Synthesis, Characterization, and Redox Properties of Electron-Deficient Porphyrins with Dual Applications #MMPMID41370049
Bhardwaj V; Kuriakose A; Vijaya Prakash G; Sankar M
Inorg Chem 2025[Dec]; ? (?): ? PMID41370049show ga
To investigate the optoelectronic properties of extensively electron-deficient porphyrins, a series of mixed functionalized porphyrins with adjacent nitro (-NO(2)) and cyano (-CN) functional groups at the beta-pyrrolic positions were designed and synthesized via nucleophilic substitution reactions. The synthesized porphyrins were characterized by several spectroscopic techniques and confirmed by single-crystal X-ray diffraction analysis. The electron-deficient nature of porphyrins, as highlighted by their redox properties, makes the macrocycle a selective optical sensor for cyanide ions with a limit of detection of nearly 1 ppm. Furthermore, porphyrins were evaluated for their nonlinear optical responses. Femtosecond laser intensity-dependent third-order nonlinear optical studies were performed using a laser with the following specifications: 800 nm, 120 fs, and 84 MHz at an intensity of 3.0 x 10(13) W/m(2). Among all analyzed porphyrins, free-base porphyrins exhibited higher nonlinear coefficients compared to metalated porphyrins. Moreover, highly substituted porphyrins showed high nonlinear coefficient values. 3-H(2) shows the highest ( approximately 119 x 10(-11)) two-photon absorption coefficient (beta) and the highest negative nonlinear refractive index (-28.2 x 10(-17)), making it suitable for optical limiting applications.
Inorg+Chem 2025 ; ? (?): ?
