- A dual-mode visual detector for toxic hydrazine
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Hydrazine (N2H4) is one of the commonly used chemical reagents in numerous industries and applications but its toxicity to humans poses a need to develop simple visual detection methods. Herein, we demonstrate a novel dual-mode system to detect and simultaneously consume hydrazine in vapour and solution by using a small photoresponsive molecule that has altered optical response (both colourimetric and fluorescent) after reacting with hydrazine. This journal is
- Branda, Neil R.,Kaur, Brahmjot,Raza, Rameez
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- Synthesis of a ferrocene-functionalized unsymmetrical benzo[b]thienyl- thienylethene photoswitch with a cyclopentene core
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A new and potentially general synthetic route toward unsymmetrical benzo[b]thienyl-thienylethene compounds is described, with specific focus on conjugation of a ferrocene to the benzo[b]thiophene subunit. The route proceeds in an overall yield of 17%. Copyright
- Zuckerman, Nathaniel B.,Kang, Xiongwu,Chen, Shaowei,Konopelski, Joseph P.
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- Synthesis of a Five-Fold-Differentiated 1,3,5,7,9-Pentasubstituted Corannulene: A Maximal Labeling Problem in the Context of Corannulene
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This work defines a maximally labeled isomer problem in the context of 1,3,5,7,9-pentasubstituted corannulenes and explores two new synthetic strategies for the construction of key C-C bonds in the corannulene nucleus: a) a Diels-Alder cycloaddition of thiophene dioxide and acenaphthene fragments; b) a manganese-mediated reductive coupling of benzylic halides, which tolerates carboxy ester functionality. It advances the area of curved aromatics based on corannulene by setting a new family of targets for chemical synthesis and providing additional general synthetic tools.
- Maag, Roman,Siegel, Jay S.
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- Synthesis and characterization of 5,5′-bis-silylated dithienylethene as a new building block of novel photochromic periodic mesoporous organosilicas
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Pure bis-silylated dithienylethene (DTE) 3-(3,3,4,4,5,5-hexafluoro-2-(2-methyl-5-(triethoxysilyl)thiophen-3-yl)cyclopent-1-enyl)-2-methyl-5-(triethoxysilyl)thiophene was prepared from 3-(3,3,4,4,5,5-hexafluoro-2-(5-iodo-2-methylthiophen-3-yl)cyclopent-1-enyl)-5-iodo-2-methylthiophene by iodine–lithium exchange. The synthesis and purification method were optimized after many attempts of different coupling methods and purification techniques to ovoid the hydrolysis and self-condensation reaction and to obtain a pure product. The obtained bis-silylated dithienylethene (BS-DTE) is a versatile building block for potential applications, such as synthesis of new photochromic periodic mesoporous organosilica (PPMO). The structure of the obtained precursor was characterized by 1H, 13C and 29Si liquid NMR. Many attempts have been performed to prepare DTE-PMO but, the C–Si bond in the final material was fragile and could not resist to the hydrothermal treatment during the synthesis. The thermal stability of DTE-PMO will be studied in a future work.
- Abboud, Mohamed
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- In Situ Photoconversion of Multicolor Luminescence and Pure White Light Emission Based on Carbon Dot-Supported Supramolecular Assembly
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Constructing multicolor photoluminescence materials that allow for the integration of suitable external stimuli in order to control luminescence color conversions is a challenging objective. Multicolor luminescent output that is regulated in an in situ photo-controlled manner is not a common phenomenon. Herein, a photoluminescent supramolecular assembly, prepared in two stages, is described that displays in situ photo-tuning broad-spectrum output. Benefiting from the reversible photo-switched constitutional interconversion of diarylethenes, the fluorescence of a guest molecule, styrylpyridinium-modified diarylethene, can be switched on/off by alternating ultraviolet and visible light irradiation. Upon complexation of this guest with a host, cucurbit[8]uril, the fluorescence intensity of the resulting binary supramolecular nanofiber shows a drastic enhancement when compared with that of the free guest, which can also be quenched and recovered reversibly by light irradiation. Significantly, such cationic supramolecular nanofibers also interact with anionic carbon dots to form broad-spectrum output ternary supramolecular assemblies, the fluorescence of which can be changed efficiently from yellow to blue in an in situ photo-controlled manner. Pure white light emission can be realized expediently in the luminescence color-conversion process. The use of light as an external stimulus to regulate fluorescent color conversion provides us with an opportunity to design and construct more advanced anti-counterfeiting materials as well as visual display instruments.
- Wu, Huang,Chen, Yong,Dai, Xianyin,Li, Peiyu,Stoddart, J. Fraser,Liu, Yu
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- Photoswitchable organic nanoparticles and a polymer film employing multifunctional molecules with enhanced fluorescence emission and bistable photochromism
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Get turned on: Fluorescent photochromic organic nanoparticles (FPONs) of 1 (see picture) show a strongly enhanced fluorescence emission with increasing concentration and bistable photochromism. High-contrast on/off fluorescence switching has been successfully implemented in size-tuned FPONs of 1 and also in a photo-rewritable polymer film highly loaded with 1. (Chemical equation presented).
- Lim, Seon-Jeong,An, Byeong-Kwan,Sang, Don Jung,Chung, Myung-Ae,Soo, Young Park
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- Creating coordination-based cavities in a multiresponsive supramolecular gel
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Abstract Creating cavities in varying levels, from molecular containers to macroscopic materials of porosity, have long been motivated for biomimetic or practical applications. Herein, we report an assembly approach to multiresponsive supramolecular gels by integrating photochromic metal-organic cages as predefined building units into the supramolecular gel skeleton, providing a new approach to create cavities in gels. Formation of discrete O-Pd2L4 cages is driven by coordination between Pd2+ and a photochromic dithienylethene bispyridine ligand (O-PyFDTE). In the presence of suitable solvents (DMSO or MeCN/DMSO), the O-Pd2L4 cage molecules aggregate to form nanoparticles, which are further interconnected through supramolecular interactions to form a three-dimensional (3D) gel matrix to trap a large amount of solvent molecules. Light-induced phase and structural transformations readily occur owing to the reversible photochromic open-ring/closed-ring isomeric conversion of the cage units upon UV/visible light radiation. Furthermore, such Pd2L4 cage-based gels show multiple reversible gel-solution transitions when thermal-, photo-, or mechanical stimuli are applied. Such supramolecular gels consisting of porous molecules may be developed as a new type of porous materials with different features from porous solids. Metal-organic cages were utilized as building units for the first time to generate supramolecular gels, providing a synthetic approach to cavity-containing gels that display multi-responsiveness towards environmental physical and chemical stimuli (see figure).
