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首页> 外文期刊>Comments on Inorganic Chemistry: A Journal of Critical Discussion of the Current Literature >LUMINESCENT METALLACARBORANES
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LUMINESCENT METALLACARBORANES

机译：发光金属碳硼烷

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摘要

Metallacarborane complexes comprising MC_xB_y (x = l-3,y = 3-10) polyhedral frameworks are not well known for their photophysical properties. While the subject of metallacarborane luminescence remains a hitherto under-explored topic, we have recently discovered surprising optoelectronic responses from a small clutch of rhenium-and ruthenium-carborane species. Thus the complexes [3,3,3-(CO)_3-8-I-closo-3,l,2-ReC_2B_9H_(10)]~ - and [3-CO-3,3-K~2-Me_2N -(CH_2)_2NMe_2-closo-3,l,2-RuC_2B_9H_(11)] display low temp0erature (77 K) phosphorescences with single-exponential decays (lambda_(em) = 455 nm (tau = 1.65 ms) and lambda_(em) = 450 nm (tau = 0.77 ms), respectively), while the structurally novel complex [7,10-mu-H-7-CO-7,7-(PPh_3)]2-isonida-7,8,9-ReC_2B_7H_9] is photoemissive in solution at ambient temperatures (lambda_(em) = 442 nm) with a variable biexponential dual fluorescent decay in frozen (77 K) glass. We have also observed frozen glass and solid state blue emission (lambda_(em) approx = 400 nm) from the complex [3,3-(CO)2-3-NO-closo-3,l,2-ReC_2B9H_(11)]. This work provides an opportunity to collate these results together and examine the related underlying causes for these emissions by interpretation of photophysical, electrochemical and spectroelectrochemical measurements. The results are related to the only other observed luminescence for a metallacarborane with an inclusive metal vertex, reported for the complex [commo-3,3'-Ni(l,2-C_2B_9H_(11)_2), by virtue of a dynamic element leading to polyhedral skeletal reorganization of the metallacarborane framework in the excited state.
机译：包含MC_xB_y（x = 1-3，y = 3-10）多面体骨架的金属碳硼烷络合物因其光物理性质而众所周知。尽管金属碳硼烷发光的主题仍然是迄今尚未得到充分探讨的话题，但我们最近发现，从少量的clutch和钌-碳硼烷物种的离合器中获得了令人惊讶的光电响应。因此，复合物[3,3,3-（CO）_3-8-I-closo-3，l，2-ReC_2B_9H_（10）]〜和[3-CO-3,3-K〜2-Me_2N- （CH_2）_2NMe_2-closo-3，l，2-RuC_2B_9H_（11）]显示低温度（77 K）磷光，具有单指数衰减（lambda_（em）= 455 nm（tau = 1.65 ms）和lambda_（em）分别为450 nm（tau = 0.77 ms），而结构新颖的复合物[7,10-mu-H-7-CO-7,7-（PPh_3）] 2-isonida-7,8,9-ReC_2B_7H_9在环境温度（λ（em）= 442 nm）下在溶液中具有光发射性，并且在冷冻（77 K）玻璃中具有可变的双指数双荧光衰减。我们还观察到了来自复合物[3,3-（CO）2-3-NO-closo-3，l，2-ReC_2B9H_（11）的冷冻玻璃和固态蓝光发射（λ_（em）大约= 400 nm） ]。这项工作提供了一个机会，可以将这些结果整理在一起，并通过解释光物理，电化学和光谱电化学测量来检查这些排放的相关根本原因。该结果与具有动态金属元素的金属碳碳烷的唯一观察到的其他发光有关，该发光是通过动态元素报道的[commo-3,3'-Ni（l，2-C_2B_9H_（11）_2）配合物导致金属碳硼烷骨架处于激发态的多面体骨架重组。

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