Exploring new electrochemiluminescence (ECL) luminophores
with
strong ECL emission is highly desirable for developing ultrasensitive
ECL sensors. Herein, a pyrene-based hydrogen-bonded organic framework
(Py-HOF) featuring prominent ECL performance was prepared by utilizing
1,3,6,8-tetrakis(p-benzoic acid) pyrene (H4TBAPy) with an aggregation-induced enhanced emission (AIEE) property
as a building block, exhibiting a stronger ECL emission than those
of H4TBAPy monomers, H4TBAPy aggregates, the
low-porosity Py-HOF-210 °C and Py-HOF-180 °C. We have coined
the term “the porosity- and aggregation-induced enhanced ECL
(PAIE-ECL)” for this intriguing phenomenon. The Py-HOF displayed
superb and stable ECL intensity, not only because the luminophore
H4TBAPy was assembled into the Py-HOF via four pairs of
O–H···O hydrogen bonds, which constrained the
intramolecular movements to reduce nonradiative transition, but also
because the H4TBAPy in Py-HOF was stacked in a slipped
face-to-face mode to form J-aggregates that benefited the ECL enhancement.
Furthermore, the high porosity of Py-HOF allowed the enrichment of
coreactants and facilitated the migration of ions, electrons, and
coreactants, which made it possible for the inner and outer H4TBAPy to be electrochemically excited. Considering the remarkable
ECL performance, Py-HOF was first employed as an ECL probe combined
with a 3D DNA nanomachine amplification strategy to assemble a hypersensitive
“on–off” ECL sensor for the microRNA-141 assay,
presenting a satisfactory linear range (100 aM to 1 nM) with a detection
limit of 14.4 aM. The PAIE-ECL manifested by Py-HOF provided a bright
avenue for the design and synthesis of outstanding HOF-based ECL materials
and offered new opportunities for the development of ECL biosensors
with excellent sensitivity.