- Wei, Shi-Chao,Pan, Mei,Fan, Yuan-Zhong,Liu, Haoliang,Zhang, Jianyong,Su, Cheng-Yong
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- Switchable Mesomeric Betaines Derived from Pyridinium-Phenolates and Bis(thienyl)ethane
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Syntheses of push–pull substituted non-symmetric bis(thienyl)ethenes (BTEs) possessing a central perfluorocyclopentene core are described. The substituent effects of anisole, phenole, and phenolate as well as pyridine, pyridinium, and N-methylpyridinium substituents, joined through their 3- or 4-positions to the central BTE core, respectively, cover the range from very strongly electron-donating [σ(4-phenolate)=?1.00] to extremely strongly electron-withdrawing [σ(pyridinium-4-yl)=+2.57] in the title mesomeric betaines. The different isomers possessing 4-yl/4-yl, 4-yl/3-yl and 3-yl/3-yl substituents represent different combinations of conjugated and cross-conjugated partial structures and cause different spectroscopic properties. In addition, through-space conjugation between the 2- and 2′-position of the thiophenes can be observed which circumvents the charge-separation of through-bond cross-conjugation. The BTE possessing the push–pull chromophore consisting of 3-anisole and 4-pyridinium substituents (24) displays the best extinction coefficients within the series of compounds described here (?=33.8/15.7 L/mol ? cm), while the mesomeric betaine possessing an N-methylpyridinium-4-yl and a 4-phenolate substituent (29) displays considerable bathochromic shifts to λmax=724 nm in its closed form.
- Adams, J?rg,Dahle, Sebastian,Hübner, Eike G.,Lederle, Felix,Maus-Friedrichs, Wolfgang,Nagorny, Sven,Schmidt, Andreas,Udachin, Viktor,Weingartz, Thea
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p. 3178 - 3189
(2021/07/02)
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- The mechanodonor-acceptor coupling (MDAC) approach for unidirectional multi-state fluorochromism
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Uni-directional multi-state fluorochromic scaffolds are valuable photofunctional molecules and yet scarce. We report a general approach for their design, i.e., mechanodonor-acceptor coupling (MDAC). A photochromic molecule is a mechanodonor, due to its capability to convert photonic energy into mechanical force. Upon proper coupling, it can be used to drive a mechanochromic molecule for uni-directional multi-state fluorochromism. The embodiment of this approach is a rhodamine-dithienylethylene hydride (RDH), which has been successfully employed in super-resolution localization microscopy[Figure not available: see fulltext.]
- Gu, Luyan,Zhang, Lujia,Luo, Xiao,Zheng, Ying,Ye, Zhiwei,Lv, Meng,Chen, Jinquan,Chen, Chunlai,Xiao, Yi,Zhu, Weihong,Qian, Xuhong,Yang, Youjun
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p. 253 - 262
(2021/01/06)
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- Development of High-Performance Pyrimidine Nucleoside and Oligonucleotide Diarylethene Photoswitches
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Nucleosidic and oligonucleotidic diarylethenes (DAEs) are an emerging class of photochromes with high application potential. However, their further development is hampered by the poor understanding of how the chemical structure modulates the photochromic properties. Here we synthesized 26 systematically varied deoxyuridine- and deoxycytidine-derived DAEs and analyzed reaction quantum yields, composition of the photostationary states, thermal and photochemical stability, and reversibility. This analysis identified two high-performance photoswitches with near-quantitative, fully reversible back-and-forth switching and no detectable thermal or photochemical deterioration. When incorporated into an oligonucleotide with the sequence of a promotor, the nucleotides maintained their photochromism and allowed the modulation of the transcription activity of T7 RNA polymerase with an up to 2.4-fold turn-off factor, demonstrating the potential for optochemical control of biological processes.
- Kolmar, Theresa,Büllmann, Simon M.,Sarter, Christopher,H?fer, Katharina,J?schke, Andres
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supporting information
p. 8164 - 8173
(2021/03/08)
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- Development of Red-Shifted and Fluorogenic Nucleoside and Oligonucleotide Diarylethene Photoswitches
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The reversible modulation of fluorescence signals by light is of high interest for applications in super-resolution microscopy, especially on the DNA level. In this article we describe the systematic variation of the core structure in nucleoside-based diarylethenes (DAEs), in order to generate intrinsically fluorescent photochromes. The introduction of aromatic bridging units resulted in a bathochromic shift of the visible absorption maximum of the closed-ring form, but caused reduced thermal stability and switching efficiency. The replacement of the thiophene aryl unit by thiazol improved the thermal stability, whereas the introduction of a benzothiophene unit led to inherent and modulatable turn-off fluorescence. This feature was further optimized by introducing a fluorescent indole nucleobase into the DAE core, resulting in an effective photoswitch with a fluorescence quantum yield of 0.0166 and a fluorescence turn-off factor of 3.2. The site-specific incorporation into an oligonucleotide resulted in fluorescence-switchable DNA with high cyclization quantum yields and switching efficiency, which may facilitate future applications.
- Kolmar, Theresa,Becker, Antonia,Pfretzschner, Ronja A.,Lelke, Alina,J?schke, Andres
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supporting information
p. 17386 - 17394
(2021/10/20)
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- Light-Triggered Metal Coordination Dynamics in Photoswitchable Dithienylethene-Ferrocene System
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The C2-symmetric photochromic molecule 3, containing dithienylethene (DTE) and ferrocene units connected by an alkyne bridge, represents a unique probe where a metal (Hg2+) binds with the central DTE moiety. Both photoisomerized states of 3 (open, 3o; closed, 3c) are found to interact with Hg2+ ion by the S atoms of the DTE core; however, the binding constants (from a UV-vis study) and DFT calculations suggest that the open isomer (3o) binds with the metal ion more strongly than that of the closed isomer (3c). Notably, the course of metal binding does not perturb the inherent photoisomerization properties of the DTE core and the photoswitchability persists even in the metal-coordinated form of 3, however, with a comparatively slower rate. The quantum yields for photocyclization (φo→c) and photocycloreversion (φc→o) in the free form are 0.56 and 0.007, respectively, whereas the photocyclization quantum yield in the Hg2+ complexed species is 0.068, 8.2 times lower than the photocyclization quantum yield (φo→c) of free 3o. Thus, the rate of photoisomerization can be modulated by a suitable metal coordination to the DTE core. The dynamics of photoswitchability in the metal-coordinated form of DTE has been explored by experimental means (UV-vis and electrochemical studies) as well as quantum chemical calculations.
