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Rational regulation of the properties of photochromic materials is a challenging and meaningful work. In the present work, NDI-based complexes, namely, [Cd

Recently, stimuli-responsive materials have attracted great attention, while most of them respond to single or two stimuli. Thus, it is essential to design multifunctional stimuli-responsive materials and develop their applications. The strategy that constructing high-dimensional coordination polymers facilitates the application scope of a viologen-based photochromic system is put forward and confirmed for the first time. Herein, a novel multistimuli-responsive viologen-based Zn-MOF with a two-dimensional framework has been successfully designed and synthesized. Complex

A trinuclear zinc complex (1) exhibits mechanochromic and acidochromic luminescence properties with five-color switching. The structure of complex 2 shows that the acetonitrile molecules induce fine-tuning of the structures compared with 1.

A new strategy for the synthesis of multifunctional stimuli-responsive room-temperature phosphorescent materials and their application in multiple dynamic encryption was reported.

A zinc(ii) complex exhibits high-contrast and multicolor switching in response to mechanical, acid–base vapor and electrical stimulation under ambient light and 365 nm UV light.

The acetonitrile solvate of a Schiff base molecule (HL) with acetonitrile (HL·2CH3CN) and its Cd(II) complex (Cd(HL)2Cl2, 1) were 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. While 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 crystalline to 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 a phase transformation from crystalline to 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 restore 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.

A diamond-like cuprous coordination polymer based on the [Cu8I6]2+ cluster has been successfully synthesized. This complex exhibits thermochromic and mechanochromic luminescence properties as well as good performance for the sorption and release of I2.

A triphenylamine (TPA)-based 2H-quinazoline Zn(II) complex (Q-TPA-Zn) exhibiting dual fluorescence and phosphorescence emission in the solid state was designed and prepared. It possesses mechanochromic luminescence and thermochromic luminescence properties. In the solid state, the white afterglow luminescence could be observed at 77 K (CIExy: 0.27, 0.33) while cyan luminescence could be observed at 297 K. After thermolysis at 300 °C, Q-TPA-Zn could be transformed into Schiff base complex S-TPA-Zn with white fluorescence in the powder state (CIExy: 0.32, 0.38), in methanol (CIExy: 0.32, 0.39), and in dimethylformamide (CIExy: 0.26, 0.32) at room temperature. This arises from dual emission of normal* emission and tautomeric* emission induced by excited-state intramolecular proton transfer (ESIPT) from the benzimidazole NH group to the Schiff base N atom. Q-TPA-Zn could also be transformed into its isomeric form, S-TPA-Zn, through photochemical ring-opening reaction upon irradiation under 365 nm in the solution, exhibiting high-contrast photochromic luminescence. Interestingly, S-TPA-Zn could further be transformed into its zwitterionic isomer after continuous irradiation. The same ring-opening reaction could also take place for the orgainc compound Q-TPA via heating or 365 nm irradiation. The ring-opening reaction mechanism and ESIPT emission were interpreted via theoretical calculation.

It is necessary to develop stable and fast multistimuli responsive materials due to the growing demand in our daily life. In this work, a new viologen-based Cd-complex (1) exhibits multiple thermochromic and photochromic behaviors through 10 states with 7 colors. For example, it responds to both Cu Kα/Mo Kα X-ray sources and UV dual light quickly with a color change from colorless to dark blue (1X) (Cu Kα/Mo Kα X-ray sources) and cyan (1-UV) (UV light), respectively. Interestingly, it exhibits a three-step coloration phenomenon when heated, which is unprecedented in viologen compounds. Crystal 1 undergoes a color change to pink, blue, and brown under 130, 180, and 240 °C, respectively. In addition, upon fumigation, both 1P and 1Q undergo a decoloration process to colorless (1K) and yellow (1T), respectively. Four more states (1P, 1K, 1T, and 1O) obtained via dehydration-hydration treatment are all photochromic. More importantly, via single-crystal-single-crystal transformation (SC-SC), the photochromic and thermochromic behaviors of 1 were investigated from the molecular level, which is also rather rare for thermochromic species. The detailed electron donor and the pathways for electron transfer were clearly given according to the results of crystal structure. The colorful states upon external stimuli may be attributed to the multiple pathways for electron transfer.

A multi-binding site chemosensor, N-(3-methoxy-2-hydroxybenzylidene)-3-hydroxy-2-naphthahydrazone (H3L), with excited-state intramolecular proton transfer (ESIPT) behaviour was prepared and characterized. It possesses no aggregation-induced emission (AIE) characteristics but can detect Cd2+ and Zn2+ ions selectively in the "off-on" mode based on the AIE of their complexes in the media of THF/HEPES and THF/H2O, respectively, which will provide a new strategy for target detection based on AIE. The detection limits of Zn2+ and Cd2+ were 9.85 × 10-9 M and 1.27 × 10-7 M, respectively. The aggregates of the complexes formed in the detection system were confirmed by DLS data and SEM images. The corresponding Zn2+ (1) and Cd2+ (2) complexes were prepared to investigate the response mechanism. Powder X-ray diffraction and single crystal X-ray diffraction proved that complex 1 is the species formed in the detection system. The chemosensor coordinates with the Cd2+ and Zn2+ ions in different formation and coordination modes, leading to the emission position of the aggregates at 560 and 645 nm, respectively, based on which Cd2+ ions were successfully differentiated from Zn2+ ions. Moreover, the detection of Cd2+ and Zn2+ ions was realized qualitatively via test paper and quantitatively in water.

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.

