Mechano- and Photoresponsive Behavior of a Bis(cyanostyryl)benzene Fluorophore

The mechanoresponsive behavior and photochemical response of a new bis(cyanostyryl)benzene fluorophore (CSB-5) were investigated. Green fluorescence with λ_em,max of 507 nm was found for CSB-5 in chloroform solution, mirroring the behavior of a previously reported similar dye (CSB-6). Alternatively, crystalline samples of CSB-5 exhibited orange fluorescence with λ_em,max of 620 nm, attributable to excimer emission. Although the emission color change was not clearly noticeable by naked eye, CSB-5 exhibited mechanochromic luminescence, due to transformation into the amorphous state upon grinding the crystalline powder. Interestingly, rubbed films of CSB-5 prepared on glass substrates exhibited a pronounced emission color change from orange to green when exposed to UV light. This response is the result of a photochemical reaction that occurs in the amorphous state and which causes a decrease of the excimer emission sites so that the emission color changes from excimer to monomer. The crystalline material did not display such a photoinduced emission color change and the difference in photochemical reactivity between crystalline and amorphous states was exploited to pattern the emission color of rubbed films.     

Blue/red linear dichroic emission from a highly anisotropic crystal of triarylmethane dye conjugated with phenoxo-zinc complexes

We have developed a novel triphenylmethane-based hexanuclear zinc complex that exhibits peculiar photochemical and photophysical properties. Upon UV irradiation, the compound turned from colorless to reddish purple, while the color of emission turned from blue to red. The color change was attributed to an oxidation of the ligand part. It was suggested that an intramolecular energy-transfer mechanism operates to give rise to the red emission. The UV treatment of a single crystal results in simultaneous emission of orthogonally polarized blue and red light. This color switching, namely linear dichroic emission was so distinct that one can recognize with by sight through optical microscope. The columnar arrangement of molecules in the crystal clearly accounts for the observed polarization of the emission.     

Reversible mechanochromic luminescence of [(C6F5Au)2(mu-1,4-diisocyanobenzene)

Reversible mechanochromic luminescence of [(C6F5Au)2(mu-1,4-diisocyanobenzene)] is reported. Grinding of the complex induced a photoluminescent color change, which was restored by exposure to a solvent. This cycle was repeated 20 times with no color degradation in the emissions. Their optical properties, X-ray crystallographic analysis, IR, and XRD measurements strongly suggested that the change in the molecular arrangement is responsible for this mechanochromic property. Intermolecular aurophilic bondings presumably play a key role in the altered emission.     

Multi-Color Photoluminescence Based on Mechanically and Thermally Induced Liquid-Crystalline Phase Transitions of a Hydrogen-Bonded Benzodithiophene Derivative

Controlling assembled structures of π-conjugated liquid-crystalline molecules is of great interest in the development of stimuli-responsive luminescent materials due to their molecular motility in the ordered states. Herein, we describe a mechanoresponsive hydrogen-bonded benzodithiophene liquid-crystalline molecule that exhibits a tricolor photoluminescence switching at ambient temperature. The compound shows a shear-induced phase transition from a rectangular columnar to a metastable optically anisotropic mesophase, which is accompanied by the luminescent color change from yellow to sky-blue. The metastable mesophase exhibits a time-responsive transformation to another metastable mesophase showing a blue-green emission through isothermal aging at room temperature. The luminescent color of aged sample reverts back to the initial yellow color by thermal annealing at 150 °C. These dynamic structural changes accompanied by the emission color changes are governed by distinct π-stacking modes and hydrogen-bonded patterns. The shear-induced luminescent color change from yellow to blue is found to occur above the shear strain of 390 % at which the shear stress is 2.4×10⁵ Pa as determined from dynamic viscoelastic measurements.     

Environment‐Sensitive Fluorescent Probe: A Benzophosphole Oxide with an Electron‐Donating Substituent

Electron‐donating aryl groups were attached to electron‐accepting benzophosphole skeletons. Among several derivatives thus prepared, one benzophosphole oxide was particularly interesting, as it retained high fluorescence quantum yields even in polar and protic solvents. This phosphole‐based compound exhibited a drastic color change of its fluorescence spectrum as a function of the solvent polarity, while the absorption spectra remained virtually unchanged. Capitalizing on these features, this phosphole‐based compound was used to stain adipocytes, in which the polarity of subcellular compartments could then be discriminated on the basis of the color change of the fluorescence emission.     

