- Julolidine-based organic dyes with neutral and anion anchoring groups for dye-sensitized solar cells
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Two simple organic dyes (J1 and J2) containing julolidine as the electron donor were synthesized. The simple structure of julolidine attached to the cyanoacetic acid group formed two compounds (anion and neutral forms of E-CCVJ), which showed two different efficiencies when applied to dyesensitized solar cells (DSSCs). Overall conversion efficiencies of 0.91% and 1.21% were obtained for DSSCs based on the cyanoacetic acid (J1) and cyanoacetate (J2) derived dyes, respectively. Compared to the cyanoacetic acid terminated dye, the current density, open circuit voltage and conversion efficiency of the solar cells based on cyanoacetate dye were increased by approximately 24%, 8% and 32%, respectively. The electrochemical impedance analysis showed that the better charge transfer of TiO2 (e-) and electron lifetime (τe) for J2 dye as compared with J1. The power conversion efficiency was found to be quite sensitive to small structural changes to the anchoring moiety.
- Bao, Le Quoc,Hai, Nguyen Thi,Lee, Chi Hwan,Thogiti, Suresh,Kim, Jae Hong
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- The influence of tetrahydroquinoline rings in dicyanomethylenedihydrofuran (DCDHF) single-molecule fluorophores
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We have synthesized several series of DCDHF fluorophores with the amine donor either acyclic or constrained in one or two tetrahydroquinoline rings. The absorption and the fluorescence emission wavelengths and quantum yields have been determined and correlated with the specific donor structures. Generally, inclusion of the donor in a ring annulated to the benzene or naphthalene aromatic (Ar) π-core results in a bathochromic shift of absorption and emission accompanied by an increase in the quantum yield. Thus, the tetrahydroquinoline donor provides an efficient way to tailor the properties of fluorophores with substituted amines as electron-donating groups.
- Wang, Hui,Lu, Zhikuan,Lord, Samuel J.,Willets, Katherine A.,Bertke, Jeffrey A.,Bunge, Scott D.,Moerner,Twieg, Robert J.
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- A selective and sensitive fluorescent albumin probe for the determination of urinary albumin
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In this communication, we report a simple albumin probe based on a fluorescent molecular rotor for the detection of trace albumin levels in urine. In the presence of albumin, the probe exhibits remarkable 400-fold fluorescence enhancement with high selectivity and sensitivity. The probe was successfully applied in the quantitative detection of urinary albumin.
- Wu, Ying-Yi,Yu, Wan-Ting,Hou, Tai-Cheng,Liu, Tao-Kai,Huang, Chi-Ling,Chen, I.-Chia,Tan, Kui-Thong
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- Julolidine fluorescent molecular rotors as vapour sensing probes in polystyrene films
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We introduce a new sensing polymer system for detection of volatile organic compounds (VOCs) based on the optical response of polystyrene (PS) films doped with julolidine fluorescent molecular rotors (FMRs). The julolidine FMRs exhibited viscosity-dependent changes in the fluorescence intensity, that was enhanced when glycerol was added to ethanol solutions and when they were dispersed in PS films. Thus, reduction in medium mobility slowed down internal motions and allowed for a major radiative decay pathway. The FMR/PS films were exposed to several VOCs, and showed a significant decrease in fluorescence emission when exposed to chloroform, whereas a negligible variation in their emission occurred when methanol was utilized. This vapour sensing behaviour was much more evident when a perfluorodecyl chain was linked to the julolidine core being the molecule segregated at the film surface. This responsive behaviour was affected by solvent composition and its reproducible response was easily determined by luminescence experiments.
- Martini, Giulio,Martinelli, Elisa,Ruggeri, Giacomo,Galli, Giancarlo,Pucci, Andrea
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- Dual-mode tunable viscosity sensitivity of a rotor-based fluorescent dye
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The design and fabrication of new type viscosity sensor on molecular scale will enrich the detection means in both physical and life sciences. In this work, a rotor-containing fluorescent dye was prepared, which can reveal a typical viscosity-sensitive behavior due to the environment-induced non-radiative decay. The viscosity-sensitive behavior of this dye could be tunable (locked and activated) in aqueous environment, either with the reversible light-driven trans/cis-photoisomerization of the cyanostilbene moiety, or with the reversible assembly/disassembly process of β-cyclodextrin (β-CD) to the rotor part. Such dual-mode tunable viscosity sensitivity can be well distinguished by fluorescent spectra. A slope method, on double-logarithmic plots of the fluorescent signal to the corresponding environmental viscosity, makes a quantitative estimation to the tunable viscosity sensitivity, featuring the 'Activated' and the 'Locked' state in this molecular-scale viscometer.