Multi-stimuli responsive materials have been attractive for their wide potential applications. The most important but still a challenge is the design of the material and the explanation of how the stimuli affect the molecular structure. Grinding is the most reported mechanical stimuli. But it is very difficult to obtain single-crystals directly after grinding to provide the molecular-level understanding of mechanochromic luminescence (MCL) properties because anisotropic forces can induce crystal collapse, making them unsuitable for single-crystal X-ray analysis. Here we designed a TPE-based Schiff base, N-(2-hydroxy-1-naphthylidene)-1-tetraphenylethenylamine (HL), and first obtained its enol (HLe) and keto (HLk) forms separately. Multi-stimuli response was realized with the aid of transformation of two tautomers. Both the tautomers can respond to grinding. The single crystal X-ray diffraction data of HLe and HLk crystals before and after grinding show that the torsion angles of HLe and HLk molecules change after grinding, which results from the variation of molecular packing and the fine-tuning of molecular conformation. The blue shift of emission bands for HLe and HLk was ascribed to the synergetic effect of crystal size and conformation variation. HLk is vapochromic and could respond to volatile organic solvents via vapor-fuming to generate HLe. This arises from proton transfer from –NH to OC of HLk, in which vapor-induced proton transfer and molecular arrangement variation play a crucial role. There exists the tautomerization of enol and keto forms in solution. HLe and HLk show aggregation-induced emission (AIE) property in THF/H2O, but only the aggregates of HLk form could be obtained no matter whether the original solute was HLe or HLk. HL could also respond to Cu(II) and Al(III) ions in solution. It is an on–off chemosensor for Cu(II) and a chemodosimeter for Al(III) ions.

The development of smart luminescent materials, especially those stimulus-responsive fluorescent materials that can switch between different colors repeatedly under external stimulation based on a single molecule, is of great significance but a challenge. In this work, a novel zinc(II)-Schiff base complex (ZnL2) was obtained and characterized. Upon exposure to the HCl and NH3 vapors, it displayed remarkable tricolor acidochromic behavior with high contrast and rapid response under the ambient light as well as UV light (365 nm). The XPS analyses of ZnL2 crystals before and after HCl/NH3 fuming show that the acidochromism originates principally from the adsorption of vapor and the gas-solid reaction equilibrium on the crystal surface. The reddish-brown color of the HCl-fumigated ZnL2 crystals could be attributed to the generation of HL at the surface of ZnL2, and red-shifted emission could be ascribed to the self-absorption effect. The single crystal X-ray diffraction data indicate that these processes cause slight changes in the molecular conformation and crystal packing. ZnL2 shows reversible mechanochromic luminescence behavior between yellow and orange emission during the grinding-fuming/heating cycles due to the modulation between amorphous and crystalline states. Moreover, ZnL2 was successfully made into test paper for the rapid detection of HCl/NH3 vapors and mechanical stimuli.

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.

A new Fe-based amorphous–crystalline composite without non-metallic elements, Fe55Cr15Mo15Ni10W5, was prepared by melt-spinning. The formation ability and structure information were investigated by X-ray diffractometer (XRD), energy-dispersive spectrometer (EDS) and scanning electron microscope (SEM). The mechanical properties of the amorphous–crystalline composite were investigated by nanoindentation. A molecular dynamics simulation study was performed to simulate the formation of Fe55Cr15Mo15Ni10W5 amorphous alloy. The mechanical properties were obtained by compression simulations simultaneously. The results indicate that the Fe55Cr15Mo15Ni10W5 ribbon is an amorphous–crystalline composite structure with good ductility, and the hardness of the amorphous–crystalline composite is about 75% higher than that of master ingot. The simulation mechanical properties are in good agreement with the results of nanoindentation at the nanoscale.

We first report single crystal X-ray analysis of ground crystals of mechanochromic luminescence (MCL) that shows single crystal-to-single crystal transformation (SCSCT). Single crystals of [ZnL2] (...

Objective To investigate the safety and efficacy of a self-developed novel multi-electrode radiofrequency ablation catheter (Spark) for catheter-based renal denervation (RDN). Methods A total of 14 experimental miniature pigs were randomly divided into four groups (55°& 5-watt, 55°& 8-watt, 65°& 5-watt, and 65° & 8-watt groups). Spark was used for left and right renal artery radiofrequency ablation. Blood samples collected from renal arteries and veins as well as renal arteriography were performed on all animals before, immediately after, and three months after procedure to evaluate the effects of Spark on the levels of plasma renin, aldosterone, angiotensin I, and angiotensin II as well as the pathological changes of renal arteries. Results One pig died of an anesthetic accident, 13 pigs successfully underwent the bilateral renal artery ablation. Compared with basic measurements, pigs in all the four groups had significantly decreased mean arterial pressure after procedure. Histopathological analysis showed that this procedure could result in intimal hyperplasia, significant peripheral sympathetic nerve damage in the renal arteries such as inflammatory cell infiltration and fibrosis in perineurium, uneven distribution of nerve fibers, tissue necrosis, severe vacuolization, fragmented and unclear nucleoli myelin degeneration, sparse axons, and interruption of continuity. In addition, the renal artery radiofrequency ablation could significantly reduce the levels of plasma renin, aldosterone, angiotensin I, and angiotensin II in pigs. Conclusions The results suggest that this type of multi-electrode catheter-based radiofrequency ablation could effectively remove peripheral renal sympathetic nerves and reduce the activity of systemic renin-angiotensin system in pigs, thus facilitating the control of systemic blood pressure in pigs.