Cd2+ -induced Fluorescent Metallogel: A Case of CHEF and ACQ Phenomena.

A fluorescent metallogel (1 %w/v) has been synthesized from deprotonation of a non-fluorescent adipic acid-derived ligand H2 AL with LiOH followed by coordination with Cd2+ in DMF. Cd2+ not only induces the coordination complex formation but also leads to aggregation, formation of nanofibers of about ≈12 nm average diameter and gelation. The metallogel was also found to be reversibly stimuli-responsive towards heating and mechanical shaking whereas it was resistant to ultrasound. The involvement of chelation-enhanced fluorescence (CHEF), aggregation-induced emission (AIE) and aggregation-caused quenching (ACQ) during the course of gelation has been well established by fluorescence experiments. Further, the coordination complex involved in metallogel formation has been well characterized by ESI-MS and Job's plot. The synthesized metallogel has a true gel phase as shown by detailed rheological studies. The mechanism of gelation is well established by using FTIR, UV-vis, fluorescence, lifetime measurement, Job's plot, ESI-MS, PXRD and TEM techniques.

Investigation of the Mechanism Behind Conductive Fluorescent and Multistimuli-responsive Li+ -enriched Metallogel Formation.

A fluorescent metallogel (2.6 % w/v) has been obtained from two non-fluorescent components viz. phenyl-succinic acid derived pro-ligand H2 PSL and LiOH (2 equiv.) in DMF. Li+ ion not only plays a crucial role in gelation through aggregation, but also contributed towards enhancement of fluorescence by imposing restriction over excited state intramolecular proton transfer (ESIPT) followed by origin of chelation enhanced fluorescence (CHEF) phenomenon. Further, the participation of CHEF followed by aggregation-caused quenching (ACQ) and aggregation-induced emission (AIE) in the gelation process have been well established by fluorescence experiments. Transmission electron microscopy (TEM) analysis disclosed the sequential creation of nanonuclei followed by nanoballs and their alignment towards the generation of fibers of about 3, 31 and 40 nm diameter, respectively. The presence of a long-range fibrous morphology inside the metallogel was further attested by scanning electron microscopy (SEM). Rheological studies on the metallogel showed its true gel-phase material nature. Nyquist impedance study shows a resistance value of 7.4 kΩ for the metallogel which upon applying ultrasound increased to 8.5 kΩ, while an elevated temperature of 70 °C caused reduction in the resistance value to 4.8 kΩ. The mechanism behind metallogel formation has been well established by using FTIR, UV-vis, SEM, TEM, PXRD, 1 H NMR, fluorescence and ESI-MS.

An Li+-enriched Co2+-induced metallogel: a study on thixotropic rheological behaviour and conductance.

An alkali base and counterion-selective red metallogel (1% w/v) has been synthesized by mixing the adipic acid-derived ligand H2AL with LiOH, followed by the addition of 1 equivalent of Co(OAc)2 in DMF. The addition of Co(OAc)2 not only resulted in the formation of a 2 : 2 (M : L) complex, but also led to the consecutive steps of aggregation, fiber creation, entrapment of the solvent and eventually gelation. The metallogel formation and the mechanism behind gelation have been well characterized and established using various instrumental techniques such as FTIR spectroscopy, UV-vis spectroscopy, FE-SEM, TEM, PXRD, ESI-mass spectrometry, Job's plot and rheology analysis. Nyquist plots suggested a large decrease in the resistance value from 11.3 kΩ to 4.2 kΩ for the solution obtained from the ligand deprotonated by LiOH (AL2-) and Co(OAc)2 containing the metallogel. The Nyquist plot and resistance of the metallogel have also been studied under the influence of temperature and ultrasound stimuli. The extensive rheological measurements provide information about the strength of the gel network and the highly reversible nature and thixotropic behaviour of the metallogel.