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.

Dalton Transactions : an International Journal of Inorganic Chemistry
Atasi MukherjeeManab Chakravarty

Abstract

This paper describes the synthesis of an unprecedented oxo-bridged rheniumI/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 ReI/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 comp...Continue Reading

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