- Adarsh, Nayarassery N.,Karmakar, Manisha,Mondal, Bijan,Pal, Adwitiya,Thakur, Arunabha
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p. 6086 - 6098
(2021/05/06)
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- Carborane photochromism: a fatigue resistant carborane switch
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A dithienylethene molecule involving carborane clusters shows remarkable fatigue resistance and high contrast visual colour changes when irradiated with alternating ultraviolet and visible light. The fluorescence of this assembly can be switched on and off when irradiated in the solid state but not in the solution state.
- Aldred, Matthew P.,Chen, Ying,Fox, Mark A.,Harder, Rachel A.,Li, Chong,Yufit, Dmitry S.,Zhu, Ming-Qiang
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supporting information
p. 9466 - 9469
(2021/09/22)
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- Mechanistic Insights into the Triplet Sensitized Photochromism of Diarylethenes
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Operating photoswitchable molecules repetitively and reliably is crucial for most of their applications, in particular in (opto)electronic devices, and related to reversibility and fatigue resistance, which both critically depend on the photoisomerization mechanism defined by the substitution pattern. Two diarylethene photoswitches bearing biacetyl triplet sensitizers either at the periphery or at the core were investigated using both stationary as well as transient UV/Vis absorption spectroscopy ranging from the femtosecond to the microsecond time scale. The diarylethene with two biacetyl moieties at the periphery is switching predominantly from the triplet excited state, giving rise to an enhanced fatigue resistance. In contrast, the diarylethene bearing one diketone at the photoreactive inner carbon atom cyclizes from the singlet excited state and shows significantly higher quantum yields for both cyclization and cycloreversion.
- Fredrich, Sebastian,Morack, Tobias,Sliwa, Michel,Hecht, Stefan
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supporting information
p. 7672 - 7677
(2020/06/01)
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- Norbornadiene-bridged diarylethenes and their conversion into turn-off fluorescent photoswitches
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We describe the synthesis and characterization of novel diarylethene photoswitches that contain a norbornadiene bridge and operate as p-type positive photochromes. One of the double bonds of norbornadiene is furthermore utilized to attach a fluoresceine tetrazine by an iEDDA cascade reaction, thereby forming a turn-off mode fluorescent photoswitch. This journal is
- Büllmann, Simon M.,J?schke, Andres
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supporting information
p. 7124 - 7127
(2020/07/14)
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- Light-driven coordination anions-directed regulation of chromism in three metal complexes assembled by cyano-equipped dithienylethene ligand
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Three coordination compounds were self-assembled successfully with Ag(I) ions and photo-responsive ligands featuring a cyano-equipped dithienylethene unit. Anions with different coordinating abilities were selected to construct distinct topologies, which are evidenced by X-ray crystallographic analysis. CF3 COO? and CF3 SO3? are involved into coordination in 1 and 3, respectively, whereas in 2 BF4? present merel y as ionic guests counterbalancing the framework charge. Anions also show their subtle effects on coordinated atoms, interactions, and ligand configurations. The quite different structures of 1–3 indicate an interesting anion-directed structural self-assembly. Followed examinations on photochromism illustrated that the reversible photo-isomerizations of three complexes are all retained after complexzation with Ag(I) center. Various degrees of bathochromic shifts in absorptions were observed as compared with that of the metal-free ligand. Therefore, the photo-switching of these compounds could be modulated conveniently and finely by varying simply the coordination anions and then triggering by light irradiation. The discussions of structure-properties relationship concluded that anions exert their effects on coordination structure through adjusting the configurations of ligands in complexes. Strong coordinating anions facilitate a pronounced conformational change of ligand whereas un-coordinating anion leads to smaller variation. The distinct structural changes of ligand result finally the different perturbation of photochromic behavior.
- Han, Jia-cai,Han, Jing,Li, Qing,Liu, Xiang,Quan, Chun-yan,Yu, Zhong
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- Photochromic dithienylethenes characterized by: In situ irradiation NMR-spectroscopy and electrochemically induced responsiveness on gold substrates
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Photochromic compounds comprising small molecules and polymers have been shown to be of great interest in the field of stimuli-responsive materials for applications as sensors and (nano-) devices. In this regard dithienylethenes (DTEs) have been proven to be especially valuable because of their tolerance to chemicals and their good stability making them tunable and reversibly switchable between an open and a closed structure featuring different optical properties. By utilizing a potent in situ irradiation NMR spectroscopy approach, it is possible to determine the photochromic switching capability of two DTE derivatives in solution leading to crucial information about the structures, the equilibria of the chemical ring-opening and closing of the DTEs as well as the longtime stability of these molecular switches. In particular the perfluorinated thioether bearing compound shows remarkable stability with little fatigue related to the irreversibly cyclized byproduct known for DTEs. The thioether-bearing DTEs can be deprotected and used for immobilization on gold substrates which are characterized by water contact angle measurements prior to and after DTE functionalization. Finally, the electrochemically induced switching capability of the perhydro DTE is investigated by cyclic voltammetry proving its fast, quantitative and reversible cyclization. We envisage these materials for applications as sensors and optical switching devices.
