RESUMO
Room temperature phosphorescence (RTP) materials are increasingly recognized for their superior luminescent properties, which are pivotal in applications such as anti-counterfeiting, information storage, and optoelectronics. Despite this, the sensitivity of most RTP systems to humidity presents a significant challenge in achieving durable RTP performance in aqueous environments. This study proposes a strategy to enhance organic room-temperature phosphorescence through racemization. By incorporating external racemates of various chiral phosphors-NDBD-Ph, NDBD-Ph-Ph, NDBD-CH3, and NDBD-O-CH3-into a polyacrylonitrile (PAN) matrix, we significantly enhance the RTP properties (quantum yield, lifetime, and afterglow-time) of the resultant films. This enhancement can be attributed to the increased density of racemic molecules in the matrix and the increased spin-orbit coupling (SOC), facilitating the development of a long-lasting polymer RTP system in water. Notably, the racemic rac-NDBD-Ph@PAN film exhibits a persistent bright turquoise afterglow, even after immersion in water for a month. Furthermore, for the first time, we achieved an enhanced green to cyan RTP response to pH variations under both acidic and alkaline conditions (pH = 2-12), with the maximum phosphorescence emission intensity increasing up to threefold. The remarkable water stability, reversible response characteristics, and enhanced phosphorescence properties of this system offer promising potential for dynamic information encryption in aqueous environments.
RESUMO
It is challenging to develop highly stable lanthanide luminescent sensors for detecting heavy metal ions and nitroaromatics in view of the human health and environmental security. To this end, two water stable Ln-MOFs with the chemical constitution of {[Ln(HL)]·3DMF·3H2O}n (Ln = Eu, LZG-Eu and Ln = Tb, LZG-Tb) have been developed solvothermally using a multidentate ligand (H4L) with the central phenyl backbone bisubstituted by 2,6-pyridine-dicarboxylic acid at the para-position, H4L = 1,4-bis(2',2'',6',6''-tetracarboxy-1,4':4,4''-pyridyl)benzene. Single crystal analysis demonstrates that two novel Ln-MOFs feature 4,4,4-connected nets with an unprecedented topology symbol of {42·6·83}2{42·62·82}{42·84} and contain two kinds of one-dimensional channels. Powder X-ray diffraction as well as the luminescence determination results indicate that they retain their crystallinity and structural integrity in harsh acidic and basic conditions with pH in the range of 4-11. Moreover, they are highly luminescent, which makes them excellent chemical sensors for detecting Cu2+ and 4-NP (4-nitrophenol) with high selectivity and sensitivity in aqueous media such as deionized water, tap water, and river water based on distinct quenching effects. To the best of our knowledge, their detection limits are lower than those documented so far. In addition, the quenching efficiency of 4-NP was retained in the presence of interfering ions even after the compounds were used for five cycles, which makes them attractive, reliable, visual, and recyclable luminescent Ln-MOF sensor materials for 4-NP. The recognition mechanism for Cu2+ could be attributed to the dissociation of the main framework induced by Cu2+ and the subsequent formation of a Cu2+ coordination species and that for 4-NP is considered to be multi-quenching mechanisms dominated by competition absorption.