- Zhu, Liang-Liang,Qu, Da-Hui,Zhang, Dong,Chen, Zhao-Fei,Wang, Qiao-Chun,Tian, He
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- Fluorescent polystyrene films for the detection of volatile organic compounds using the twisted intramolecular charge transfer mechanism ?
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Thin films of styrene copolymers containing fluorescent molecular rotors were demonstrated to be strongly sensitive to volatile organic compounds (VOCs). Styrene copolymers of 2-[4-vinyl(1,1-biphenyl)-4-yl]-cyanovinyljulolidine (JCBF) were prepared with different P(STY-co-JCBF)(m) compositions (m% = 0.10–1.00) and molecular weights of about 12,000 g/mol. Methanol solutions of JCBF were not emissive due to the formation of the typical twisted intramolecular charge transfer (TICT) state at low viscosity regime, which formation was effectively hampered by adding progressive amounts of glycerol. The sensing performances of the spin-coated copolymer films (thickness of about 4 μm) demonstrated significant vapochromism when exposed to VOCs characterized by high vapour pressure and favourable interaction with the polymer matrix such as tetrahydrofurane (THF), CHCl3 and CH2Cl2. The vapochromic response was also reversible and reproducible after successive exposure cycles, whereas the fluorescence variation scaled linearly with VOC concentration, thus suggesting future applications as VOC optical sensors.
- Borelli, Mirko,Iasilli, Giuseppe,Minei, Pierpaolo,Pucci, Andrea
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- Solvatochromism and intramolecular charge transfer in dialkylamino-substituted halogenated thienyl chalcone analogues
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Herein, we present the study of two complementary intramolecular charge transfer (ICT) transitions in two sets of dialkylamino-substituted halogenated thienyl chalcones. We demonstrate that while the first (and stronger) ICT takes place from the 4-(dialkylamino)phenyl moiety to the enone, the second ICT involves the thienyl substituent as the donor. The former is evidenced by a robust solvatochromic shift in both absorption and emission spectra, implying a large increase in the dipole moment upon excitation to the lowest excited state. The latter, a short-range ICT process, is confirmed upon photoexcitation of the higher energy bands, and its enhancement by the larger polarizability of the iodine substituent. With the help of (TD)-DFT calculations and the solvatochromic method, we quantified the extent of these effects and set the stage for further developments towards the design of new chalcone-based dyes. We demonstrated that theoretical calculations allow fine-tuning the sensitive balance between these complementary ICT processes.
- Echevarria, Lorenzo,Fernández-Terán, Ricardo,Hernández, Florencio Eloy,Sucre-Rosales, Estefanía,Urdaneta, Neudo
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- A fluorescent molecular rotor probe for tracking plasma membranes and exosomes in living cells
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A rotor-based probe MRMP-1 was designed and synthesized. MRMP-1 can bind to plasma membranes very quickly and stably with remarkable fluorescence enhancement. It can be used to monitor the dynamic changes in cell membranes in real-time under stimuli conditions. Importantly, MRMP-1 is the first rotor-based fluorescent sensor to label exosomes in living cells.
- Au-Yeung, Sung King,Chen, Qingxin,Feng, Ling,Hailu, Hagos Birhanu,Liu, Zhiyang,Pang, Qiuxiang,Sun, Hongyan,Xie, Yusheng,Yang, Mengsu,Yao, Xi,Zhang, Jie,Zhang, Liang
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supporting information
p. 8480 - 8483
(2020/08/13)
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- Novel aza-BODIPY based small molecular NIR-II fluorophores for: In vivo imaging
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The development of new NIR-II fluorophores, particularly those with facile syntheses, high fluorescence quantum yields, and stable and tunable photophysical properties, is challenging. Herein, we report a new class of small molecular NIR-II fluorophores based on aza-dipyrromethene boron difluoride (aza-BODIPY) dyes. We demonstrate promising photophysical properties of these dyes, such as large Stokes shift, superior photostability, and good fluorescence brightness as nanoparticles in aqueous solution. Because of these properties and high resolution and deep penetration NIR-II imaging ability, the aza-BODIPY based dyes show great potential as NIR-II imaging agents.