Solid-state fluorescence organic materials as a tool for spectral modification of ZnS-based screen-printed thick layer electroluminescence devices

This work is focused on modification of spectral characteristic of light emitted by alternating current powder-based ZnS electroluminescent device by addition of a color conversion material. A suitable diketopyrrolopyrrole (DPP) derivative with absorption spectrum compatible with emission spectrum of phosphor was found and was added into the printing formulation. Electroluminescent panel was printed by screen printing method and the influence of fluorophore was evaluated from the emission spectra of the electroluminescent device. Color space coordinates of emitted light of pure phosphor and phosphor modified by DPP were plotted into the CIE space for better visualization of the color change. It was found that the presence of fluorophore increased the value of measured quantity—absolute spectral irradiance—more than seven times at 587 nm which corresponds to the maximum of fluorescence emission of DPP. This approach provides useful tool to obtain colors of various wavelengths and therefore various hues without the need to look for new challenging and expensive chemical modifications of the phosphor.     

N‐Boc‐Indolylbenzothiadiazole Derivatives: Efficient Full‐Color Solid‐State Fluorescence and Self‐Recovering Mechanochromic Luminescence

Herein, the solid‐state emission with good fluorescence quantum yields of N‐Boc‐indolylbenzothiadiazoles as a new class of fluorophores is described. Their solid‐state emission covers the wide range of the visible spectrum and the emission color can be tuned easily by changing the substituents on the two heteroaromatic rings. Among these, 3‐methylindolyl derivatives exhibit moreover autonomously self‐recovering mechanochromic luminescence, whereby the original solid‐state emission could be recovered spontaneously at room temperature after exposure to a mechanical stimulus. The emission color, as well as the recovery time for the color change could be tuned via the introduction of different substituents on the benzothiadiazole ring. We propose that the mechanism of the autonomously self‐recovering mechanochromic luminescence of 3‐methylindolylbenzothiadiazoles is based on a partial amorphization of the crystals upon exposure to the mechanical stimulus, followed by autonomous recovering in the form of recrystallization.     

Control of Multicolor and White Emission by Adjusting the Equilibrium between Fluorophores,Lewis Acids,and Their Complexes in Polymers

Multicolor emissive materials consisting of a single luminophore, a Lewis acid, and their complex were developed. The emission colors can be tuned by changing the concentration of the solution and the ratio of mixed solvents. Various emission colors in the solid state were observed when the complexes were added to polymers in different amounts. The color change is due to equilibrium disruption between the single luminophore, the Lewis acid, and the complex thereof. White emission was observed by appropriately controlling the equilibrium by changing the amount of the complex in the polymer.     

Color Tunable Emission and Oxygen Sensing from a Discrete Europium−Pyrene Assembly

We report the synthesis of a new pyrene, dipicolinic acid-based ligand ( L₁H ) and its corresponding multi-emissive and multifunctional europium complex [Eu( L₁ )₃] that is capable of single component color switchable emission from red to blue and also white. At high concentration (10 mM) the single component system results in near pure white emission (CIE coordinates x,y=0.329, 0.324). Furthermore, the system showed ratiometric oxygen sensing with oxygen significantly quenching the pyrene centered emission but not the Eu³⁺ emission, resulting in an overall emission color change from blue to red on increasing oxygen content.     

Control of Multicolor and White Emission by Adjusting the Equilibrium between Fluorophores,Lewis Acids,and Their Complexes in Polymers

Multicolor emissive materials consisting of a single luminophore, a Lewis acid, and their complex were developed. The emission colors can be tuned by changing the concentration of the solution and the ratio of mixed solvents. Various emission colors in the solid state were observed when the complexes were added to polymers in different amounts. The color change is due to equilibrium disruption between the single luminophore, the Lewis acid, and the complex thereof. White emission was observed by appropriately controlling the equilibrium by changing the amount of the complex in the polymer.     

Photophysical properties and photochemical rearrangement of single crystal salicylideneaniline in solution

Salicylideneaniline originally crystallized from a solution has lemon yellow color. Irradiation with near ultraviolet causes the color change from yellow to red. The red state changes spontaneously back to yellow in 2ms. This change is accelerated by visible light. Kinetic data are reported in the temperature range between 10 and 60 degrees C, for the dark fading reactions of the colored isomers formed by the near ultraviolet irradiation. Observed the decay kinetics was first order reactions. Activation energies and entropies of activation are reported for ethanol. The observation of T-T absorption and emission were complicated due to the colored isomer formation during the optical pumping.     

Design of a ratiometric fluorescent probe for benzenethiols based on a thiol-sulfoxide reaction

A novel thiol-sulfoxide reaction based ratiometric probe for benzenethiols was synthesized and evaluated. The probe features a chemospecific reduction over a pH range of 1-10 by benzenethiols with a marked emission color change, enabling the highly selective detection and is promising for applications.     

