- An AIE active Y-shaped diimidazolylbenzene: Aggregation and disaggregation for Cd2+ and Fe3+ sensing in aqueous solution
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A simple Y-shaped dimb with AIE properties was designed and synthesized. It showed selective fluorescence turn-on toward Cd2+ ion in MeCN-water (2:8, v/v) through aggregation, and also selective fluorescence turn-off toward Fe3+ ion in MeCN-water (1:99, v/v) through disaggregation.
- Li, Chengming,Gao, Chao,Lan, Jingbo,You, Jingsong,Gao, Ge
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Read Online
- Cobalt-Catalyzed Hydroalkynylation of Vinylaziridines
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Transition metal-catalyzed hydroalkynylation reactions are efficient transformations allowing the straightforward formation of functionalized alkynes. Therein, we disclose the cobalt-catalyzed hydroalkynylation of vinylaziridines giving rise to both linea
- Biletskyi, Bohdan,Kong, Lingyu,Tenaglia, Alphonse,Clavier, Hervé
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supporting information
p. 2578 - 2585
(2021/03/18)
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- Near-Infrared Fluorescent Probes with Rotatable Polyacetylene Chains for the Detection of Amyloid-β Plaques
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The plaques of accumulated β-amyloid (Aβ) in the parenchymal brain are accepted as an important biomarker for the early diagnosis of Alzheimer's disease (AD). Many near-infrared (NIR) probes, which were based on the D-π-A structure and bridged by conjugat
- Zhang, Longfei,Gong, Xin,Tian, Chuan,Fu, Hualong,Tan, Hongwei,Dai, Jiapei,Cui, Mengchao
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p. 497 - 506
(2021/01/26)
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- Are alkynyl spacers in ancillary ligands in heteroleptic bis(diimine)copper(I) dyes beneficial for dye performance in dye-sensitized solar cells?
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The syntheses of 4,40-bis(4-dimethylaminophenyl)-6,60-dimethyl-2,20-bipyridine (1), 4,40-bis(4-dimethylaminophenylethynyl)-6,60-dimethyl-2,20-bipyridine (2), 4,40-bis(4-diphenylaminophenyl)-6,60-dimethyl-2,20-bipyridine (3), and 4,40-bis(4-diphenylaminophenylethynyl)-6,60-dimethyl-2,20-bipyridine (4) are reported along with the preparations and characterisations of their homoleptic copper(I) complexes [CuL2][PF6] (L = 1-4). The solution absorption spectra of the complexes exhibit ligand-centred absorptions in addition to absorptions in the visible region assigned to a combination of intra-ligand and metal-to-ligand charge-transfer. Heteroleptic [Cu(5)(Lancillary)]+ dyes in which 5 is the anchoring ligand ((6,60-dimethyl-[2,20-bipyridine]-4,40-diyl)bis(4,1-phenylene))bis(phosphonic acid) and Lancillary = 1-4 have been assembled on fluorine-doped tin oxide (FTO)-TiO2 electrodes in dye-sensitized solar cells (DSCs). Performance parameters and external quantum efficiency (EQE) spectra of the DSCs (four fully-masked cells for each dye) reveal that the best performing dyes are [Cu(5)(1)]+ and [Cu(5)(3)]+. The alkynyl spacers are not beneficial, leading to a decrease in the short-circuit current density (JSC), confirmed by lower values of EQEmax. Addition of a co-absorbent (n-decylphosphonic acid) to [Cu(5)(1)]+ lead to no significant enhancement of performance for DSCs sensitized with [Cu(5)(1)]+. Electrochemical impedance spectroscopy (EIS) has been used to investigate the interfaces in DSCs; the analysis shows that more favourable electron injection into TiO2 is observed for sensitizers without the alkynyl spacer and confirms higher JSC values for [Cu(5)(1)]+,.
