Ruthenium(II) complex-grafted conductive metal-organic frameworks with conductivity- and confinement-enhanced...

Improving the electrochemiluminescence (ECL) performance of luminophores is an ongoing research hotspot in the ECL realm. Herein, a high-performance metal-organic framework (MOF)-based ECL material (Ru@Ni₃(HITP)₂, HITP = 2,3,6,7,10,11-hexaiminotriphenylene) with conductivity- and confinement-enhanced ECL was successfully constructed by using conductive MOF Ni₃(HITP)₂ as the carrier to graft Ru(bpydc)₃^4- (H₂bpydc = 2,2'-bipyridine-4,4'-dicarboxylic acid) into the channels of Ni₃(HITP)₂. Compared to Ru@Cu₃(HITP)₂ and Ru@Co₃(HITP)₂ with relatively low conductivity, the ECL intensity of Ru@Ni₃(HITP)₂ was prominently increased about 6.76 times and 18.8 times, respectively, which demonstrated that the increase in conductivity induced the ECL enhancement of the MOF-based ECL materials. What's more, the hydrophobic and porous Ni₃(HITP)₂ can not only effectively enrich the lipophilic tripropylamine (TPrA) coreactants in its channels to enhance the electrochemical oxidation efficiency of TPrA, but also provide a conductive reaction micro-environment to boost the ECL reaction between Ru(bpydc)₃^3- intermediates and TPrA^• in confined spaces, thus realizing a remarkable confinement-enhanced ECL. Considering the excellent ECL performance of Ru@Ni₃(HITP)₂, an ultrasensitive ECL biosensor was prepared based on the Ru@Ni₃(HITP)₂ ECL indicator combining an exonuclease I-aided target cycling amplification strategy for thrombin determination. The constructed ECL biosensor showcased a wide linear range from 1 fM to 1 nM with a low detection limit of 0.62 fM. Overall, the conductivity- and confinement-enhanced ECL based on Ru@Ni₃(HITP)₂ provided effective and feasible strategies to enhance ECL performance, which paved a promising avenue for exploring high-efficient MOF-based ECL materials and thus broadened the application scope of conductive MOFs.