- Bai, Lei,Sun, Pengfei,Liu, Yi,Zhang, Hang,Hu, Wenbo,Zhang, Wansu,Liu, Zhipeng,Fan, Quli,Li, Lin,Huang, Wei
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supporting information
p. 10920 - 10923
(2019/09/18)
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- Synthesis, Structure, and Properties of Amino-Substituted Benzhydrylium Ions – A Link between Ordinary Carbocations and Neutral Electrophiles
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Optimized synthetic procedures for the straightforward access to eleven amino-substituted diarylmethylium tetrafluoroborates are described. These benzhydrylium ions cover a range of seven orders of magnitude in electrophilicity and provide a link between ordinary carbocations and neutral electrophiles. Five of these highly stabilized benzhydrylium tetrafluoroborates were characterized by single-crystal X-ray crystallography. While the experimentally determined bond lengths and angles in the solid state perfectly agree with those calculated by DFT methods for the gas phase and aqueous solution, crystal packing accounts for large differences in the twist angles of the aryl groups found in the solid state as compared to calculated structures.
- Mayer, Robert J.,Hampel, Nathalie,Mayer, Peter,Ofial, Armin R.,Mayr, Herbert
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supporting information
p. 412 - 421
(2018/09/14)
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- Near-infrared two-window fluorescence probe based on Aza-BODIPY, as well as preparation and application thereof
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The invention relates to design synthesis and application of a near-infrared two-window fluorescence probe based on Aza-BODIPY, and belongs to the field of organic fluorescence probes. A near-infraredtwo-area dyestuff (NIR-II, 1000-1700nm) has a long emission wavelength and less light scattering and tissue autofluorescence interference so as to obtain better resolution ratio and imaging depth inbioimaging. An Aza-BODIPY fluorescent dye has a longer absorption emission wavelength, a narrower peak width at half height and a larger molar extinction coefficient, and is widely applied to the fields such as photodynamic therapy. The structural formula of the near-infrared two-window fluorescence probe designed and synthesized by the invention is as shown in the figure (I). According to the probe, electron-donating group julolidine is introduced onto the classic Aza-BODIPY structure, and the molecular rigidity is improved. The probe has excellent light stability and a capacity of resistingdisturbance. The probe successfully realizes near-infrared two-window imaging during the mice imaging experiment.
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Paragraph 0049-0053; 0059-0061; 0065-0067
(2019/02/25)
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- Synthesis of unsymmetrical 4-oxo-2-vinyl-4H-chromene-3-carbonitrile dyes via Knoevenagel reaction
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New 4-oxo-2-vinyl-4H-chromene-3-carbonitrile derivatives have been synthesized by the Knoevenagel reaction of 2-methyl-4-oxo-4H-chromene-3-carbonitrile with aromatic and heteroaromatic aldehydes. Spectral properties of the obtained compounds have been studied.
- Levchenko,Chudov,Zinoviev,Lyssenko,Demin,Poroshin,Shmelin,Grebennikov
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supporting information
p. 2788 - 2792
(2018/06/08)
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- Synthesis and characterisation of long wavelength-absorbing donor/acceptor-substituted methine dyes
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By the reaction of aromatic or heteroaromatic formyl compounds or their corresponding iminium salts with active methylene compounds a series of new methine dyes with long-wavelength absorption in the near-infrared spectral range were prepared.