- Becker, Mariia,Constable, Edwin C.,Housecroft, Catherine E.,Risi, Guglielmo
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- Copper-Mediated Deacylative Coupling of Ynones via C-C Bond Activation under Mild Conditions
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The intermolecular deacylative coupling of unstrained ynones via C-C bond activation was accomplished by a CuCl-bpy system under mild reaction conditions. This protocol features facile cleavage of the C-C bond at room temperature, broad substrate scope, and efficient construction of important symmetric and unsymmetrical 1,3-diyne adducts through homo or cross coupling of ynones, respectively. The preliminary mechanistic investigations indicated that an acyl copper(III) complex is likely involved in this process.
- Feng, Lili,Hu, Tingjun,Zhang, Saisai,Xiong, Heng-Ying,Zhang, Guangwu
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supporting information
p. 9487 - 9492
(2019/12/02)
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- A Porous and Solution-Processable Molecular Crystal Stable at 200 °c: The Surprising Donor-Acceptor Impact
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We report a curious porous molecular crystal that is devoid of the common traits of related systems. Namely, the molecule does not rely on directional hydrogen bonds to enforce open packing, and it offers neither large concave faces (i.e., high internal f
- Cheng, Shengxian,Ma, Xiaoxia,He, Yonghe,He, Jun,Zeller, Matthias,Xu, Zhengtao
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p. 7411 - 7419
(2019/12/02)
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- Reversible mechanofluorochromism of aniline-terminated phenylene ethynylenes
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Seven three-ring phenylene-ethynylene (PE) structural analogs, differing only in the lengths of alkyl chains on terminal aniline substituents, show 50-62 nm bathochromic shifts in emission maxima in response to mechanical force (mechanofluorochromism, MC)
- Sharber, Seth A.,Shih, Kuo-Chih,Mann, Arielle,Frausto, Fanny,Haas, Terry E.,Nieh, Mu-Ping,Thomas, Samuel W.
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p. 5415 - 5426
(2018/06/27)
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- Trimethylsilyl-Protected Alkynes as Selective Cross-Coupling Partners in Titanium-Catalyzed [2+2+1] Pyrrole Synthesis
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Trimethylsilyl (TMS)-protected alkynes served as selective alkyne cross-coupling partners in titanium-catalyzed [2+2+1] pyrrole synthesis. Reactions of TMS-protected alkynes with internal alkynes and azobenzene under the catalysis of titanium imido comple
- Chiu, Hsin-Chun,Tonks, Ian A.
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supporting information
p. 6090 - 6094
(2018/05/30)
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- Multi-color photoluminescence induced by electron-density distribution of fluorinated bistolane derivatives
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The aim of this study was to design and develop new fluorinated light-emitting materials with multi-color photoluminescence that are not limited by their states. For this purpose, fluorinated bistolanes with an amino substituent, such as carbazol-9-yl, di
- Yamada, Shigeyuki,Morita, Masato,Konno, Tsutomu
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- Catalyst-free hydrochlorination protocol for terminal arylalkynes with hydrogen chloride
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We present a simple and straightforward protocol for hydrochlorination of terminal arylalkynes to vinyl chlorides using hydrogen chloride under mild reaction conditions. This protocol does not involve any metal catalysts or additives. It is simple, inexpensive, and easy to prepare, and exhibits good reaction activity. The hydrochlorination proceeds smoothly to yield unique regioselective products via the Markovnikov addition rule.
