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Excimer emission induced by metal ion coordination in 1,8-naphthalimide-tethered iminopyridine ligands

机译:金属离子配位在1,8-萘二甲酰亚胺上的亚氨基吡啶配体引起的准分子发射

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摘要

Ligands 2-5,containing the light-emitting subunit 1,8-naphthalimide,have been prepared and their photophysical properties studied by absorption and emission spectroscopy.Ligand 2 interacts i nsolutionw ith several cations according to a 1:2 (metal:ligand) stoichiometry,the 1:3 species being not favoured probably because of steric hindrance,while ligands 3-5 form 1:3 adducts with all the investigated metal ions.The interaction of ligands 2-5 with metal ions induces considerable variation on the photophysical properties of the light-emitting subunit.The coordiantion of genuine transition metal ions (Fe~(ii),Co~(II),Ni~(II),Cu~(II)) causes the emission intensity to decrease in all the investigated systems,while Zn~(II) or Cd~(II) induce a fluorescence enhancement (system 2) or the formation of a new band in the emission spectra (systems 3-5) which can be ascribed to an intramolecualr excimeric species.Excimeric emission is not observed in the complexes of 2,possibly because the ethylenic chain bridging the naphthalimide and the iminopyridine units is too short to allow the intramolecualr interaction.The excimeric species disappears on increasing the metal ion (Zn~(II) or Cd~(II)) concentration,as a result of the "disassembling" of the 1:3 complexesa nd the consecutive formation of 1:2 and 1:1 species,in which the intramolecualr interaction is less probable or no longer possible.The appearance and disappearance of an excimer band in the emission spectrum can be described as a convenient way to monitor a metal-driven assembling/disassembling process.
机译:制备了包含发光亚基1,8-萘二甲酰亚胺的配体2-5,并通过吸收和发射光谱研究了它们的光物理性质。配体2按照1:2(金属:配体)的形式与几种阳离子相互作用。化学计量学,1:3的物种可能不是因为空间位阻而受到青睐,而配体3-5与所有研究的金属离子形成1:3加合物。配体2-5与金属离子的相互作用引起光物理性质的显着变化真正的过渡金属离子(Fe〜(ii),Co〜(II),Ni〜(II),Cu〜(II))的配位导致所有研究系统的发射强度降低。 Zn〜(II)或Cd〜(II)会诱导荧光增强(系统2)或在发射光谱中形成新谱带(系统3-5),这可归因于分子内的激基物质。在2的配合物中没有观察到,可能是因为烯桥接萘二甲酰亚胺和亚氨基吡啶单元的链太短,以至于不允许分子内相互作用。由于金属的“分解”(Zn〜(II)或Cd〜(II))浓度增加,赋形异构体消失了。 1:3络合物与1:2和1:1物种的连续形成,其中分子内相互作用不太可能发生或不再可能发生。发射光谱中受激准分子带的出现和消失可被描述为方便监视金属驱动的组装/拆卸过程的方法。

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