- Von Irmer, Jonas,Frie?, Florian,Herold, Dominik,Kind, Jonas,Thiele, Christina M.,Gallei, Markus
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supporting information
p. 14088 - 14097
(2019/12/02)
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- Symmetric 9,10-bisthienylanthracene compound, and preparation method and application thereof
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The invention especially relates to a symmetric 9,10-bisthienylanthracene compound, belonging to the technical field of aggregation-induced luminescent materials. According to the invention, a styrylgroup in a traditional anthracene compound is substituted by a thiofuran biphenyl group so as to obtain the symmetric 9,10-bisthienylanthracene compound with a simple molecular structure and obvious AIE properties. The molecular end of the compound is easily modified by changing different groups so as to regulate the luminescent properties of the compound. The symmetric 9,10-bisthienylanthracene compound of the invention can be obtained by a simple Suzuki coupling reaction; raw materials used in the invention are low in cost, and the compound is simple to synthesize and favorable for industrial production and has great application prospects. The compounds BMPTA, BPTA and BCPTA can be used as fluorescent markers for HeLa cells and have potential application value in the field of cell dyes;and the compounds BMPTA and BPTA have obvious mechanical discoloration characteristics, and can be used for preparing mechanical force-regulated illuminating elements and the like.
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Paragraph 0076; 0077
(2019/10/01)
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- Sensitive Assays by Nucleophile-Induced Rearrangement of Photoactivated Diarylethenes
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Upon light-induced isomerization, diarylethenes (DAEs) equipped with reactive aldehyde moieties rearrange selectively in the presence of amines, accompanied by decoloration. In a comprehensive study, the probe structure was optimized with regard to its inherent reactivity in the nucleophile-triggered rearrangement reaction. Detailed structure-reactivity relationships could be derived, in particular with regard to the type of integrated (het)aryl moieties as well as the location of the formyl residue, and the probes' intrinsic reactivity with primary and secondary amines was optimized. Utilizing an ancillary base, the initially formed rearrangement product can engage in a subsequent catalytic cycle, leading to an amplified decoloration process. This additional catalytic pathway allows us to enhance the sensitivity of our method and successfully discriminate between amines and thiols. Moreover, probes that exhibit strong analyte-induced fluorescence modulation have been designed to further decrease the detection limit by using a more sensitive read-out. The optimized DAE probes are promising molecular components for future programmable sensing materials and devices.
- Fredrich, Sebastian,Bonasera, Aurelio,Valderrey, Virginia,Hecht, Stefan
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supporting information
p. 6432 - 6440
(2018/05/31)
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- Guest-Induced Structural Transformations in a Porous Halogen-Bonded Framework
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Structural evidence obtained from in situ X-ray diffraction shows that halogen bonding is responsible for the formation of a dynamic porous molecular solid. This material is surprisingly robust and undergoes reversible switching of its pore volume by activation or by exposure to a series of gases of different sizes and shapes. Volumetric gas sorption and pressure-gradient differential scanning calorimetry (P-DSC) data provide further mechanistic insight into the breathing behavior.
- Nikolayenko, Varvara I.,Castell, Dominic C.,van Heerden, Dewald P.,Barbour, Leonard J.
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supporting information
p. 12086 - 12091
(2018/09/11)
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- Mild-Base-Promoted Arylation of (Hetero)Arenes with Anilines
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Transition metal-free radical arylation of heteroarenes is achieved at room temperature by simply adding aqueous sodium carbonate to a solution of the corresponding heteroarene and arenediazonium salt, which can even be formed in situ. Such an easy, inexpensive and mild methodology has been optimized and applied to the expeditious modification of interesting molecular cores like naphthylimide or bisthienylcyclopentenes.
- Monzón, Diego M.,Santos, Tanausú,Pinacho-Crisóstomo,Martín, Víctor S.,Carrillo, Romen
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p. 325 - 333
(2018/01/15)
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- Light-Activated Sensitive Probes for Amine Detection
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Our new, simple, and accurate colorimetric method is based on diarylethenes (DAEs) for the rapid detection of a wide range of primary and secondary amines. The probes consist of aldehyde- or ketone-substituted diarylethenes, which undergo an amine-induced decoloration reaction, selectively to give the ring-closed isomer. Thus, these probes can be activated at the desired moment by light irradiation, with a sensitivity that allows the detection of amines at concentrations as low as 10?6m in solution. In addition, the practical immobilization of DAEs on paper makes it possible to detect biogenic amines, such as cadaverine, in the gas phase above a threshold of 12 ppbv within 30 seconds.
- Valderrey, Virginia,Bonasera, Aurelio,Fredrich, Sebastian,Hecht, Stefan
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supporting information
p. 1914 - 1918
(2017/02/05)
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- Comprising benzimidazole group of asymmetric perfluoro pentene photochromic fluorescent probe compound and its preparation method and application
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The invention discloses an asymmetric perfluorocyclopentene photochromic fluorescent probe compound containing a benzimidazole group as well as a preparation method and an application of the asymmetric perfluorocyclopentene photochromic fluorescent probe compound. The photochromic material can keep good photochromic performance in a solution and a crystalline phase, has excellent performance such as good chemical and thermal stability, remarkable fatigue resistance, relatively high cyclizing quantum yield, relatively strong fluorescence property and very good sensitivity in an open loop state and a closed loop state in the solution, can be used for high-density holographic optical storage with storage attribute comparable with that of rewritable photon type storage and an symmetric type perfluorocyclopentene material, is relatively low in cost in preparation material and relatively great in application prospect.
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Paragraph 0024; 0033; 0034; 0035
(2017/08/25)
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- Imidazole - the thiophen is fragrant heterocyclic ultra-short wavelength photochromic diaryl ethylene compound synthetic methods and application
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The invention discloses a method for synthesizing an ultrashort-wavelength photochromic diarylethene compound by using imidazole-thiophene aromatic heterocycle and an application of the compound. A photochromic material can maintain good photochromic performance in a solution or film, has weaker fluorescence when the open-loop state ranges from 265 nm to 276 nm, has high fluorescence when the closed-loop state ranges from 400 nm to 550 nm, can be applied to a fluorescent photoswitch, an anti-forgery technology, a short-wavelength high-density holographic optical storage material and the like, and compared with the symmetrical thiophene or benzothiophene octafluorocyclopentene material, the material preparing cost is lower, and the application prospect is broader.
