Synthesis,photochromic mechanism and properties of a novel biindenylidenedione compound containing ferrocene units

A novel biindenylidenedione compound, [2,2′‐bi‐1H‐indene]‐3,3′‐bis [(4‐oxo‐4‐ferrocenylbutanoyloxy)propyl]‐3,3′‐ dihydroxy‐1,1′‐dione was synthesized and characterized fully by ¹H NMR, IR, MS and elemental analysis. The photochromic and photo‐induced radical properties were investigated by means of UV–vis and electron spin resonance spectroscopy, respectively. The results show that the title compound simultaneously exhibits photochromism in the solid state as well as generating stable free radicals under irradiation with 330 nm light. This fact provides evidence for the photochromic mechanism of this kind of compounds. Copyright © 2008 John Wiley & Sons, Ltd.     

一种新的含吡唑啉酮氨基硫脲化合物的晶体结构及其光致变色性质

A new photochromic organic compound of thiosemicarbazone, 4-（p-bromo-α-methylaminothiocarbonyl hydrazonobenzal）-2,5-dihydro-3-mcthyl-5-oxo-1-phcnyl pyrazolc, was synthesized and characterized by elemental analyses, IR, ^1H NMR spectra, and X-ray single-crystal diffraction analysis. The compound exhibited an interesting photochromism in the solid state when irradiated by ultraviolet light at 365 nm. The photochromic kinetics was studied by the time-dependent powder UV-Vis reflectance spectra. The intcrmolecular and intramolecular hydrogcn-bonding interactions may be responsible for the photochromic phenomenon.     

Synthesis,Characterization and Photochromic Properties of Novel Naphthopyrans with Hydrazone Unit Residue

A series of naphthopyrans with hydrazone unit ( 8a – 8m ), were synthesized and characterized by ¹H NMR, ¹³C NMR, IR and HRMS. The photochromic properties were investigated under continuous irradiation, in particular regard to the fatigue resistance and the lifetime of the colored open form in solution and polymers. The results showed that these compounds had both good photochromic properties and high fatigue resistance. Detailed studies showed that representative compound 8d (3,3‐di‐4‐methoxybenzoic acid methylenehydrazino‐[3H]‐naphtho [2,1‐b]pyran) had good photochromic properties in THF solution, in solid state, and in polymers, and exhibited a significant bathochromic shift in the spectra of the open forms compared to known naphthopyrans 9 (3,3‐diphenyl‐[3H]‐naphtho[2,1‐b]pyran). On the other hand, the higher melting points of target compounds are promising for the polymer film preparation through hot‐melt method.     

Synthesis of Novel Photochromic 6‐Benzyloxo‐spirobenzopyran Compounds

The synthesis of four novel derivatives of 1′,3′,3′‐trimethylspiro‐[2H‐1]‐benzopyran‐6‐benzyloxo‐2,2′‐indoline is reported. The synthetic approach to these compounds involves the preparation of the key compound, 3‐formyl‐4‐hydroxybenzophenone, by means of the Reimer–Tiemann reaction. The photochromic compounds were isolated and characterized by ¹H and ¹³C NMR as well as FT‐IR and UV‐VIS spectrometry. Comparative studies performed in these compounds showed a higher molar extinction coefficient and red shift of maximum absorption wavelength when the benzyloxo group is introduced in the spirobenzopyran molecule.     

3-烷基/对烷氧基苯基-3-羟基-联茚满烯二酮衍生物的合成，晶体结构与固态光致变色及光致自由基性质研究

本文合成了一系列3-烷基/对烷氧基苯基-3-羟基-联茚满烯二酮新化合物,并通过¹H NMR, IR, MS 和元素分析数据进行了结构表征,其中化合物1,5,6的结构通过单晶X-Ray衍射进行了确证。分别用固体紫外光谱和电子自旋共振光谱研究了化合物的光致变色性能和光致自由基性质,结果表明：该类化合物在200W高压水银灯光源照射下产生光致变色现象,同时具有光致自由基性质。本文还根据分子结构和及分子内的作用力讨论了性质与结构之间的关系。     

New photochromic 1,1,3-trimethylspiro[benzo[<Emphasis Type="Italic">e</Emphasis>]indoline-2,3′-[3<Emphasis Type="Italic">H</Emphasis>]-pyrano[3,2-<Emphasis Type="Italic">f</Emphasis>]quinoline]

A new photochromic spiropyran of the benzoindoline series containing the quinoline moiety was synthesized. Its structure was determined by IR and ¹H NMR spectroscopy. The crystal structure of the new compound was established by X-ray diffraction. The photochromic properties of the synthesized spiropyran were investigated.     

