Enhanced Electrochemiluminescence of Porphyrin-Based Metal–Organic Frameworks Controlled via Coordination Modulation

• Published in: Analytical chemistry (Washington) Vol. 92; no. 2; pp. 1916 - 1924
• Main Authors: Cai, Wen-Rong, Zeng, Hai-Bo, Xue, Huai-Guo, Marks, Robert S, Cosnier, Serge, Zhang, Xue-Ji, Shan, Dan
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 21.01.2020
• Subjects: Chemical Sciences; Chemistry; Coordination; Coordination chemistry; coordination polymers; Crystal growth; Electrochemiluminescence; Emitters; Hydrogen peroxide; ions; ligands; Metal-organic frameworks; Morphology; Optoelectronics; solvents; spectroscopy; sulfonic acids; voltammetry; Zinc
• ISSN: 0003-2700; 1520-6882; 1520-6882
• DOI: 10.1021/acs.analchem.9b04104

Precise control over the composition, morphology, and size of porphyrin-based metal–organic frameworks is challenging, but the extension of these hybrid materials will enable the creation of novel electrochemiluminescence (ECL) emitters. The coordination of various entities is made from Zn2+ ions and meso-tetra­(4-carboxyphenyl)­porphine (TCPP), modulated by both solvent and bathophenanthrolinedisulfonic acid disodium salt (BPS) as capping agent, resulting in limited crystal growth of Zn-TCPP in DMF/H2O (v/v, 1:1) and the formation of nanoscale TCPP-Zn-BPS. The role of BPS is also evaluated using Zn-TCPP and BPS-Zn-TCPP as controls, prepared in the absence of BPS and different coordinating sequences of ligands, respectively. The newly obtained TCPP-Zn-BPS exhibits a variety of different morphologies, as well as spectral and optoelectronic properties. The ECL behavior of TCPP-Zn-BPS is investigated by using H2O2 as co-reactant. The amplification of ECL is further studied by ECL spectroscopies and cyclic voltammetry, with the corresponding mechanism proposed.