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Paragraph 0060; 0062; 0063; 0064
(2017/07/31)
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- Asymmetric octafluorocyclopentene compound with continuous selectivity for Hg2+ and Cys, preparation method and application thereof
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The invention discloses [1-[2-methyl-3-benzothiophene], 2-(2-methyl-5-(4-phenyl)-(2-benzoylquinoline-8-benzothiazolyl)-3-thienyl)] octafluorocyclopentene, a preparation method and an application thereof. The preparation method comprises the following steps: by taking benzothiophene as a raw material, replacing by methyl iodide and bromizing and then reacting with octafluorocyclopentene, thereby generating mono-substituted octafluorocyclopentene; by taking 2-thiotolene as a raw material, bromizing and causing n-butyllithium to react with tributyl borate; connecting aldehyde-terminated benzene with thiophene ring through Stuzki coupling; protecting by adopting ethylene glycol and then reacting with the mono-substituted octafluorocyclopentene; reducing into alcoholic hydroxyl group and becoming methylene-containing bromine; reacting with 8-hydroxyquinoline-2-aldehyde group; and finally reacting with 2-amino thiophenol, thereby acquiring a target compound. The compound prepared according to the invention can be used for continuously detecting specific ions and amino acid and has an excellent selectivity.
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Paragraph 0016; 0034; 0040
(2017/07/20)
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- Photochromic indazole - thiophene mixed linkage type dithienylethene compound and its synthetic method and application
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The present invention belongs to the field of chemical synthesis, and discloses a photochromic indazole-thiophene hybrid type perfluorinated cyclopentene compound and preparation method thereof. The photochromic indazole-thiophene hybrid type perfluorinated cyclopentene compound can be mainly used in doping with a polymer material, preparation into a diaphragm, ultra-high density, rewritable organic photon information storage material, the preparation of optical switch element, and the preparation of photochromic light emitting devices.
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Paragraph 0030; 0032; 0033; 0034
(2017/08/26)
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- Bistable Solid-State Fluorescence Switching in Photoluminescent, Infinite Coordination Polymers
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Photo-functional infinite coordinated polymers (ICPs) were synthesized that consist of the photochromic dithienylethene (DTE) and a luminescent bridging unit to give enhanced fluorescence in the solid state. We could fabricate well-ordered micropatterns of these ICPs by a soft-lithographic method, which repeatedly showed high contrast on–off fluorescence switching.
- Kim, Jincheol,You, Youngmin,Yoon, Seong-Jun,Kim, Jong H.,Kang, Boseok,Park, Sang Kyu,Whang, Dong Ryeol,Seo, Jangwon,Cho, Kilwon,Park, Soo Young
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supporting information
p. 10017 - 10022
(2017/08/01)
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- Photochromic coenzyme Q derivatives: Switching redox potentials with light
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Coenzyme Q is an important redox cofactor involved in a variety of cellular processes, and is thus found in several cell compartments. We report a photochromic derivative of coenzyme Q that combines the molecular structures of the redox active cofactor and a photochromic dye. Light irradiation triggers an electronic rearrangement reversibly changing the redox potential. We used this effect to control the intermolecular redox reaction of the photochromic coenzyme Q derivative with dihydropyridine in solution by light irradiation. On mitochondria, the altered redox properties showed an effect on the respiratory chain. The experiments demonstrate that the redox reactions can be initiated inside the system of interest through irradiation with light and the accompanied photoisomerization.
- Simeth, Nadja A.,Kneuttinger, Andrea C.,Sterner, Reinhard,K?nig, Burkhard
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p. 6474 - 6483
(2017/08/29)
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- PHOTOCHROMIC COMPOUND, DOUBLE FLUORESCENT MATERIAL, TEMPERATURE SENSOR, AND TEMPERATURE PROBE MATERIAL
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PROBLEM TO BE SOLVED: To provide a photochromic compound that emits light in both isomers of a ring-opening body and a ring-closed body, has double fluorescence properties, and has temperature responsiveness, and provide an application material comprising the compound. SOLUTION: The present invention provides a photochromic compound represented by a compound of formula (2), and an application material comprising the compound [A is trifluoromethyl, cyano or nitro; B is dimethylamino, diphenylamino or carbazole; X and Y independently represent a heteroaromatic ring; Z1-6 independently represent H, halogen, alkyl]. SELECTED DRAWING: Figure 3 COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0044
(2017/10/31)
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- Reversible Photomodulation of Electronic Communication in a π-Conjugated Photoswitch-Fluorophore Molecular Dyad
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The extent of electronic coupling between a boron dipyrromethene (BODIPY) fluorophore and a diarylethene (DAE) photoswitch has been modulated in a covalently linked molecular dyad by irradiation with either UV or visible light. In the open isomer, both moieties can be regarded as individual chromophores, while in the closed form the lowest electronic (S0→S1) transition of the dyad is slightly shifted, enabling photomodulation of its fluorescence. Transient spectroscopy confirms that the dyad behaves dramatically different in the two switching states: while in the open isomer it resembles an undisturbed BODIPY fluorophore, in the closed isomer no fluorescence occurs and instead a red-shifted DAE behavior prevails.
- Moreno, Javier,Schweigh?fer, Felix,Wachtveitl, Josef,Hecht, Stefan
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supporting information
p. 1070 - 1075
(2016/01/16)
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- The role of alkyl substituents in deazaadenine-based diarylethene photoswitches
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Diarylethenes are an important class of reversible photoswitches and often claimed to require two alkyl substituents at the carbon atoms between which the bond is formed or broken in the electrocyclic rearrangement. Here we probe this claim by the synthesis and characterization of four pairs of deazaadenine-based diarylethene photoswitches with either one or two methyl groups at these positions. Depending on the substitution pattern, diarylethenes with one alkyl group can exhibit significant photochromism, but they generally show poor stability towards extended UV irradiation, low thermal stability, and decreased fatigue resistance. The results obtained provide an important direction for the design of new efficient DNA photoswitches for the application in bionanotechnology and synthetic biology.
