Tetraphenylenthene-Based Conjugated Microporous Polymer for Aggregation-Induced Electrochemiluminescence

Abstract

We demonstrate the aggregation-induced electrochemiluminescence (AIECL) generated by 1,1,2,2-tetrakis­(4-bromophenyl)­ethane (TBPE)-based conjugated microporous polymers (TBPE-CMPs) and its biosensing application. We synthesized three TBPE-CMPs (i.e., TBPE-CMP-1, -2, -3) using three different molecules including tris­(4-ethynylphenyl)­amine (TEPA), 4,4′-diethynylbiphenyl (DEP), and 2,4,6-tris­(4-ethynylphenyl)-1,3,5-triazine (TEPT). The TBPE-CMPs can act as electrochemiluminescence (ECL) emitters to generate AIECL. Among them, TBPE-CMP-1 exhibits the highest ECL efficiency (1.72%) due to the improved electron–hole recombination efficiency and efficient suppression of nonradiative transition. Moreover, the ECL properties of TBPE-CMPs can be tuned by the introduction of different conjugated molecules that can decrease the energy gap to facilitate the injection of an electron into the conjugated polymer backbone. Importantly, TBPE-CMP-1 can be used to construct an ECL sensor for the detection of dopamine, whose electro-oxidation products (e.g., leucodopaminechrome (LDC), dopaminechrome (DC), 5,6-dihydroxyindole (DHI), and 5,6-indolequinone (IDQ)) may function as energy acceptors to quench the ECL emission of TBPE-CMP-1. This ECL sensor exhibits high sensitivity and good anti-interference capability against ascorbic acid and uric acid.

Polymer Electrochemiluminescence Featuring Thermally Activated Delayed Fluorescence

“…To testify such viewpoint, co‐reactant ECL of fluorescent polymer F8BT/TPrA couple [4] was also characterized in parallel (Figure S17). The relative ECL efficiencies (Φ ECL ) of the PCzAPT10‐modifed GCE/40 mM TPrA couple and the F8BT‐modified GCE/40 mM TPrA couple were measured according to the routine procedures, [1j,6,16] in which the Ru(bpy) 3 2+ /TPrA couple (0.1 mM Ru(bpy) 3 2+ , 40 mM TPrA, 0.1 M TBAP in ACN) was used as the standard (Φ ECL‐0 =100 %) [1j] . As shown in Table 1, Φ ECL of F8BT/TPrA couple (Φ ECL‐1 ) was 44 %, while the Φ ECL of PCzAPT10/TPrA couple (Φ ECL‐2 ) was as high as 194 %.…”

“…Irrespective of annihilation or co‐reactant mode, [1a] full‐color ECL behavior was realized for them by sequentially electrochemical injection of holes/electrons into the highest occupied molecular orbital (HOMO)/the lowest unoccupied molecular orbital (LUMO) of those polymers to generate excitons, followed by radiative decay. Other fluorescent polymers featuring intrachain resonance energy transfer [5] or aggregation‐induced emission (AIE) [6] etc. were also developed, with the purpose to further enhance their solid‐state ECL efficiency and detection capability for sensor applications.…”

Aggregation-Induced Emission in Electrochemiluminescence: Advances and Perspectives

“…TPE was also recently used to generate conjugated microporous polymers by Suzuki cross-coupling of 1,1,2,2-tetrakis(4-bromophenyl)ethylene (TBPE) with tris(4-ethynylphenyl)amine. [70] The system displays an 1.72 % relative ECL efficiency vs. [Ru(bpy) 3 ] 2+ and was applied to sense dopamine using the o-benzoquinone-based quenching principle previously described, reaching linearity in the interval of 10 nM to 500 μM with a detection limit of 0.85 nM. The application of TPE-conjugated polymers for sensing has been scaled to a more practical level by the group of Hua et al [48] , a common nuclear waste, which is capable of transferring energy to the Pdots, thereby increasing the ECL signal.…”

Green Nanocomposites for Energy Storage

“…Most importantly, polyanilines, polypyroles, polythiophenes, and poly(3,4-ethylenedioxythiophene) have been used. Recently, bio-based conducting polymers and nanocomposites have been adopted in the photovoltaics and optoelectronics industries [104,105]. The inclusion of green nanofillers in p-type conjugated polymers may develop donor-acceptor heterostructures for photo energy conversion [106].…”