Preparation of a spirooxazine grafted PMMA and its photochromic properties

A novel spirooxazine (SO) compound was designed and synthesized. Macromolecular materials, called SO-g-hPMMAs (where the g means grafting and the h means partial hydrolysis), were prepared using PMMA (polymethylmethacrylate) with different degrees of hydrolysis. SO-g-5%hPMMA was prepared by reacting SO-containing active C-Br bonds with 5% partially hydrolyzed PMMA. The SO was characterized using ¹H NMR and infrared. Beyond that, photochromic properties were studied in detail. We discuss the effects of hydrochloric acids and hPMMAs of different hydrolysis degrees on photochromic properties of SO-g-hPMMA. Additionally, mechanical properties of the material were studied. Results indicate that the colored ring-opening form (PMC) of SO-g-hPMMA exhibits a good performance in terms of thermal stability, in contrast to the homologous SO. Experiments additionally demonstrate that hydrochloric acid improves the PMC’s thermal stability. SO-g-9%hPMMA demonstrated a good performance of photochromic properties compared to those with different degrees of hydrolysis.     

Photochromic and thermochromic spiranes 33. Synthesis of a new indolinonaphthoxazino- bisspiropyran and investigation of its photochromic characteristics

A new unsymmetrical bisspiropyran was synthesized on the basis of 2,4-dihydroxyisophthalic aldehyde with naphthoxazinone and indoline fragments in the structure. The structure of the obtained compound was proved by the data from ¹H NMR and IR spectroscopy and X-ray crystallographic analysis. The photochromic characteristics of the obtained compound were investigated. It was established by means of the data from B3LYP/6-31G** quantum-chemical calculations that irradiation of a solution of the obtained biphotochrome with unfiltered light leads to opening of both pyran fragments. This is the first corroborated example of the twofold cleavage of C_spiro–O bonds for compounds of this class.     

DFT/TDDFT Investigation of the Modulation of Photochromic Properties in an Organoboron‐Based Diarylethene by Fluoride Ions

The diarylethene derivative 1,2‐bis‐(5′‐dimesitylboryl‐2′‐methylthieny‐3′‐yl)‐cyclopentene ( 1 ) containing dimesitylboryl groups is an interesting photochromic material. The dimesitylboryl groups can bind to F^?, which tunes the optical and electronic properties of the diarylethene compound. Hence, the diarylethene derivative 1 containing dimesitylboryl groups is sensitive to both light and F^?, and its photochromic properties can be tuned by a fluoride ion. Herein, we studied the substituent effect of dimesitylboron groups on the optical properties of both the closed‐ring and open‐ring isomers of the diarylethene molecule by DFT/TDDFT calculations and found that these methods are reliable for the determination of the lowest singlet excitation energies of diarylethene compounds. The introduction of dimesitylboron groups to the diarylethene compound can elongate its conjugation length and change the excited‐state properties from π→π* transition to a charge‐transfer state. This explains the modulation of photochromic properties through the introduction of dimesitylboron groups. Furthermore, the photochromic properties can be tuned through the binding of F^? to a boron center and the excited state of the diarylethene compound is changed from a charge‐transfer state to a π→π* transition. Hence, a subtle control of the photochromic spectroscopic properties was realized. In addition, the changes of electronic characteristics by the isomerization reaction of diarylethene compounds were also investigated with theoretical calculations. For the model compound 2 without dimesitylboryl groups, the closed‐ring isomer has better hole‐ and electron‐injection abilities, as well as higher charge‐transport rates, than the open‐ring isomer. The introduction of dimesitylboron groups to diarylethene can dramatically improve the charge‐injection and ‐transport abilities. The closed isomer of compound 1 ( 1 C ) has the best hole‐ and electron‐injection abilities, whereas the charge‐transport rates of the open isomer of compound 1 ( 1 O ) are higher than those of 1 C . Importantly, 1 O is an electron‐accepting and ‐transport material. These results show that the diarylethene compound containing dimesitylboryl groups has promising potential to be applied in optoelectronic devices and thus is worth to be further investigated.     