- Xu, Cai-Xia,Ma, Cun-Hua,Xiao, Fu-Rong,Chen, Hong-Wei,Dai, Bin
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supporting information
p. 1683 - 1685
(2016/11/12)
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- Synthesis and Simple Immobilization of Palladium(II) Acyclic Diaminocarbene Complexes on Polystyrene Support as Efficient Catalysts for Sonogashira and Suzuki-Miyaura Cross-Coupling
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Immobilization of palladium(II) acyclic diaminocarbene (Pd(II)-ADC) complexes on a resin support surface has been easily performed by metal-mediated addition of amino groups of benzhydrylamine-polystyrene to the coordinated isocyanide ligand of cis-PdCl2(CNR)2 (R = t-Bu, Cy). The investigation of the benzhydrylamine reaction with palladium-coordinated isocyanides in solution has revealed that, depending on the reaction conditions, two carbene-type complexes can be obtained as a result of the addition to the CN triple bond, as well as a third complex which is formed via substitution of the isocyanide ligand by benzhydrylamine. Nucleophilic addition of an amino group to the isocyanide ligand has led to a cis-acyclic diaminocarbene complex or a cationic diaminocarbene complex with trans configuration and an intramolecular hydrogen-bonded chloride anion (the nature of this noncovalent interaction was analyzed by DFT calculations, including AIM analysis). The unsupported and resin-supported palladium catalysts have demonstrated high catalytic activity in both Sonogashira and Suzuki-Miyaura cross-coupling. The supported catalyst can be recovered and repeatedly reused without a significant loss in efficiency. The degree of the palladium binding with polystyrene, the oxidation state, and the palladium leaching level were investigated by XPS and XRF analyses.
- Mikhaylov, Vladimir N.,Sorokoumov, Viktor N.,Korvinson, Kirill A.,Novikov, Alexander S.,Balova, Irina A.
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p. 1684 - 1697
(2016/07/06)
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- Systematic variation of cyanobuta-1,3-dienes and expanded tetracyanoquinodimethane analogues as electron acceptors in photoactive, rigid porphyrin conjugates
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We report on a homologous series of nine electron donor-acceptor systems featuring push-pull chromophores as electron acceptors, which are accessible by a cycloaddition-retroelectrocyclization (CA-RE) reaction. The conjugates comprise a ZnII porphyrin as electron donor, which is connected through either a rigid phenylene-ethynylene-phenylene (PEP)-bicyclo[2.2.2]octane or a PEP-trans-decahydroquinoline spacer to different anilino-substituted multicyanobutadienes or extended tetracyanoquinodimethane analogues with first reduction potentials ranging from-1.78 to-0.58 V vs. Fc+/Fc. Characterization of the conjugates includes X-ray crystallography, electrochemistry, DFT calculations, and fluorescence spectroscopy. The extent of ZnII porphyrin fluorescence quenching correlates with the strength of the electron acceptor. Overall, we demonstrate the synthetic feasibility of rationally modulating the acceptor strength by means of the CA-RE reaction in geometrically well-defined electron donor-acceptor conjugates.
- Urner, Lorenz M.,Sekita, Michael,Trapp, Nils,Schweizer, W. Bernd,W?rle, Michael,Gisselbrecht, Jean-Paul,Boudon, Corinne,Guldi, Dirk M.,Diederich, Franois
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supporting information
p. 91 - 108
(2015/02/19)
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- Position of substitution: A facile way to tune the spectroscopic properties of dimethylamino-substituted arylene-ethynylenes
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A series of dimethylamino-substituted arylene-ethynylenes were synthesised by Sonogashira coupling reactions and characterised by the methods of 1H, 13C NMR, UV-Vis, fluorescence, HRMS and theoretical calculations. Effects on spectroscopic properties caus
- Fang, Jing-Kun,Sun, Tengxiao,Fang, Yu,Xu, Zhimin,Zou, Hui,Liu, Yuan,Ge, Fangting
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p. 487 - 491
(2015/11/03)
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- A twisted-intramolecular-charge-transfer (TICT) based ratiometric fluorescent thermometer with a mega-Stokes shift and a positive temperature coefficient
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The fluorescence intensity of N,N-dimethyl-4-((2-methylquinolin-6-yl)ethynyl)aniline exhibits an unusual intensification with increasing temperature, by activating more vibrational bands and leading to stronger TICT emissions upon heating in dimethyl sulfoxide. Based on the different temperature dependence at various wavelengths, as shown in the TICT fluorescence spectrum, this dye can be employed to ratiometrically detect temperature.
