III chromophores in HHH-[MLnL(3)](5/6+) (Ln = Nd, Yb, Er; M = Cr, Ru) eventually produces lanthanide-based near infrared (NIR) emission, after directional energy migration within the complexes. Depending on the kinetic regime associated with each specific d-f pair, the NIR luminescence decay times can be tuned from micro- to milliseconds. The origin of this effect, together with its rational control for programming optical functions in discrete heterobimetallic entities, are discussed.
机译：惰性和旋光性拟八面体（CrN6）-N-III和（RuN6）-N-II发色团已通过自组装结合到杂双金属三链螺旋HHH- [CrLnL（3）]（6+）和HHH中-[RuLnL（3）]（5+）。 [CrLnL（3）]（CF3SO3）（6）（Ln = Nd，Eu，Yb，Lu）和[RuLn（3）]-（CF3SO3）（5）（Ln = Eu，Lu）的晶体结构表明螺旋结构可以容纳不同大小的金属离子，而金属间的M（...）Ln距离不会发生较大变化。这些系统非常适合揭示影响金属间nd-> 4f通讯的分子因素。 HHH- [MLnL（3）]（5/6 +）（Ln = Nd，Yb，Er; M = Cr，Ru）中的（CrN6）-N-III和（RuN6）-N-III发色团的可见辐射在复合物中的定向能量迁移后，最终产生基于镧系元素的近红外（NIR）发射。根据与每个特定d-f对相关的动力学机制，NIR发光衰减时间可以从微秒调整到毫秒。讨论了这种效应的起源，以及对离散异双金属实体中的光学功能进行编程的合理控制。

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