Solid‐State Photochromic Behavior and Thermal Bleaching Kinetics of Two Novel Pyrazolone Phenylsemicarbazones

Two novel photochromic compounds, 1,3‐diphenyl‐4‐benzal‐5‐hydroxypyrazole 4‐phenylsemicarbazone ( 1 a ) and 1,3‐diphenyl‐4‐(4‐nitrobenzal)‐5‐hydroxypyrazole 4‐phenylsemicarbazone ( 2 a ), are synthesized and characterized by elemental analysis, mass spectrometry, FTIR spectroscopy, and ¹H NMR spectroscopy. Their properties, including photochromic behavior, fluorescence properties, and thermal bleaching kinetics, are investigated. The results show that the two compounds exhibit improved photochromic performance in coloration and thermal bleaching rates, excellent photostability, high fatigue resistance, and reversible fluorescence switching properties in the solid state in comparison to reported pyrazolone thiosemicarbazones. The thermal bleaching process obeys first‐order kinetics. Bleaching of powders at 130 °C is completed within 90 s for 1 b (the colored isomer of 1 a ) and 150 s for 2 b (the colored isomer of 2 a ). The activation energy for the thermal bleaching process is determined to be 69 and 95 kJ mol^?1, with frequency factors of 9.5×10⁷ and 9.4×10¹⁰ s^?1 for 1 b and 2 b , respectively.     

Cyanoacetamide Intermediate in Heterocyclic Synthesis: Synthesis and Biological Evaluation of Hitherto New Dioxoisoindoline Heterocyclic Derivatives

Innovative poly‐substituted heterocyclic rings incorporating dioxoisoindoline ( 2 – 25 ) were synthesized through the reaction of dioxoisoindoline derivative 2 as starting compound with various types of reagents. All compounds were characterized by appropriate means of (¹H‐NMR, ¹³C‐NMR, IR, and mass). The prepared compounds were evaluated as antimicrobial agents against Escherichia coli, Staphylococcus aureus, and Candida albicans microorganisms. The tested compounds exhibited low to moderate antibacterial activities and promising results as antifungal agents.     

New Photochromic Salt Spiropyran with Benzyl Substituent

A new salt spiropyran of indoline series containing benzyl substituent in the 8'-position of the [2H]-chromene moiety of the molecule has been synthesized and studied. The structure of the obtained compound has been confirmed by methods ¹H NMR and IR spectroscopy. The study of spectral characteristics and photochromic behavior of the target compound has shown that growing of its single crystal resulted in destruction on account of hydrolysis in acetonitrile. The ¹H NMR spectra of the initial salt spiropyran and product of hydrolysis have been compared.     

Photochromism and Metal Complexation of a Macrocyclic Styryl Naphthopyran

A macrocyclic benzo‐15‐crown‐5 ether unit tethered to a photochromic naphthopyran by a styryl spacer ( MEN ) is shown to form a 1:1 complex with magnesium(II). The structure and dynamics of the specific host–metal interactions were investigated by PFG‐NMR analysis. A combination of UV/Vis and variable temperature multi‐dimensional ¹H NMR photokinetic analysis of the crown‐containing styryl naphthopyran and its metal complex was used to probe the effect of metal complexation on the photochromism.     

New Salt Spiropyran of Indoline Series with Fluorine Substituent

Synthesis, study of structure and photochromic properties of new salt spiropyran of indoline series containing a fluorine substituent in the 6′-position of the 2H-chromene moiety have been described in the work. The structure of the compound has been confirmed by ¹H NMR spectroscopy and X-ray diffraction analysis. Comparison of the structure of the compound with the previously studied analogue containing a methyl group instead of a fluorine atom in the 6′-position of the [2H]-chromene moiety has been made. This compound has been found to be photochromic, long-wavelength absorption maximum of its open form shows a bathochromic shift, and lifetime is increased three times as compared with the methyl analogue.     

A Multifunctional MnII Phosphonate for Rapid Separation of Methyl Orange and Electron‐Transfer Photochromism

A Mn^II phosphonate of the general formula [Mn(H₂L)₂(H₂O)₂(H₂bibp)] adopts a layered motif with protonated H₂bibp²⁺ cations embedded in the channels (H₄L=thiophene‐2‐phosphonic acid; bibp=4,4′‐bis(1‐imidazolyl)biphenyl). The title compound exhibits excellent adsorptive removal of methyl orange (MO) dye from aqueous solution. Its advantageous features include fast adsorption, high uptake capacity, selective removal, and reusability, which are of great significance for practical application in wastewater treatment. Meanwhile, the compound displays rapid photochromism upon irradiation with visible light at room temperature. Extensive research has demonstrated that such behavior is based on a ligand‐to‐ligand charge‐transfer (LLCT) mechanism. The irradiated sample possesses an ultra‐long‐lived charge‐separated state. Moreover, not only is the compound the first Mn‐based photochromic MOF, but it is also one of the very few examples showing LLCT with non‐photochromic components.     

