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A Superstable Luminescent Lanthanide Metal Organic Gel Utilized in an Electrochemiluminescence Sensor for Epinephrine Detection with a Narrow Potential Sweep Range.

Metal organic gels (MOGs) as a new type of porous soft-hybrid supramolecular material have attracted widespread interest in various aspects due to their unique optical properties. In this work, we report a novel electrochemiluminescence (ECL) emission (679 nm) lanthanide MOG, which has been synthesized by a simple and rapid method at room temperature. This MOG (Tb-Ru-MOG) consists of a central metal ion, terbium (III), and two different ligands, tris(4,4'-dicarboxylicacid-2,2'-bipyridyl) ruthenium (II) dichloride (Ru(dcbpy)32+) and 4'-(4-carboxyphenyl)-2,2':6',2″-terpyridine (Hcptpy). Compared with the classic system of tris(2,2'-bipyridyl) ruthenium (II) dichloride (Ru(bpy)32+)/S2O82-, Tb-Ru-MOG/S2O82- owns a narrower potential sweep range (0.00 to -0.85 V) and a more stable and stronger ECL signal. Interestingly, the ECL intensity only decreased 2.0 and 0.1% after continuous scanning for 8000 s and storing at room temperature for 3 months. The possible ECL mechanism has been discussed in detail, which is mainly attributed to the internal synergies (antenna effect and energy transfer) and external co-reactant. Inspired by the unique luminescence characteristics of Tb-Ru-MOG, the application in electroanalytical chemistry was identified by the ECL on-off response for epinephrine with a linear range from 1.0 × 10-10 to 1.0 × 10-3 mol·L-1 and a detection limit of 5.2 × 10-11 mol·L-1. The results suggest that the as-proposed Tb-Ru-MOG will provide a robust pathway for new ECL luminophores in analysis.