- Sarter, Christopher,Heimes, Michael,J?schke, Andres
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supporting information
p. 1103 - 1110
(2016/07/06)
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- Light-Switchable Polymers of Intrinsic Microporosity
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The interest in (micro)porous systems is greater than ever before with microporous polymers finding application in areas such as gas storage/separation and catalysis. In contrast to the vast majority of publications on microporous polymers seeking ever higher values for surface area or uptake capacity for a particular gas, this work presents a means to render a microporous system responsive to electromagnetic stimuli. The incorporation of a diarylethene (DAE) derivative in the backbone of a polymer of intrinsic microporosity (PIM) produces a microporous system that exhibits photochromism as proven by UV-vis absorption and NMR studies. In the resulting DAE-PIM, surface area is not a fixed unalterable property but can be influenced by the external and nondestructive stimulus light in a reversible manner. Furthermore, in combination with Matrimid, free-standing membranes can be produced that display light-switchable diffusivity and permeability for carbon dioxide and oxygen. In this way, material scientists are offered the potential to employ only one system that can assume several states with different properties for each.
- Becker, Daniel,Konnertz, Nora,B?hning, Martin,Schmidt, Johannes,Thomas, Arne
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p. 8523 - 8529
(2016/12/23)
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- PHOTOCHROMIC COMPOUND, AND REWRITABLE OPTICAL RECORDING MOLECULAR MATERIAL, FLUORESCENCE LABEL MATERIAL, AND SECURITY INK PREPARED THEREWITH
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PROBLEM TO BE SOLVED: To provide a photochromic molecule showing light emission in both isomers of a ring-opened body and a ring-closed body. SOLUTION: A photochromic compound comprises a photochromism unit having a hexatriene skeleton, and a fluorescence emission unit bound to carbon at a ring-forming position of the hexatriene skeleton of the photochromism unit. SELECTED DRAWING: Figure 3 COPYRIGHT: (C)2016,JPO&INPIT
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Paragraph 0061
(2016/12/01)
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- Photon-Quantitative 6π-Electrocyclization of a Diarylbenzo[b]thiophene in Polar Medium
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The high reactivity of 6π-electrocyclization in polar solvents has remained one of the important challenges for diarylethenes because of the emergence of a twisted intramolecular charge transfer (TICT) state at the excited state in such polar media, which usually quenches the photocyclization reaction. Herein we report on the preparation and highly efficient photocyclization of 2,3-diarylbenzo[b]thiophenes with nonsymmetric side-aryl units in a polar solvent. While the dithiazolylbenzo[b]thiophene showed a suppressed quantum yield of 6π-electrocyclization of 54% in methanol, the replacement of a thiazole unit with a thiophene ring led to a photon-quantitative 6π-cyclization reaction. The nonsymmetrical modification into the side-aryl units was considered to enhance the CH/π interactions between side-aryl units to support a photoreactive conformation in methanol. The stabilization of the photochromic reactive conformation is expected to suppress the formation of the TICT state at the excited state, leading to highly efficient photoreactivity.
- Li, Ruiji,Nakashima, Takuya,Galangau, Olivier,Iijima, Shunsuke,Kanazawa, Rui,Kawai, Tsuyoshi
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supporting information
p. 1725 - 1730
(2015/08/06)
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- Synthesis and photochromic properties of a bis(diarylethene)-naphthopyran hybrid
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The synthesis and photochromic properties of a triphotochromic molecule consisting of one naphthopyran flanked by two diarylethene units investigated by UV-Visible and Nuclear Magnetic Resonance spectroscopies are reported. Six different states resulting from the open/closed naphthopyran associated with one or two open/cyclized diarylethenes have been characterized. The photochemical and thermal interconversion between the six states of the triphotochromic target was followed allowing to determine the existing pathways upon irradiation with 313 and 365 nm light excitation, and during thermal evolution. Switching of the naphthopyran group is possible, independently of the state of the diarylethene groups. However, the diarylethene groups cannot be closed if the naphthopyran group is open.
- Erko, Firealem G.,Cseh, Liliana,Berthet, Jér?me,Mehl, Georg H.,Delbaere, Stéphanie
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p. 102 - 109
(2015/03/05)
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- ROBUST PHOTOCHROMIC COMPOUNDS WITH SILICON- OR PHOSPHORUS-CONTAINING HETEROCYCLIC RING AND PRODUCTION THEREOF
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In one embodiment, provided are a new class of diarylethene-containing photochromic compounds with the incorporation of silicon-or phosphorus-containing heterocycles into the "ethene" part of the diarylethene backbone that has been shown to be capable of displaying tunable, robust and thermally stable photochromic properties. Also provided are methods for synthesizing these compounds, as well as uses of these compounds as these compounds may be used as the photochromic layer in an optical recording material and other optical functioning devices.
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Page/Page column 26
(2016/01/01)
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- Photoswitching of the triplet excited state of diiodobodipy-dithienylethene triads and application in photo-controllable triplet-triplet annihilation upconversion
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Dithienylethene (DTE)-2,6-diiodoBodipy triads were prepared with the aim to photoswitch the triplet excited state of the 2,6-diiodoBodipy moiety. Bodipy was selected due to its low T1 state energy level to avoid sensitized photocyclization of DTE, which is very often encountered in DTE photoswitches, so that the photochemistry of DTE and the organic chromophore can be addressed independently. This is the first time that DTE was covalently connected with an organic triplet photosensitizer. For the triad with DTE-o structure, selective photoexcitation into the diiodoBodipy part did not initiate photocyclization of DTE-o. Upon photoirradiation at 254 nm, thus the DTE-o → DTE-c transformation, the intersystem crossing (ISC) of 2,6-diiodoBodipy moiety was competed by the photoactivated resonance energy transfer (RET), with Bodipy as the intramolecular energy donor and DTE-c as energy acceptor. The fluorescence of Bodipy was quenched and the triplet state lifetime of Bodipy was reduced from 105.1 to 40.9 μs. The photoreversion is O2-independent, but can be greatly accelerated upon selective photoexcitation into the diiodoBodipy absorption band (at 535 nm). We concluded that ISC is not outcompeted by RET. The photoswitching of the triplet state was transduced to the singlet oxygen photosensitizing, as well as triplet-triplet annihilation upconversion.