Thermo‐ and Acid‐Responsive Photochromic Spironaphthoxazine‐Containing Organogelators

A series of photochromic spironaphthoxazine derivatives has been designed, synthesized, and characterized by using ¹H NMR spectroscopy, FAB mass spectrometry, and elemental analysis. Their photophysical and photochromic behavior have been investigated. Two of the compounds (G¹²‐en‐SA‐SO and G¹⁶‐en‐SA‐SO) have been shown to be capable of forming stable thermoreversible organogels in organic solvents, tested by the “stable‐to‐inversion of a test tube” method. Addition of p‐toluenesulfonic acid was found to induce the formation of stable organogels at concentrations below that of the critical gelation concentration (c.g.c.), with a concomitant change in color from colorless to purple. Transmission electron microscopy and scanning electron microscopy of the xerogels showed typical fibrous structures in the micrometer scale. The activation parameters for the bleaching reaction of G⁸‐en‐SA‐SO in the solution state and G¹⁶‐en‐SA‐SO in the gel state have been determined in ethanol through kinetic studies at various temperatures. The results showed that the rate of the bleaching reaction in the gel state was much slower than that in the solution state.     

Synthesis and structure of novel phosphonodipeptides containing a uracil or thymine group

A series of novel phosphonodipeptides containing a uracil or thymine group was synthesized in 54.2–74.1% yields by means of a peptide coupling reaction with DCC as the dehydrating agent and 1‐hydroxybezotriazole as the activating agent of the carboxyl group. All products were characterized by ¹H NMR, ³¹P NMR and IR spectra, and by elemental analyses. The crystal and molecular structure of compound 6c has been determined by X‐ray diffraction. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:422–427, 2000     

胆甾-4α-甲基-8-烯-3β，7α-二醇二乙酸酯的结构与性质研究

Lophenol, cholest-4α-methyl-7-en-3β-ol (1), obtained from Dracaena cochinchinensis (Lour.) S. C. Chen, was structurally modified. It was acetylated to protect 3β-hydroxyl group, and then oxidised by selenium dioxide in acetic acid to give cholest-4a-methyl-8-en-3β, Ta-diol diacetate (3). This compound 3 is unstable in chloroform solution or when heated and easily converted to a diene compound, cholest-4a-methyl-7,14-dien-3β-ol acetate (4). The structures of 3 and 4 were elucidated by means of IR, ^1H NMR, ^13C NMR and MS, and the absolute configuration of 3 was established by X-ray crystallography. The property of 3 was also discussed in this paper. Both 3 and 4 are new compounds and were reported for the first time.     

Structural and Solution Studies of two Mercury(II) Complexes with [1,3‐Bis(2‐ethoxy)benzene]triazene

The reaction of [1,3‐bis(2‐ethoxy)benzene]triazene, [ HL ], with Hg(SCN)₂ and Hg(CH₃COO)₂, resulted in the formation of the complexes [Hg L (SCN)] ( 1 ) and [Hg L ₂] · CH₃OH ( 2 ). They were characterized by means of X‐ray crystallography, CHN analysis, FT‐IR, ¹H NMR, and ¹³C NMR spectroscopy. The structure of compound 1 consists of two independent complexes in which the Hg^II atoms are stacked along the crystallographic a axis to form infinite chains. Each Hg^II atom is chelated by one L ligand and one SCN ligand, whereas in compound 2 , the Hg^II atom is surrounded by two L ligands. In addition, 1D chains formed by metal–π interactions are connected to each other by C–H ··· π stacking interactions in the structure of 1 , which results in a 2D architecture. An interesting feature of compound 2 is the presence of C–H ··· π edge‐to‐face interactions.     

Photochromic and molecular switching behaviour of Schiff base-containing pyrazolone ring

A new Schiff base compound, 4-[[(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)methylidene] amino]-1,5-dimethyl-2-phenyl-2,3-dihydro-1H-pyrazol-3-one (I), was synthesised and characterised by elemental analysis and LC-MS, FTIR and ¹H NMR spectra. The photochromic property of the synthesised compound investigated under 365 nm UV irradiation can be observed by solid state absorption and fluorescence spectra. The kinetic study showed that the photochromic reaction was of the pseudo-first-order. The photo-isomerisation was due to photo-induced intermolecular hydrogen bonding, which resulted in enol to keto transformation. The molecular switching behaviour was studied in solution with two inputs in three different systems (OH^? and Ag⁺), (OH^? and Cd²⁺) and (OH^? and Th⁴⁺) based on the UV absorption spectra. It exhibited the logic behaviour of XNOR, AND and NOR for Ag⁺,Cd²⁺ and Th⁴⁺ in alkaline media, respectively.