Organic polymorphs based on an AEE-active tetraphenylethene salicylaldehyde Schiff-base derivative: the effect of molecular conformation on luminescence properties.

An aggregation-enhanced emission (AEE)-active tetraphenylethene salicylaldehyde Schiff-base derivative, TPE-Nap, was prepared using a facile synthesis. The AEE property of TPE-Nap was studied by luminescence and absorption spectra, and was attributed to the C[double bond, length as m-dash]N isomerization restriction and the excited-state intramolecular proton transfer (ESIPT) process. Polymorphs TPE-Nap-Y and TPE-Nap-O were prepared from TPE-Nap, and their emission color and intensity were compared. TPE-Nap-Y is a yellow block crystal with a very weak yellow emission, with its main peak at 565 nm, while TPE-Nap-O is an orange plate crystal that gave a stronger orange emission, with its main peak at 583 nm. Single crystal diffraction data were used to demonstrate the structure-property relationship. The most unique feature was that the torsion angle of TPE-Nap-Y between the benzene ring of the TPE unit and the Nap unit was 54.08°, while that of TPE-Nap-O was 14.19°. Interestingly, the TPE unit assumed propeller-like nonplanar conformations that likely led to different intermolecular interactions, such as C-H⋯O interactions (2.529 Å and 2.617 Å) in TPE-Nap-O and C-H⋯π interactions (3.224 Å and 3.791 Å) in TPE-Nap-Y. These were influenced by the torsion angle, although the molecules in both crystals were arranged in a similar end-to-end slip-stacking mode. These results inferred that the molecular conformation was evidently affected by luminescent properties. Crystals possessing a slightly twisted molecular conformation exhibited stronger emission than those possessing a heavily twisted molecular conformation. These investigations will expand the research on the relationship between the molecular conformation and the emission properties of organic solids, and might provide a new development strategy for organic polymorphs.

A cyanide-sensing detector in aqueous solution based on anion-π interaction-driven electron transfer.

A "turn on" fluorescent and colorimetric sensor, HAT(CN)6, was developed for the light-up detection of cyanide. It was implemented through its strong anion-π interaction, inducing thermal CN- → HAT(CN)6 electron transfer, to give the dianion product [HAT(CN)6]2-, which exhibits unexpected fluorescence. The sensor shows high selectivity, rapid response and a low detection limit towards CN- in aqueous solution, hence indicating its enormous potential in practical applications.

Fluorescence light-up detection of cyanide in water based on cyclization reaction followed by ESIPT and AIEE.

Schiff base 1 (2,4-di-tert-butyl-6-((2-hydroxyphenyl-imino)-methyl)phenol) containing two hydroxyl groups could undergo an oxidative cyclization reaction and then generate hydroxyphenylbenzoxazole (HBO) 2 when CN- was present as a catalyst. The multistep cyclization reaction was proved by spectroscopy, 1H NMR, 13C NMR and mass spectra. C[double bond, length as m-dash]N isomerization is the predominant decay process of the excited states, so sensor 1 is weakly emissive in solution at ambient temperature. When 1 reacts with CN-, the emission is remarkably enhanced, where 1 is converted to 2. The cyclization product HBO 2 displays bright green luminescence in micellar due to the ESIPT (excited-state intramolecular proton transfer) as well as AIEE (aggregation-induced emission enhancement) effect. The detection limit is 5.92 × 10-7 M, lower than the WHO guideline of CN- in drinking water (1.9 µM). The selective and competitive experiments reveal that sensor 1 shows high sensing selectivity and sensitivity for CN- over other anions. Test papers containing absorbed 1 were prepared and applied for practical application of cyanide detection.

Gelation-driven selection in dynamic covalent C[double bond, length as m-dash]C/C[double bond, length as m-dash]N exchange.

Knoevenagel barbiturate derivatives bearing long alkyl chains were proven to form organogels in suitable solvents based on supramolecular interactions. Their reaction with imines allows for component exchange through C[double bond, length as m-dash]C/C[double bond, length as m-dash]N recombination. The effect of various parameters (solvents, chain length, and temperature) on the C[double bond, length as m-dash]C/C[double bond, length as m-dash]N exchange reaction has been studied. Mixing Knoevenagel compound K and imine I-16 in a 1 : 1 ratio generated a constitutional dynamic library containing the four constituents K, I-16, K'-16, and I'. The reversible exchange reaction was monitored by 1H-NMR, showing marked changes in the fractions of the four constituents on sol-gel interconversion as a function of temperature. The library composition changed from statistical distribution of the four constituents in the sol state to selective amplification of the gel forming K'-16 constituent together with that of its agonist I'. The process amounts to self-organization driven component selection in a constitutional dynamic organogel system undergoing gelation. This process displays up-regulation of the gel-forming constituent by component redistribution through reversible covalent connections.

Single sensor for multiple analytes in different optical channel: Applying for multi-ion response modulation.

