An unprecedented pyridine-based dinuclear mixed-valent ReI/VII oxo-bridged complex: a solvatochromic and AIE-active probe for nanomolar detection of picric acid and trinitrotoluene

Abstract

This paper describes the synthesis of an unprecedented oxo-bridged rhenium^I/VII (Re) complex by treating Re₂(CO)₁₀ with a pyridyl-linked anthracene-based twisted π-conjugated ligand. The molecular structures of both the ligand and the complex are determined by analyzing IR, NMR, and HR-MS spectra and unequivocally determined using single-crystal X-ray diffraction studies. Unlike previous observations, the complexation occurs uniquely to yield an unprecedented oxo-bridged Re^I/VII complex. Such a complex is uncommon, and in most cases, Re(VII) appears as the ReO₄⁻ counter ion. The aggregation-induced emission (AIE) feature could have been achieved from this conformationally twisted ligand, but the emission of the ligand was quenched in the aggregated state. The complex exhibited solvatofluorochromic properties with a faint emission. The emission intensity significantly (∼6 times) increased in DMF after the addition of a water fraction of 90%, resulting in a bright orange emission. The AIE is mainly caused by restricted intramolecular rotation (RIR) and is supported by the polarity and viscosity effects. The nanoaggregate formation is captured by SEM, and DLS studies were used to determine the average particle size. After the complexation, the ligand becomes more rigid, and the RIR effect becomes prominent facilitating the AIE effect. The electron-rich aggregate's intense orange emission was used for the selective and sensitive detection of picric acid (PA) and 2,4,6-trinitrotoluene (TNT) at nanomolar levels amongst other nitroaromatics through emission quenching. The detailed mechanistic studies reveal the active role of dynamic quenching and complementary photo-induced electron transfer between the probe and TNT or PA. The easy electron transfer process from the electron-rich to the electron-poor system is confirmed by calculating the lowest unoccupied molecular orbital energy of the associated levels. The application is further extended for on-site PA and TNT detection by permeating the probe on a paper and detected at 10⁻³ M concentration with the naked eye. The PA/TNT detection efficiency is also confirmed by mixing PA or TNT with soil.