- Cao, Cheng,Liu, Xiaogang,Qiao, Qinglong,Zhao, Miao,Yin, Wenting,Mao, Deqi,Zhang, Hui,Xu, Zhaochao
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supporting information
p. 15811 - 15814
(2015/01/08)
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- Mesityllithium and p-(dimethylamino)phenyllithium for the selective alternate trilithiation of the hexaphenylbenzene framework
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We report mesityllithium and p-(dimethylamino)phenyllithium as new valuable lithiating reagents, which realize Br/Li exchange reaction of bromoarenes at relatively high temperature in THF. With these reagents, we established the general and practical protocols for the selective alternate trilithiation of the hexaphenylbenzene framework. This journal is the Partner Organisations 2014.
- Kojima, Tatsuo,Hiraoka, Shuichi
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supporting information
p. 10420 - 10423
(2014/10/15)
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- NHC catalysed trimethylsilylation of terminal alkynes and indoles with Ruppert's reagent under solvent free conditions
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An organo-catalytic protocol for the trimethylsilylation of terminal alkynes employing Ruppert's reagent (CF3SiMe3) as a trimethylsilyl source has been developed under solvent and fluoride free conditions. This method was found to be very effective as a variety of terminal alkynes bearing aliphatic or aromatic substituents underwent smooth transformation to their corresponding silylated products in excellent yields within a few minutes using N-heterocyclic carbene as an organo-catalyst. This methodology was also applied to the chemospecific N-silylation of indoles. This journal is
- Arde, Panjab,Reddy, Virsinha,Anand, Ramasamy Vijaya
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p. 49775 - 49779
(2014/12/11)
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- Palladium-catalyzed coupling between aryl halides and trimethylsilylacetylene assisted by dimethylaminotrimethyltin
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Palladium-catalyzed coupling between aryl halides, especially less reactive ones or N-heteroaryls, and trimethylsilylacetylene in the presence of dimethylaminotrimethyltin generated the coupled products in high yields. The reaction does not need CuI and base as auxiliary agents.
- Cai, Liangzhen,Yang, Dujuan,Sun, Zhonghua,Tao, Xiaochun,Cai, Lisheng,Pike, Victor W.
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experimental part
p. 1059 - 1062
(2012/01/04)
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- One-pot click synthesis of 1N-alkyl-4-aryl-1,2,3-triazoles from protected arylalkynes and alkyl bromides
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1N-Alkyl-4-aryl-1,2,3-triazoles have been prepared through a multicomponent one-pot protocol from the corresponding (arylethynyl)trimethylsilanes and alkyl bromides. In situ alkyl azide formation and alkyne deprotection followed by copper(I)-catalyzed click cycloaddition afforded the desired 1,4-disubstituted 1,2,3-triazoles in generally good to excellent yield, with only minor observation of the undesired 1,5-regioisomeric cycloadduct. The protocol eliminates the need to use reactive organic azides and terminal alkynes. Georg Thieme Verlag Stuttgart. New York.
- Ladouceur, Sebastien,Soliman, Ahmed M.,Zysman-Colman, Eli
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supporting information; experimental part
p. 3604 - 3611
(2011/12/16)
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- Benzothiazole-based fluorophores of donor-π-acceptor-π-donor type displaying high two-photon absorption
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A series of novel heterocycle-based dyes with donor-π-bridge-acceptor- π-bridge-donor (D-π-A-π-D) structural motif, where benzothiazole serves as an electron-withdrawing core, have been designed and synthesized via palladium-catalyzed Sonogashira and Suzuki-type cross-coupling reactions. All the target chromophores show strong one-photon and two-photon excited emission. The maximum two-photon absorption (TPA) cross sections ΔTPA of the prepared derivatives bearing diphenylamino functionalities occur at wavelengths ranging from 760 to 800 nm and are as large as ~900-1100 GM. One- and two-photon absorption characteristics of the title dyes have also been investigated by using density functional theory (DFT) and the structure-property relationships are discussed. The TPA cross sections calculated by means of quadratic response time-dependent DFT using the Coulomb-attenuated CAM-B3LYP functional support the experimentally observed trends within the series, as well as higher ΔTPA values of the title compounds compared to those of analogous fluorene or carbazole-derived dyes. In contrast, the traditional B3LYP functional was not successful in predicting the observed trend of TPA cross sections for systems with different central cores. In general, structural modification of the π-bridge composition by replacement of ethynylene (alkyne) with E-ethenylene (alkene) linkages and/or replacement of dialkylamino electron-donating edge substituents by diarylamino ones results in an increase of ΔTPA values. The combination of large TPA cross sections and high emission quantum yields makes the title benzothiazole-based dyes attractive for applications involving two-photon excited fluorescence (TPEF).