A Schiff-base, (2,4-di-tert-butyl-6-((2-hydroxyphenyl-imino)-methyl)phenol) (L), has been improved to function as a simultaneous multi-ion probe in different optical channel. The probe changes from colorless to orangish upon being deprotonated by F-, while the presence of Al3+ significantly enhances the fluorescence of the probe due to the inhibition of CN isomerization, cation-induced inhibition of excited-state intramolecular proton transfer (ESIPT), and chelation enhanced fluorescence (CHEF). Dual-channel "off-on" switching behavior resulted from the sequential input of F- and Al3+, reflecting the balance of independent reactions of Al3+ and F- with L and with one another. This sensing phenomenon realizes transformation between multiple states and beautifully mimics a "Write-Read-Erase-Read" logic circuit with two feedback loops.

A novel cascade strategy with supramolecular and chemodosimetric methods for designing a fluorescent ratiometric detector hypersensitive to trace water.

An intensely fluorescent zinc-salicylideneimine complex (-Zn(II)) was developed as a fluorescent ratiometric detector for the quantitative determination of trace water contents both in THF and methanol. It works based on a water-triggered cascade process: the dissociation reaction of the supramolecular ensemble and the subsequent hydrolysis reaction of its ligand.

An efficient phase-selective gelator for aromatic solvents recovery based on a cyanostilbene amide derivative.

Two novel low molecular weight organogelators (LMOGs) 1 and 2 composed of a cholesteryl group, an amide group and various terminal cyanostilbene moieties were synthesized. They could form stable gels in p-xylene. In particular, 2 with more extended π-conjugation length showed remarkable gelation ability in many aromatic solvents, chloroform and chloroform-containing mixed solvents at a relatively low concentration. FT-IR and XRD spectra indicated that the difference between 1 and 2 in the gelation properties may result from the deviation of the intermolecular hydrogen bonding and π­π stacking as driving forces for the formation of the gels. Significantly, 2 can function as an efficient room-temperature phase-selective gelator (PSG) for potential application in the separation and recovery of various aromatic solvents from its mixture with water. Meanwhile, the gelator can be easily recovered and reused several times. Furthermore, the phase-selective gelation properties of 2 can provide a simple and feasible approach for the removal of the rhodamine B (RhB) dye from water.

A highly selective fluorescent sensor for Al³âº and the use of the resulting complex as a secondary sensor for PPi in aqueous media: its applicability in live cell imaging.

An easy-to-make salicylimine (L) bearing an "O-N-O"-coordination site was used as a highly selective fluorescent sensor for Al(3+) and PPi in aqueous solution. Sensor L showed a significant fluorescence enhancement in the presence of Al(3+) over other competitive metal ions. It works based on the Al(3+)-induced formation of a 1 : 1 L-Al(3+) complex, producing a chelation-enhanced fluorescence effect, the fluorescence quantum yield reached 0.59. This L-Al(3+) ensemble is a subsequent fluorescent sensor for PPi due to the strong attraction between Al(3+) and PPi, it can selectively discriminate PPi overcoming the interference of the biological competitors including PO4(3-), ADP and ATP at physiological pH. L and L-Al(3+) exhibit high sensitivity and selectivity for Al(3+) and PPi, the detection limits were found to be as low as 2.94 × 10(-8) M and 2.74 × 10(-7) M, respectively. It was further confirmed that sensor L had potential practical applications through mapping of Al(3+) in live cells.

A real-time fluorescent sensor specific to Mg2+: crystallographic evidence, DFT calculation and its use for quantitative determination of magnesium in drinking water.

An "off-the-shelf" fluorescence "turn-on" Mg(2+) chemosensor 3,5-dichlorosalicylaldehyde (BCSA) was rationally designed and developed. This proposed sensor works based on Mg(2+)-induced formation of the 2 : 1 BCSA-Mg(2+) complex. The coordination of BSCA to Mg(2+) increases its structural rigidity generating a chelation-enhanced fluorescence (CHEF) effect which was confirmed by single crystal XRD studies of the BSCA-Mg(2+) complex and TD/DFT calculations. This sensor exhibits high sensitivity and selectivity for the quantitative monitoring of Mg(2+) with a wide detection range (0-40 µM), a low detection limit (2.89 × 10(-7) mol L(-1)) and a short response time (<0.5 s). It can also resist the interference from the other co-existing metal ions, especially Ca(2+). Consequently, this fluorescent sensor can be utilized to monitor Mg(2+) in real time within actual samples from drinking water.

A dual channel optical detector for trace water chemodosimetry and imaging of live cells.

A novel 3-5-dichlorosalicylaldehyde Schiff base chemodosimeter (compound 1) for water is designed and synthesized, and it works based on a water-triggered reaction of a Schiff base. Addition of trace amounts of water into 1 in various organic solvents leads to a fluorescence turn-on response and a simultaneous dual-channel signal modulation (both in the fluorescence and absorption spectra). Especially, 1 is found to be an outstanding fluorescence enhancement water sensor in methanol with an extremely low detection limit of 22 ppm. Consequently this probe can be utilized to detect trace water in commercial methanol. The quantitative detection of a wide range of water content is enhanced in THF and acetonitrile (0-35% v/v for THF and 0-20% v/v for acetonitrile), where the fluorescence peak intensity is nearly proportional to the amount of water added. Moreover, 1 can be used for monitoring pH through a novel ON-OFF-ON type signal modulation both in fluorescence and absorption spectra within a wide pH detection range. Thus, the chemodosimeter can not only be utilized to monitor the intracellular pH fluctuations, but also to accomplish simultaneous in situ staining of the cytosol and acidic organelles in two different channels, respectively.