- Ma, Jie,Cui, Xiaoneng,Wang, Fen,Wu, Xueyan,Zhao, Jianzhang,Li, Xingwei
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p. 10855 - 10866
(2015/01/08)
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- Photocontrolled intramolecular charge/energy transfer and fluorescence switching of tetraphenylethene-dithienylethene-perylenemonoimide triad with donor-bridge-acceptor structure
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Photochromic 1,2-dithienylethene (DTE) derivatives with a high thermal stability and fatigue resistance are appealing for optical switching of fluorescence. Here, we introduce a donor-photochromic bridge-acceptor tetraphenylethene-dithienylethene-perylenemonoimide (TPE-DTE-PMI) triad, in which TPE acts as the electron donor, PMI as the electron acceptor, and DTE as the photochromic bridge. In this system, the localized and intramolecular charge transfer emission of TPE-DTE-PMI with various Stokes shifts have been observed due to the photoinduced intramolecular charge transfer in different solvents. Upon UV irradiation, the fluorescence quenching resulting from photochromic fluorescence resonance energy transfer in TPE-DTE-PMI has been demonstrated in solution and in solid films. The fluorescence on/off switching ratio in polymethylacrylate film exceeds 100, a value much higher than in polymethylmethacrylate film, thus indicating that the fluorescence switching is dependent on matrices.
- Li, Chong,Yan, Hui,Zhang, Guo-Feng,Gong, Wen-Liang,Chen, Tao,Hu, Rui,Aldred, Matthew P.,Zhu, Ming-Qiang
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supporting information
p. 104 - 109
(2014/01/06)
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- Nonsymmetrical 3,4-dithienylmaleimides by cross-coupling reactions with indium organometallics: Synthesis and photochemical studies
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The synthesis and photochemical study of novel nonsymmetrical 1,2-dithienylethenes (DTEs) with a maleimide bridge have been carried out. The synthetic approach to the DTEs was based on successive selective palladium-catalyzed cross-coupling reactions of 5-susbtituted-2-methyl-3-thiophenyl indium reagents with 3,4-dichloromaleimides. The required organoindium reagents were prepared from 2-methyl-3,5-dibromothiophene by a selective (C-5) coupling reaction with triorganoindium compounds (R3In) and subsequent metal-halogen exchange. The coupling reactions usually gave good yields and have a high atom economy with substoichiometric amounts of R3In. The results of photochemical studies show that these novel dithienylmaleimides undergo a photocyclization reaction upon irradiation in the UV region and a photocycloreversion after excitation in the visible region, thus they can be used as photochemical switches. ON-OFF operations can be repeated in successive cycles without appreciable loss of effectiveness in the process.
- Mosquera, ngeles,Frnandez, M. Isabel,Lopez, Moiss Canle,Sestelo, Jos Prez,Sarandeses, Luis A.
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supporting information
p. 14524 - 14530
(2015/01/09)
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- PHOTOCHROMIC MATERIAL
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Photochromic dyes are disclosed. A photochromic dye can include a first photo-reactive group and a second photo-reactive group. A first photochromic reaction can be induced in the first photo-reactive group of the photochromic dye by radiation having a first wavelength, and a second photochromic reaction can be induced in the second photo-reactive group of the photochromic dye by radiation having a second wavelength.
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Paragraph 0126
(2014/07/22)
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- Enhanced photochemical sensitivity in photochromic diarylethenes based on a benzothiophene/thiophene nonsymmetrical structure
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Photosensitivity of molecules is one of the central subjects of organic photochemistry. In this article, we present how and why a benzothiophene moiety impacts the photochromic quantum yield for the photochemical pericyclic ring closing of the hexatriene moiety. Two compounds were prepared: a symmetrical one incorporating two fluorenylthiophene units, and its corresponding nonsymmetrical partner, where one of the thiophene units was replaced by a benzothiophene group. Interestingly, the latter presents relatively high cyclization quantum yield (0.74), a value close to the largest one so far reported. Based on crystal structures, VT-NMR data and DFT calculations, we demonstrate that introducing a benzothiophene in the molecular scaffold induces skeleton stiffening by means of CH-π interactions and steric repulsions, and leads to increased population of the reactive conformer in the ambient conditions.
- Galangau, Olivier,Kimura, Yuka,Kanazawa, Rui,Nakashima, Takuya,Kawai, Tsuyoshi
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supporting information
p. 7165 - 7173
(2015/01/09)
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- Conductance switching and mechanisms in single-molecule junctions
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A molecular switch: The conductance of a new molecular device based on graphene-molecule junctions was reproducibly switched between open and closed states under irradiation of external light (see picture). Three photochromic diarylethene derivatives with different substituents were used as key elements of the molecular devices. Copyright
- Jia, Chuancheng,Wang, Jinying,Yao, Changjiang,Cao, Yang,Zhong, Yuwu,Liu, Zhirong,Liu, Zhongfan,Guo, Xuefeng
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supporting information
p. 8666 - 8670
(2013/09/12)
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- Photoreversible supramolecular polymerisation and hierarchical organization of hydrogen-bonded supramolecular Co-polymers composed of diarylethenes and oligothiophenes
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Diarylethene 1 equipped with two monotopic melamine hydrogen-bonding sites and oligothiophene-functionalized ditopic cyanurate (OTCA) were mixed in a nonpolar solvent to form AA-BB-type supramolecular co-polymers (SCPs) bearing photoswitchable moieties in their main chains and extended π systems as side chains. UV/Vis, fluorescence, dynamic light scattering (DLS), TEM, and AFM studies revealed that the two functional co-monomers formed flexible quasi-one-dimensional SCPs in solution that hierarchically self-organized into helical nanofibers through H-aggregation of the oligothiophene side chains. Upon irradiating the SCPs with UV light, a transition occurred from the H-aggregated state to non-aggregated monomeric oligothiophene side chains, as shown by spectroscopic studies, which indicates the formation of small oligomeric species held together only by hydrogen-bonding interactions. TEM and AFM visualized unfolded fibrils corresponding to elongated single SCP chains formed upon removal of solvent. The helical nanofibers were regenerated upon irradiating the UVirradiated solution with visible light. These results demonstrated that the supramolecular polymerisation followed by hierarchical organization can be effectively controlled by proper supramolecular designs using diarylethenes and π-conjugated oligomers. Copyright
- Yagai, Shiki,Ohta, Keisuke,Gushiken, Marina,Iwai, Kazunori,Asano, Atsushi,Seki, Shu,Kikkawa, Yoshihiro,Morimoto, Masakazu,Kitamura, Akihide,Karatsu, Takashi
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supporting information; scheme or table
p. 2244 - 2253
(2012/03/26)
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- Photoswitchable exciton coupling in merocyanine-diarylethene multi-chromophore hydrogen-bonded complexes
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Light on: Photocontrol of J-type exciton interactions by using chromophores is reported (see picture). Hydrogen-bonded merocyanine dyes could be switched reversibly through photoinduced ring-closure/ring-opening reactions of diarylethene receptors. Addition of H-aggregation-inducing bismelamine receptors enabled the partial interconversion between J- and H-type exciton coupling. Copyright
- Yagai, Shiki,Iwai, Kazunori,Karatsu, Takashi,Kitamura, Akihide
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supporting information
p. 9679 - 9683
(2012/10/30)
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- Mechanism and fluorescence application of electrochromism in photochromic dithienylcyclopentene
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The kinetic process of key intermediates involved in the electrochemical ring opening of photochromic dithienylcyclopentenes (DTEs) has been observed for the first time, where the electronic nature of the DTEs is an important factor that determines the rate-determining step in the electrochromism. The dual chromic property has been implemented to a single molecular fluorescence memory.
