4.7 Article

Dynamic Coordination between a Triphenylamine-Functionalized Salicylaldehyde Schiff Base and a Copper(II) Ion

期刊

INORGANIC CHEMISTRY
卷 60, 期 12, 页码 8581-8591

出版社

AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.1c00523

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资金

  1. National Natural Science Foundation of China [21975054, 21602014, 22065009, 22066007]
  2. Guizhou Provincial Natural Science Foundation [2792 (2019), 5779-14 (2018)]
  3. EPSRC [EP/R023816/1]

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This article investigates the formation of metal coordination between a triphenylamine-functionalized salicylaldehyde Schiff base and a copper(II) ion, revealing the dynamic and stable nature of the coordination process. The probe exhibits high sensitivity and specificity towards copper(II) ions, making it a promising fluorescence probe for detection applications.
The coordination between a ligand and a metal is a spontaneous and uncontrollable process. In this Article, we successfully observe the formation of metal coordination in a triphenylamine-functionalized salicylaldehyde Schiff base with a copper(II) ion. The ligand TPA-Py first reacts with Cu2+ in a stepwise process to afford the dynamic complex TPA-Py@Cu2+ ([ligand]:[Cu2+] = 1:1), which further reacts with an extra copper(II) ion to afford 2TPA-Py@4Cu(2+) with the following stepwise (or cumulative) stability constants: K-1 = 4.0694 x 10(3) and K-2 = 1.0761 x 10(6), respectively. The entire metal coordination process can be visualized, and the coordination mode of the probe toward copper was further evaluated by ultraviolet-visible/fluorescence spectra, single-crystal X-ray diffraction, density functional theory calculations, high-resolution mass spectra, and nuclear magnetic resonance spectroscopic titrations. Compound TPA-Py exhibited excellent sensitivity and specificity toward copper(II) ions in THF/water media with a low limit of detection of 2.687 x 10(-7) mol L-1. In addition, TPI-An-Py can be applied to the detection of Cu2+ in real samples with satisfactory recoveries in the range of 100-112% in lake water and 98-101% in tap water. This Article not only reports an excellent fluorescence probe for copper(II) ion detection but also presents an instance for more fully understanding the metal coordination process.

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