- Heichert, Christoph,Hartmann, Horst
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p. 651 - 658
(2016/07/06)
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- Structural and photophysical properties of alkylamino substituted 2-arylidene and 2,5-diarylidene cyclopentanone dyes
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A series of alkylamino substituted 2-arylidene and 2,5-diarylidene cyclopentanone compounds were synthesized. Spectroscopic and photophysical properties of these compounds have been measured in a variety of solvents. Absorption and fluorescence maxima have been correlated with the Empirical Scale of Solvent Polarity (ET(30)). Theoretical TD-DFT spectral calculations and Lippert-Mataga analysis support the internal charge transfer (ICT) nature of the S0 → S1 excitation for these compounds, with higher degrees of ICT depicted for the alkylamino substituted 2,5-diarylidene cyclopentanones. Photophysical properties consisted of measuring the fluorescence quantum yields (Φf) and lifetimes (τf) in a variety of solvents. Radiative and nonradiative decay constants have been determined from the Φf and τf data. Variation with solvent in the nonradiative rate of decay is interpreted in terms of a competition between internal conversion and intersystem crossing. Lastly, two compounds presented have been shown to undergo excited state protonation in glacial acetic acid.
- Zoto, Christopher A.,Ucak-Astarlioglu, Mine G.,Macdonald, John C.,Connors, Robert E.
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- Amino substituted 4-pyridylbutadienes: Synthesis and fluorescence investigations
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Synthesis and spectroscopic investigations of a series of donor-π-acceptor systems containing pyridine as the electron withdrawing group and an amino derivative (dimethylamino, diphenylamino, carbazole and julolidine) as electron donating group, separated by a π-spacer are described. The effect of varying donors on absorption and emission properties was studied in different solvents. All the molecules investigated exhibit pronounced positive polarity dependent solvatochromic shifts of up to ～141 nm. Strong fluorescence quantum yields are also observed for dienes containing carbazole and diphenylamine donors. This behavior suggests the presence of highly polar emitting states as a result of π -π?intramolecular charge-transfer (ICT). The observations were corroborated by a linear relation of the fluorescence maximum (νmax) versus the solvent polarity function (Δf) from the Lippert-Mataga correlation. The emission lifetime shows a decay profile consistent with the formation of one species (1 and 3) and two species (2 and 4) in the excited state.
- Agnihotri, Harsha,Mahalingavelar, Paramasivam,Mande, Hemant,Ghalsasi, Prasanna,Kanvah, Sriram
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p. 341 - 348
(2015/09/07)
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- Synthesis of novel hemicyanine dyes for color compensating film in plasma display panels
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Five novel cyanine dyes containing julolidine and indole moieties were synthesized. Several color compensating films for plasma display panels (PDP) were prepared using these dyes. The spectroscopic and physicochemical properties of the synthesized dyes in both solution and film state were evaluated. For each color compensating film, the optimum ratio of dye to binder was determined on the basis of transmittance, half band width, and photo-stability of the color compensating film. The five synthesized dyes showed sharp absorption peaks near 590 nm (orange light) and had molar extinction coefficients above 1 × 105 M-1cm-1. The melting point of the dyes was above 200 °C and photo-stability of the color compensating films was improved by introducing substituents at the 5th position on the indole derivatives.
- Kim, Bo Hyung,Park, Se Woong,Lee, Donghyun,Kwon, I. I. Keun,Kim, Jae Pil
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p. 2453 - 2459
(2014/10/15)
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- Identifying the bond responsible for the fluorescence modulation in an amyloid fibril sensor
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An ultrafast intramolecular bond twisting process is known to be the responsible mechanism for the sensing activity of the extensively used amyloid fibril sensor thioflavin T (ThT). However, it is not yet known which one of the two possible single bonds in ThT is actually involved in the twisting process. To resolve this fundamental issue, two derivatives of ThT have been designed and synthesized and subsequently their photophysical properties have been studied in different solvents. It is understood from the present study that the rotation around the central C-C single bond, and not that around the C-N single bond, is primarily responsible for the sensor activity of ThT. Detailed viscosity-dependent fluorescence studies revealed that the ThT derivative with restricted C-N bond rotation acts as a better sensor than the derivative with free C-N bond rotation. The better sensory activity is directly correlated with a shorter excited-state lifetime. Results obtained from the photophysical studies of the ThT derivatives have also been supported by the results obtained from quantum chemical calculations.