- Lee, Sumin,You, Youngmin,Ohkubo, Kei,Fukuzumi, Shunichi,Nam, Wonwoo
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supporting information; experimental part
p. 2238 - 2241
(2012/06/18)
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- Synthesis of photochromic compounds for aqueous solutions and focusable light
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Photochromic compounds with improved performance in pure water have been prepared and characterized. They possess an asymmetrical and extended conjugation system with a 1,2-bis(3-thienyl)perfluorocyclopentene core, additional thiophene rings connected with sulfonic acid residues, as well as terminal pyrid-4-yl and 4-alkoxyphenyl groups. A multistep synthetic route to a key compound with an amino group required for further derivatization has been developed. The complete photocyclization reaction of the initial "open ring" compound (with absorption maximum at 340 nm in MeOH or water) can be performed with a diode laser in pure water or aqueous buffer solutions (without added or-ganic solvents) under irradiation at 366-375 nm, and the reverse ring-opening reaction of the colored "closed ring" compound (λmax = 628 or 624 nm in MeOH or water) takes place under irradiation with visible green or red light (>500 nm). Building block 57, with a secondary amino group, can further be used in the synthesis of practically important, reversibly switchable, fluorescent compounds in which the fluorescent dye (donor) is attached to a photochromic unit (acceptor), and the resonant energy transfer from a donor to the colored form of an acceptor provides a reversible quenching of the fluorescence signal in aqueous solutions.
- Polyakova, Svetlana M.,Belov, Vladimir N.,Bossi, Mariano L.,Hell, Stefan W.
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scheme or table
p. 3301 - 3312
(2011/08/03)
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- An organic optical transistor operated under ambient conditions
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It takes three: The key functionalities of an optical transistor, gating and amplification, are demonstrated exploiting the photophysical properties of a molecular triad (see picture). Two building blocks of the triad are highly efficient fluorophores, whereas the third building block is a photochromic molecule that can be reversibly interconverted between two bistable forms by light.
- Paers, Martti,Hofmann, Christiane C.,Willinger, Katja,Bauer, Peter,Thelakkat, Mukundan,Koehler, Juergen
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supporting information; scheme or table
p. 11405 - 11408
(2012/01/11)
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- A proton and optic dual-control molecular switch based on photochromic diarylethene bearing a rhodamine unit
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A novel fluorescent switch based on rhodamine B and photochromic diarylethene, 1-[2-methyl-5-(4-methoxylphenyl)-3-thienyl]-2-[2-methyl-5-(4- rhodamine B hydrazine-Schiff base-phenyl)-3-thienyl]perfluorocyclopentene (1), has been successfully synthesized through the condensation of rhodamine B hydrazine and 1-[2-methyl-5-(4-methoxylphenyl)-3-thienyl]-2-[2-methyl-5-(4- formylphenyl)-3-thienyl]perfluorocyclopentene. UV and FL measurements reveal that the compound exhibits good photochromic properties responsive to proton and optic dual inputs. Upon irradiation with 297 nm light, the colorless solution of compound 1 turns blue, while the blue solution becomes colorless after irradiated with visible light (λ>450 nm). Furthermore, upon an addition of H+, the fluorescence resonance energy transfers from the rhodamine unit (FRET donor) to the closed-ring diarylethene unit (FRET acceptor), although no energy transfer occurs when the diarylethene is in the open-ring form. The emission intensity of the rhodamine can be modulated with proton and UV/vis light and molecular-level signal communication has been constructed, indicating high potentials of the compound in molecular switches or naked eye recognition systems.
- Liu, Weijun,Pu, Shouzhi,Cui, Shiqiang,Liu, Gang,Fan, Congbin
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scheme or table
p. 4236 - 4242
(2011/06/25)
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- Photoreversible cellular imaging using photochrome-conjugated fullerene silica nanoparticles
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Photochromic compound-conjugated fluorescent fullerene-silica nanoparticles prepared by the reverse-microemulsion method was utilized for photoswitchable cellular imaging by repeatable irradiation of ultraviolet and visible light.
- Jeong, Jinyoung,Yun, Eunju,Choi, Yohan,Jung, Hye-Youn,Chung, Sang J.,Song, Nam Woong,Chung, Bong Hyun
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supporting information; scheme or table
p. 10668 - 10670
(2011/11/29)
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- Photoswitchable organic mixed valence in dithienylcyclopentene systems with tertiary amine redox centers
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The electronic structures of the radical cations of two dithienylperfluorocyclopentene molecules with appended tertiary amine units were investigated by electrochemical and optical spectroscopic methods. The through-bond N-N distances in the photocyclized (closed) forms of the two systems are 9.3 and 17.6 A, respectively, depending on whether the nitrogen atoms are attached directly to the two thienyl units or whether xylyl spacers are in between. In the case of the radical cation with the longer N-N distance, photocyclization of the dithienylperfluorocyclopentene core induces a changeover from class I to class II mixed valence behavior. In the case of the shorter system, the experimental data is consistent with assignment of the photocyclized form to a class III mixed valence species.
- He, Bice,Wenger, Oliver S.
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scheme or table
p. 17027 - 17036
(2011/12/13)
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