- Hrobarikova, Veronika,Hrobarik, Peter,Gajdos, Peter,Fitilis, Ioannis,Fakis, Mihalis,Persephonis, Peter,Zahradnik, Pavol
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experimental part
p. 3053 - 3068
(2010/07/15)
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- A polyanionic dendritic fluorophore for selective detection of Hg 2+ in triton X-100 aqueous media
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A serles of water-soluble fluorescent dendritic compounds composed of phenylene-ethynylene repeating units and anionic carboxylate or catlonlc ammonium peripheral groups were synthesized. The first generation fluorescent dendrlmer containing nine phenylene-ethynylene units and six carboxylate peripheral groups exhibited a highly selective fluorescence quenching by Hg 2+ Ions. The Stern-Volmer constant (K8v) was 33,700 M -1 In aqueous media In the presence of Triton X-100 surfactant.
- Niamnont, Nakorn,Siripornnoppakhun, Warathip,Rashatasakhon, Paltoon,Sukwattanasinitt, Mongkol
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supporting information; experimental part
p. 2768 - 2771
(2009/11/30)
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- Linear free-energy correlation analysis of the electronic effects of the substituents in the Sonogashira coupling reaction
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Relative rate constants (krel) for the Sonogashira coupling were determined in competitive reactions between iodobenzene and a series of para- and meta-substituted iodobenzenes and compared to the charge on iodine and the z-component of the qua
- Gottardo, Christine,Kraft, Thomas M.,Hossain, M. Selim,Zawada, Peter V.,Muchall, Heidi M.
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p. 410 - 415
(2008/09/20)
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- A novel reaction of 7,7,8,8-tetracyanoquinodimethane (TCNQ): Charge-transfer chromophores by [2 + 2] cycloaddition with alkynes
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A series of donor-acceptor molecules, featuring intense low-energy intramolecular charge-transfer bands, was prepared by regioselective [2 + 2] cycloaddition between 7,7,8,8-tetracyanoquinodimethane (TCNQ) and N,N-dialkylanilino-substituted (DAA-substitut
- Kivala, Milan,Boudon, Corinne,Gisselbrecht, Jean-Paul,Seiler, Paul,Gross, Maurice,Diederich, Francois
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p. 4731 - 4733
(2008/09/17)
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- New fluorophores with rod-shaped polycyano π-conjugated structures: Synthesis and photophysical properties
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Novel rod-shaped polycyano-oligo(phenyleneethynylene)s were synthesized by Pd cross-coupling reaction. Polycyano groups were found to greatly improve the emission efficiency (Φf) of OPEs. By the end donor modification, we achieved the creation of very intense blue light-emitting fluorophore with the SMe group (Φf) = 0.972, log ε 4.89, λ em 455 nm) and very intense yellow light-emitting fluorophore with the NMe2 group (Φf = 0.999, log ε 4.75, λem 555 nm). Contrasting Φf solvent dependency of 6 and 7 and a linear relationship between Φf and σp-X over the whole region of σp-X were also found.