- Srivastava, Anvita,Singh, Prabhat K.,Kumbhakar, Manoj,Mukherjee, Tulsi,Chattopadyay, Subrata,Pal, Haridas,Nath, Sukhendu
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experimental part
p. 9257 - 9263
(2010/10/02)
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- Fine tuning of the photophysical and electroluminescent properties of DCM-type dyes by changing the structure of the electron-donating group
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Using 2H-indene-1,3-dione as an electron-withdrawing group and aromatic amines of different structures as electron-donating groups, four new DCM-type dyes, IN-1, IN-2, IN-3, and IN-4, were designed and synthesized for application in organic light-emitting diodes (OLEDs) as red light-emitting materials. IN-2 exhibits a red shift in fluorescence but a blue shift in absorption with respect to IN-1. Similarly, IN-4 exhibits a red shift in fluorescence but a blue shift in absorption with respect to IN-3. These unique photophysical properties were utilized to optimize the electroluminescence color purity and efficiency of these red emitters in OLEDs. In EL devices with the configuration of ITO/NPB (60 nm)/Alq3 (or Gaq3): red dopant (2.0 wt%) (7 nm)/BCP (12 nm)/Alq3 (45 nm)/LiF (0.3 nm)/Al (300 nm), IN-3 in Alq3 and IN-1 in Gaq3 show CIE coordinates of (0.64, 0.36) and (0.65, 0.34), and current efficiencies of 3.24 cd A-1 and 3.02 cd A -1, respectively, much better than the other guest/host combinations. This can be ascribed to the good spectrum overlap either between IN-3 and Alq3 or between IN-1 and Gaq3, indicating that the absorption spectrum has the same importance as the fluorescence spectrum in the improvement of color purity of red emitters. The Royal Society of Chemistry 2006.
- Yao, Yi-Shan,Zhou, Qian-Xiong,Wang, Xue-Song,Wang, Yue,Zhang, Bao-Wen
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p. 3512 - 3520
(2008/12/20)
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- ORGANIC DYE, PHOTOELECTRIC TRANSDUCING MATERIAL, SEMICONDUCTOR ELECTRODE, AND PHOTOELECTRIC TRANSDUCING DEVICE
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Disclosed are an organic dye having a specific structure, a photoelectric conversion material containing the dye, a semiconductor electrode formed of a substrate having an electrically conductive surface, a semiconductor layer coated on the electrically conductive surface and the above dye adsorbed on the surface, and a photoelectric conversion device to which the above dye is applied. The present invention uses the above dye and can therefore provide a photoelectric conversion device excellent in photoelectric conversion efficiency, and the photoelectric conversion device is suitable for use in a solar cell or the like.
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Page/Page column 61
(2008/06/13)
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- CD exciton chirality method. New red-shifted chromophores for hydroxyl groups
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When hydroxyl groups are derivatized to apply the CD exciton chirality method, the absorption maxima of introduced chromophores should not overlap with that of the substrate, except for cases in which the coupling between the existing and the introduced chromophores are deliberately sought for. Thus, the availability of red-shifted chromophores that do not overlap with the substrate absorption would greatly expand the applicability of this versatile CD method. Four such red-shifted chromophores, chrom-II, -III, -IV, and -V, have been developed to convert hydroxyl groups into esters that absorb strongly in the range 360-410 nm. Using the chromophoric triazole amide, they can readily derivatize hydroxyl groups of the substrates on a microscale. The bischromophoric esters of 1(R),2(R)-cyclohexanediol (14-18) exhibited intense exciton-split CD curves with the signs correctly representing the absolute sense of twist between the two hydroxyl groups. The 1,2-diol moieties of taxinine (2) and chromomycin A3 (3) derivatives, already having strong absorptions at 260-275 nm, were esterified with the new chromophores; this gave rise to strong couplets isolated from the CD Cotton effects of starting materials, the signs of which were in agreement with the absolute configurations of these two natural products. These O-acylating chromophores should be useful for determinations of absolute configurations and conformations of chiral substrates, including biopolymers; they could also be conveniently used in conjunction with the red-shifted chromophores developed recently for primary amino groups.
- Cai, Guolin,Bozhkova, Nina,Odingo, Joshua,Berova, Nikolina,Nakanishi, Koji
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p. 7192 - 7198
(2007/10/02)
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