Department of Chemistry, Inorganic Chemistry Section , Jadavpur University , Kolkata 700032 , India.
Inorg Chem. 2018 Oct 1;57(19):12010-12024. doi: 10.1021/acs.inorgchem.8b01562. Epub 2018 Sep 21.
We report here the synthesis, characterization, and photophysics of two bis-tridentate Ru(II) complexes based on a heteroditopic ligand and thoroughly studied their stimuli-responsive behaviors toward the design of functional materials. Both complexes display emission at room temperature having lifetimes in the range of 0.5-70.0 ns, depending on coligand and solvent. Substantial modulations of absorption and emission spectral behaviors of the complexes were done upon interaction with anions, and anion-induced changes in the properties lead to recognition of selected anions in both organic and aqueous media. Photophysical properties of the complexes were also tuned by changing the pH of the medium, and p K values in both ground and excited states were determined. The presence of free pyridine-imidazole motifs in the complexes leads to substantial modulation of the optical properties and switching of the emission properties upon interaction with selected cations as well as with protons. Fe, Co, Ni, and Cu trigger emission quenching, while Zn induces finite enhancement of the emission intensity in the complexes. In essence, modulation of the optical properties and switching of luminescence properties of the complexes were accomplished by a variety of the external stimuli such as anions, cations, protons, and pH, as well as solvent polarity. Importantly, the optical outputs in response to an appropriate set of stimuli were utilized to mimic the functions of two-input IMPLICATION, NOR, and XNOR logic gates.
我们在此报告了两种基于杂双齿配体的双三齿 Ru(II) 配合物的合成、表征和光物理性质,并深入研究了它们对设计功能材料的刺激响应行为。两种配合物在室温下均显示出发射,其寿命范围为 0.5-70.0 ns,这取决于共配体和溶剂。配合物的吸收和发射光谱行为在与阴离子相互作用时会发生实质性的调制,阴离子诱导的性质变化导致在有机和水相介质中对选定的阴离子进行识别。通过改变介质的 pH 值还可以调整配合物的光物理性质,并且在基态和激发态下都确定了 p K 值。配合物中游离的吡啶-咪唑基序的存在导致光学性质的实质性调制,并在与选定的阳离子以及质子相互作用时,发射性质的开关。Fe、Co、Ni 和 Cu 引发发射猝灭,而 Zn 则在配合物中诱导发射强度的有限增强。实质上,通过各种外部刺激(如阴离子、阳离子、质子和 pH 值以及溶剂极性)来调节配合物的光学性质和发光性质的开关。重要的是,对适当的一组刺激的光学输出被用于模拟两个输入 IMPLICATION、NOR 和 XNOR 逻辑门的功能。