- Yamaguchi, Yoshihiro,Ochi, Takanori,Wakamiya, Tateaki,Matsubara, Yoshio,Yoshida, Zen-Ichi
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p. 717 - 720
(2007/10/03)
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- Synthesis and electrogenerated chemiluminescence of donor-substituted phenylquinolinylethynes and phenylisoquinolinylethynes: Effect of positional isomerism
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In furtherance of our research on the design, synthesis and study of electrogenerated chemiluminescence (ECL) of new donor substituted phenylquinolinylethynes, we report here more new series with the aim of studying the effect of positional isomerism on their overall photophysical properties with a special focus on ECL. For this study we have chosen 2-, 3-, and 4-(p-substituted phenyl)ethynylquinolines, and 1- and 4-(p-substituted phenyl)ethynylisoquinolines. These ethynes were synthesized in good yields by modified Sonogashira coupling of the corresponding terminal alkyne with the respective haloquinolines. The photophysical properties and ECL were studied in acetonitrile solvent and the various results are discussed.
- Elangovan, Arumugasamy,Yang, Shu-Wen,Lin, Jui-Hsien,Kao, Kuo-Ming,Ho, Tong-Ing
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p. 1597 - 1602
(2007/10/03)
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- Sonogashira coupling reaction with diminished homocoupling
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(Matrix presented) The side product from homocoupling reaction of two terminal acetylenes in the Sonogashira reaction can be reduced to about 2% using an atmosphere of hydrogen gas diluted with nitrogen or argon. Terminal arylethynes, diarylethynes, and a few new arylpyridylethynes with donor substituents have been synthesized in very good yields. Comparative control experiments suggest that the homocoupling yield is determined by concentration of both catalyst and oxygen.
- Elangovan, Arumugasamy,Wang, Yu-Hsiang,Ho, Tong-Ing
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p. 1841 - 1844
(2007/10/03)
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- The photochemical characteristics of aromatic enediyne compounds substituted with electron donating and electron withdrawing groups
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trans- and cis-1-(4-Dimethylaminophenyl)-6-(4-nitrophenyl)hex-3-ene-1,5-diynes (trans- and cis-DANE) were synthesized and their photochemical properties were studied. The absorption spectra of trans-DANE red-shifted compared with the parent compound bisph
- Miki, Yoshihiro,Momotake, Atsuya,Arai, Tatsuo
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p. 2655 - 2660
(2007/10/03)
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- First synthesis and electrogenerated chemiluminescence of novel p-substituted phenyl-2-quinolinylethynes
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A series of p-substituted phenyl-2-quinolinylethynes as blue-green emitters were synthesized using a modified Sonogashira coupling reaction and their electrogenerated chemiluminescence properties are reported.
- Elangovan, Arumugasamy,Chen, Ting-Yu,Chen, Chih-Yuan,Ho, Tong-Ing
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p. 2146 - 2147
(2007/10/03)
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- Chalcogenopyranones from disodium chalcogenide additions to 1,4- pentadiyn-3-ones. The role of enol ethers as intermediates
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Enol ethers 9 are formed as a mixture of E- and Z-isomers from the addition of ethanol to 1,4-pentadiyn-3-ones 2 in sodium ethoxide/ethanol. The enol ethers react with disodium chalcogenides to give the corresponding 2,6- disubstituted chalcogenopyranones
- Leonard, Kristi,Nelen, Marina,Raghu, Madhavi,Detty, Michael R.
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p. 707 - 717
(2007/10/03)
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- 2,4,6-triarylchalcogenopyrylium dyes related in structure to the antitumor agent AA1 as in vitro sensitizers for the photodynamic therapy of cancer
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Cationic chalcogenopyrylium dyes 2-4 were synthesized in six steps from 4-(dimethylamino)phenylethyne (7), have absorption maxima in methanol of 594, 631, and 672 nm, respectively, and generate singlet oxygen with quantum yields [Φ(1O2/su
- Leonard, Kristi A.,Nelen, Marina I.,Anderson, Linda T.,Gibson, Scott L.,Hilf, Russell,Detty, Michael R.
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p. 3942 - 3952
(2007/10/03)
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