Electrochemiluminescence of a Vinyl‐Functionalized Ruthenium Complex and Its Monolayer Formed through the Photoinduced Thiol‐Ene Click Reaction

Abstract

Vinyl-functionalized bipyridine ruthenium complex, bis(2,2'-bipyridine)(4,4'-di(4-vinylphenyl)-2,2'-bipyridine)ruthenium(II) hexaflurophosphate [Ru(bpy) 2 (dvbpy)](PF 6 ) 2 , was synthesized and the electrochemiluminescence (ECL) generated in the presence of co-reactant, namely tri-n-propylamine (TPrA), was investigated by using an ECL spooling technique. This complex was then covalently attached to the indium tin oxide electrode surface through photoinduced thiol-ene click chemistry to prepare a solid-state ECL sensor. The covalently immobilized [Ru (bpy) 2 (dvbpy)] 2 + monolayer film exhibited excellent stability toward ECL generation. The analytical sensitivity of the solidstate ECL sensor was evaluated through the detection of TPrA in the aqueous solution. A low limit of detection (LOD) of 0.25 mM and a wide linear range (ca. 10 À7 -10 À4 M) were obtained, indicating its potential usefulness in chemical and biochemical analysis.

Potential-Resolved Multicolor Electrochemiluminescence for Multiplex Immunoassay in a Single Sample

“…Ru­(bpy) 3 2+ ( 5 ) is recognized as a benchmark ECL luminophore. The neutral luminophore, tris­(2-phenylpyridine)­iridium­(III) (Ir­(ppy) 3 , 2 ), is one of the first iridium complexes used in ECL research. ,− The other four luminophores, namely, [4,4′-bis­( tert -butyl)-2,2′-bipyridine]­bis­[3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl]­phenyl]­iridium­(III) (Ir­(dFCF 3 ppy) 2 (dtbbpy) + , 1 ), [4,4′-bis­( tert -butyl)-2,2′-bipyridine]­bis­[2-(2-pyridinyl)­phenyl]­iridium­(III) (Ir­(ppy) 2 (dtbbpy) + , 3 ), [4,4′-bis­(4-vinylphenyl)-2,2′-bipyridine]­bis­[(2-pyridinyl)­phenyl]­iridium­(III) (Ir­(ppy) 2 (dvbpy) + , 4 ), and [4,4′-bis­(4-vinylphenyl)-2,2′-bipyridine]­bis­(2,2′-bipyridine)­ruthenium­(II) (Ru­(bpy) 2 (dvbpy) 2+ , 6 ), were synthesized in this work according to previous reports. − The full experimental details on the synthesis, NMR, and spectroscopic characterizations are provided in Scheme S1 and Figures S1 and S2 (see the Supporting Information, SI, for details). Figure S2 compares UV–vis absorption and photoluminescence (PL) spectra of six ECL luminophores.…”

“…Their absorption maximum wavelength (λ max,Abs ) and the maximum molar absorptivity (ε max,Abs ), the maximum PL wavelength (λ max,PL ), and the approximate spectroscopic energy of the excited state ( E 0–0 = 1239.81/λ max, FL ) are summarized in Table . The PL quantum yields (Φ PL ) of the luminophores were determined using quinine and Ru­(bpy) 3 2+ as the standards, ,, which were 3.79, 0.52, 7.11, 6.18, 1.80, and 2.29, respectively (see calculation details in SI, Figure S3 and Table S1).…”

Highly Active Electrochemiluminescence of Ruthenium Complex Co-assembled Chalcogenide Nanoclusters and the Application for Label-Free Detection of Alkaline Phosphatase

“…Electrochemiluminescence (ECL), also known as electrogenerated chemiluminescence, is a widely used analytical technology, especially in the fields of biological applications, due to excellent detection performances, such as a low background, controllability of time and space, high selectivity, and so forth. − Although numerous ECL luminophores have been developed, − ruthenium­(II) complexes are the mostly used luminophores owing to the inherent high ECL intensity and efficiency, good chemical stability, which result in high sensitivity, and a low detection limit in analysis and have been successfully commercialized for in vitro diagnosis in a variety of sample types. ,− In a homogenous analysis system, Ru­(bpy) 3 2+ and analogues are mostly dispersed in a detection reservoir, which faces with several drawbacks such as waste of costly reagents, complex experimental design, and difficulty in minimizing the instruments. ,, As a comparison, the immobilization of ruthenium complexes provides a favorable approach to fabricate solid-state ECL sensors with high sensitivity and long-term stability, and thus, diverse heterogeneous analysis approaches by immobilizing Ru­(bpy) 3 2+ and its derivatives to the electrode surface have been developed, which involve covalently bonding the ruthenium complexes to the matrix or electrode surface − and the incorporation of ruthenium complexes to composite films by directly adsorption, , ion exchange or electrostatic interactions, − and so forth. While the covalent immobilization of ruthenium complexes generally suffers from the complicated organic synthesis and separation procedures, noncovalent interactions always lead to the leaching of ruthenium complexes from the electrode surface and a hindered electron-transfer process and mass-transfer process, which cause a low ECL efficiency.…”

Covalently-bonded single-site Ru-N2 knitted into covalent triazine frameworks for boosting photocatalytic CO2 reduction

“…28), in which the electrons were excited from an occupied metal-localized orbital to a vacant ligand-localized orbital, thus resulting in the longwavelength light absorption. 45,46 Notably, an obvious red-shift of the optical absorption edge occurred upon increasing the content of Ru units in the structure, plus with a decrease in the optical band gap from 2.75 to 2.28 eV by their Tauc plots (Supplementary Fig. 29), respectively.…”