Metal-organic frameworks (MOFs) as crystalline materials have been extensively applied in the electrochemical sensing. However, the influence of the counteranion of MOFs on electrochemical analysis was rarely reported. In this work, three Ag-MOFs [Ag₃(L)₃](NO₃)₃ (A1), [Ag₃(L)₃](CF₃SO₃)₃ (A2) and [Ag₂(L)(NO₃)₂] (A3) with the same ligand of 1,1,2,2-tetrakis(4-(1H-pyrazol-1-yl)phenyl)ethene (L) but different counteranions were utilized to explore their electrochemical detection performance for chloride (Cl⁻) ions based on the electrochemical redox of solid-state AgCl. It is interesting to find that the solid-state AgCl derived from A2 with CF₃SO₃⁻ counteranions exhibits inverse conductance signal output compared with that derived from A1 with counteranions of non-coordinated NO₃⁻ or by A3 with coordinated NO₃⁻. Besides, the signals of peak potentials for the solid-state AgCl derived from these Ag-MOFs are stable, which showed excellent linear relationship and high sensitivity, favorable for the further applications. This is the first example of the counteranions of MOFs determined electrochemical sensing of chloride, and revealed the importance of the counteranions of MOFs in the field of the electrochemical sensing.

金属有机框架（MOFs）作为晶体材料已广泛应用于电化学传感。然而，MOFs 的抗衡阴离子对电化学分析的影响却鲜有报道。在这项工作中，三个 Ag-MOF [Ag ₃ (L) ₃ ](NO ₃ ) ₃ ( A1 )、[Ag ₃ (L) ₃ ](CF ₃ SO ₃ ) ₃ ( A2 ) 和 [Ag ₂ (L) (NO ₃ ) ₂ ] ( A3) 与 1,1,2,2-四(4-(1H-pyrazol-1-yl)phenyl)ethene (L) 相同的配体，但使用不同的抗衡阴离子来探索其对氯化物 (Cl ^- )的电化学检测性能基于固态 AgCl 的电化学氧化还原的离子。有趣的是，从A2和 CF ₃ SO ₃ ^-反阴离子得到的固态 AgCl与来自A1的非配位 NO ₃ ^-反离子或A3配位的 NO ₃ ^{-相比表现出反电导信号输出。}. 此外，由这些Ag-MOFs衍生的固态AgCl的峰电位信号稳定，表现出良好的线性关系和高灵敏度，有利于进一步的应用。这是MOFs的反阴离子确定氯离子电化学传感的第一个例子，揭示了MOFs的反阴离子在电化学传感领域的重要性。