Synthesis and application of quantum dots FRET-based protease sensors

Preparation of FRET-based quantum dots as protease sensors-RGDC peptide molecules are bound to the surface of CdSe/ZnS quantum dots. The peptide molecules are then labeled with rhodamine dye molecules. The emission color of the quantum dots change from green to orange due to fluorescence resonance energy transfer (FRET) between the quantum dots and the bound rhodamine molecules. Cleavage of the peptide by selective proteases releases the rhodamine molecules from the quantum dots surface, which results in decreasing FRET efficiency between the quantum dots and the rhodamine molecules. The emission color of the quantum dots changes back to green.     

Optical mercury sensing using a benzothiazolium hemicyanine dye

[structure: see text] The selectivity and sensitivity of a benzothiazolium hemicyanine dye toward mercury(II) in aqueous solutions are described. Mercury ions coordinate to the dye forming a 1:1 complex. This interaction induces a color change in the dye at micromolar concentrations of mercury. Furthermore, the color change and quenching of the dye emission are selective for mercury when compared with other ions such as lead(II), cadmium(II), zinc(II), or iron(II).     

New thermally stable piezofluorochromic aggregation-induced emission compounds

New piezofluorochromic compounds with high thermal stabilities and aggregation-induced emission behavior were developed. The spectroscopic properties and morphological structures of these compounds were reversed upon pressing (or grinding)/annealing (or fuming). The switchable color change feature and aggregation-induced emission make the compounds promising candidates for optical recording, pressure-sensing, and light-emitting systems.     

A multi-functional fluorescent sensor for Zn2+ and HSO4− based on a new diarylethene derivative

A new photochromic diarylethene derivative with a hydralazine unit was designed and synthesized. It was not only acted as a Zn²⁺ sensor with the fluorescent color change from dark blue to bright orange, but also acted as a fluorescent sensor for HSO₄^? with the fluorescent color change from dark blue to bright blue. Furthermore, the derivative also exhibits multi-addressable switching properties by the stimulations of lights and chemical reagents. Based on these characteristics, two combinational logic circuits were constructed with the emission intensity as the output signals, and the UV/vis lights, chemical species as the input signals.     

AIE Ligand Constructed Zn(Ⅱ)Complex with Reversible Photo-induced Color and Emission Changes

Fluoran salicylaldehyde hydrazone metal complex(FSHMC)is a kind of recently reported photo-responsive system,which has the advantages of simple synthesis,multiple colors as well as distinct color change before and after UV light irradiation.However,the emission property of FSHMC is relatively unitary.In solid state,especially,only fluorescence quench is induced after UV light irradiation,which limits their applications.In this work,a typical aggregation-induced emission(AIE)moiety of tetraphenylethene(TPE)was introduced to the design of FSHMC.The obtained FSHMC,2-Zn,exhibited reversible color and fluorescence changes upon UV light irradiation.Due to the AIE feature of compound 2,2-Zn exhibited different emission changes upon UV light irradiation in THF and in solid matrix,because of the fluorescence resonance energy transfer(FRET)process from TPE moiety to rhodamine B moiety.     

A new class of platinum (II) vapochromic salts

Luminescent chloride and hexaflurophosphate salts of Pt(Me2bzimpy)Cl+ (Me2bzimpy = 2,6-bis(1-methylbenzimidazol-2-yl)pyridine) are reported. As solids, both compounds are vapochromic, undergoing pronounced and reversible changes of color and emission in the presence of volatile organic compounds. The chloride salt responds to vapors of methanol, chloroform, ethanol, and acetonitrile, undergoing a distinct change in color from yellow to red within seconds. The PF6- salt responded selectively to acetonitrile vapor, changing from yellow to violet while sorbing 1.0 +/- 0.1 equiv. For either salt, leaving vapor-exposed samples in air for several days or heating for several minutes restored the original color. UV-visible absorption spectra and solid-state room temperature and 77 K emission spectra are reported, and the accumulated data are consistent with a decrease in Pt...Pt separation accompanying vapor sorption.     

四苯乙烯衍生物的合成、性能及其对铀酰离子的荧光识别

聚集诱导发光(AIE)效应在铀酰离子痕量检测方面具有广阔的应用前景。本文以四苯乙烯(TPE)为母体,设计合成了一种TPE席夫碱类化合物T2,并对其溶液态和聚集态的光学性质进行了表征。结果表明,T2具有AIE特性。并且,当向T2中加入铀酰离子后,体系荧光发射峰从540nm蓝移到500nm,肉眼可见由黄色到黄绿色的明显颜色变化,表明化合物T2可用于检测水体中的铀酰离子。     

Hg and Cu selective detection using a dual channel receptor based on thiopyrylium scaffoldings

2,4,6-Triphenylthiopyrylium functionalized with an aza-oxa-thia macrocycle is able to selectively recognize Hg²⁺ cation by a color change and Cu²⁺ cation by a remarkable significant emission enhancement.