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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]

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]

Multistimuli responsive materials based on the viologen coordination polymers have attracted much interest in the past few years due to the increasing demand for smart materials. In this paper, based on a viologen ligand 1-(3-carboxybenzyl)- 4,4′-bipyridinium chloride (Hcbbpy) and zinc(II) ion, a new crystalline complex, namely, {[Zn(cbbpy)Cl 2 ]·H 2 O} n (1) has been designed and synthesized. In complex 1 , every cbbpy ligand as a bridge links two Zn2+ ions via carboxylate O atom and pyridine N atom to extend to a 1D zigzag chain. The 1D chains are extended to 3D supramolecular structure through π···π stacking and hydrogen bonding. More importantly, 1 exhibits fast photochromic behaviors in response to UV and X-ray due to the formation of viologen radicals. Complex 1 also shows photo-modulated luminescence property in the solid state. In addition, complex 1 can be deposited on filter paper and displays the potential application as inkless print material. [Display omitted] • A new viologen complex was successfully synthesized and characterized. • Complex 1 shows fast response to UV light and X-ray irradiation. • Complex 1 can be deposited on filter paper and displays as inkless print material. [ABSTRACT FROM AUTHOR]

Nowadays, photoactive viologen units have been widely encapsulated in metal-organic frameworks and assembled into multifunctional materials with photochromism and other light regulating properties. A novel host-guest MOF material, {[Zn(bcbpy) 0.5 (IPA)]·CH 3 CN} n (1), has been constructed by a viologen ligand 1,1′-bis((3-carboxylatobenzyl)-4,4′-bipyridinium)-dichloride (H 2 bcbpy·2Cl), isophthalic acid (IPA) and zinc(II) chloride. Complex 1 exhibits UV and X-ray dual photochromism and photo-controlled luminescence properties. Complex 1 also exhibits a temperature-dependent phosphorescence from cyan to yellow when the temperature increases from 77 to 297 K. 1T will be obtained when 1 is heated in air at 230 °C for 30 min, 1T shows less sensitive photochromic property than 1 due to its longer C–H⋯O hydrogen bond distance for electron transfer pathway. In addition, complex 1 has the potential application as an inkless and erasable printing material due to the excellent photochromic property. [Display omitted] • A UV and X-ray dual photochromic complex 1 was synthesized and characterized. • Complex 1 exhibits photo-controlled luminescence properties. • Complex 1 exhibits temperature-dependent phosphorescence properties. • Complex 1 has the potential to be used as an inkless and erasable printing material. [ABSTRACT FROM AUTHOR]