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An acetonitrile solvate of a Schiff base molecule (HL) with acetonitrile (HL·2CH3CN) and its Cd(II) complex (Cd(HL)2Cl2, 1) was designed and synthesized. The different conformation of HL in HL·2CH3CN is adjusted by the hydrogen bonding O–H⋯O between HL molecules, together with N–H⋯N between HL molecules and acetonitrile molecules. Meanwhile, the conformation of HL in complex 1 is adjusted by coordination interactions between Zn ions and atoms O and N, together with hydrogen bonding N–H⋯Cl. The presence of the triphenylamine group makes HL·2CH3CN and complex 1 loosely packed. Upon grinding, HL·2CH3CN and complex 1 both showed high-contrast mechanochromic luminescence (MCL) change from blue to green and cyan to yellow, respectively. These changes can be eliminated by fumigation with organic vapor. The results of powder X-ray diffraction (PXRD) show that their MCL is due to the phase transformation from a crystalline state to an amorphous state. In addition, HL·2CH3CN and complex 1 also exhibited high-contrast acidochromism upon exposure to HCl and NH3 vapor. X-ray photoelectron spectroscopy (XPS) and PXRD studies show that the protonation of the –NH– group together with phase transformation from a crystalline state to an amorphous state is attributed to the fluorescence switching. For HL·2CH3CN, the protonation process was accompanied by the departure of acetonitrile molecules. The emission of HL was restored to the amorphous state rather than the original crystalline state emission after further exposure to NH3 vapor, while 1-HCl could revert to the original crystalline state emission. In addition, HL·2CH3CN and complex 1 have been successfully used to produce writable and acid-responsive test papers. [ABSTRACT FROM AUTHOR]

Multifunctional luminescent materials have attracted intensive interest. However, the mechanisms behind them are still to be explored. In this work, three Zn(II) complexes based on Schiff bases (HL1 and HL2) that contain rotatable aromatic rings were designed and prepared. They exhibited different mechanochromic luminescence (MCL) and acidochromism. The polymorphous ZnL12 and ZnL1a2 crystallize in different crystal systems with different conformations. The ligands in ZnL12 adopt a more twisted conformation than those in ZnL1a2. ZnL12 exhibits MCL with high contrast, while ZnL1a2 exhibits a negligible MCL property. This may be due to the looser packing of the complex induced by the more twisted conformation of the ligand HL1. ZnL12 could undergo crystal phase transformation into ZnL1a2 by grinding/fuming cycles. To increase the flexibility of the ligand, a methylene group was introduced to result in HL2, which can improve the mechanochromic luminescence effect of the Zn(II) complex with high color contrast. The ligands involved in coordination generally adopt a more twisted conformation than those free ligands due to the steric hindrance, resulting in more obvious MCL for complexes. By comparing the luminescence of ligands and their complexes under acid–base stimulation, it is found that the acidochromic properties could be attributed to the generation of ligands at the surface of complexes via the gaseous HCl-solid Zn(II) complex reaction. The high contrast mechanochromic and acidochromic luminescence properties would lead to promising potential applications of these complexes in smart fluorescent materials, and would also provide some ideas for the design of multi-stimuli responsive molecules. [ABSTRACT FROM AUTHOR]

Three AIE (aggregation-induced emission)-ESIPT (excited-state intramolecular proton transfer) active 2-(2-hydroxyphenyl)benzothiazole derivatives, HL1, HL2 and HL3 with one, two and three rotatable phenyl groups, were obtained and characterized. Their AIE properties in THF/HEPES solution were investigated in detail. HL2 shows the best AIE performance with 71-fold fluorescence enhancement, while HL3 only shows a 9-fold enhancement. With the AIE property, HL1 and HL2 could act as fluorescence chemosensors to detect Cu2+ ions via the "turn off" mode in THF/HEPES media. With the ESIPT property, HL1 and HL2 could also detect Zn2+ ions via the "turn on" mode in EtOH/HEPES media. During the detection process, both demonstrate rapid response and high contrast before and after the addition of metal ions. The species formed in the detection system were investigated. The results of X-ray single-crystal diffraction confirm that Zn2+ is coordinated with the oxygen atom and Schiff base nitrogen atom instead of the benzothiazole nitrogen atom in the tetrahedron geometry. Moreover, the chemosensors were successfully constructed into handy fluorescence test papers for Cu2+ and Zn2+ detection. [ABSTRACT FROM AUTHOR]

A novel Schiff base ligand HL ·CH 3 COOH with excited-state intramolecular proton transfer (ESIPT) and its zinc (Ⅱ) complex 1 were successfully synthesized, and both of them show high-contrast mechano- and acidochromic luminescence. [Display omitted] A new Schiff base compound (HL ·CH 3 COOH) with D-A structure and its zinc(II) complex (1) were successfully obtained. Due to the introduction of diethylamino and rotatable aromatic rings, both HL ·CH 3 COOH and the complex adopt loosely packing patterns. HL ·CH 3 COOH exhibits keto-form emission due to the excited-state intramolecular proton transfer (ESIPT) process, while complex 1 shows enol-form emission. They all show reversible mechanochromic luminescence (MCL) behavior, which is caused by the phase transformation from crystalline state to amorphous state revealed by Powder X-ray diffraction (PXRD) studies, and is accompanied by the departure of CH 3 COOH molecules for HL ·CH 3 COOH. HL ·CH 3 COOH and complex 1 can be protonated under the fumigation of HCl, resulting in the acidochromic properties, accompanied with the phase transformation. HCl also destroyed the interactions between CH 3 COOH and Schiff base molecules, leading to the departure of acetic acid molecules. More interestingly, HL ·CH 3 COOH also exhibited NH 3 -stimuli response properties due to the prohibition of the ESIPT process. [ABSTRACT FROM AUTHOR]

In this work, we successfully synthesized two Schiff base (HL) complexes, ZnLCl 2 (1) and [Cd 2 L 2 Cl 4 ]·CH 3 CN (2), via the one-pot reaction of metal salts with 4-[bis(4-bromophenyl)amino]benzaldehyde and 3-hydroxy-2-naphthoic acid hydrazide. Complex 2 exhibits not only acidochromic properties but also NH 3 -induced discoloration behavior, which is rarely reported among triphenylamine derivatives or complexes. However, complex 1 shows no color change upon fuming with HCl or NH 3 vapor. The experimental results show that acidochromism may be due to the decomposition of the structure by HCl vapor, while NH 3 -induced discoloration is mainly attributed to the phase change of 2 from crystalline to amorphous state. In addition, complexes 1 and 2 showed high-contrast mechanochromic luminescence (MCL) change from yellow to orange and green to yellow, respectively. Complexes 1 and 2 also exhibit electrochromic behavior with color change from yellow to brown. Moreover, complex 2 was successfully made into test paper for mechanical stimuli and the rapid detection of HCl and NH 3 vapor. The complex 2 can be fixed on a mask coat to fabricate a 2 -based wearable hazardous gas sensor, suggesting that 2 is expected to develop into the next generation wearable sensors for detection of HCl and NH 3 vapor. [Display omitted] • Complexes 1 and 2 showed reversible mechanochromic luminescence behavior. • 2 exhibits acidochromic properties and NH 3 -induced discoloration behavior. • Complexes 1 and 2 also exhibit electrochromic behavior. • 2 can be made into test paper for repeated writing and HCl/NH 3 vapor detecting. • 2 can be made wearable sensor for detection of HCl and NH 3 vapor. [ABSTRACT FROM AUTHOR]