- Coordinating Electron Transport Chains to an Electron Donor
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Two electron transport chains (2 and 3) featuring two fullerenes with different electron acceptor strengths have been synthesized, characterized, and coordinated to a light harvesting/electron donating zinc porphyrin. Electrochemical assays corroborate th
- Villegas, Carmen,Wolf, Maximilian,Joly, Damien,Delgado, Juan Luis,Guldi, Dirk M.,Martín, Nazario
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- Solvent-Modulated Emission Properties in a Superhydrophobic Oligo(p-phenyleneethynylene)-Based 3D Porous Supramolecular Framework
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A chromophoric oligo(p-phenyleneethynylene) (OPE) bola-amphiphile with dioxyoctyl side chains (H2OPE-C8) has been self-assembled with CdII to form a 1D coordination polymer, {Cd(OPE-C8)(DMF)2(H2O)} (1), which is further interdigitated to form a 2D network. Such 2D networks are further interwoven to form a 3D supramolecular framework with surface-projected alkyl chains. The desolvated framework showed permanent porosity, as realized from the CO2 adsorption profile. 1 showed high water contact angles, portraying its superhydrophobic nature. 1 also showed a linker-based cyan luminescence. Solvent removal led to a bathochromic shift in emission into the green region. Resolvation with N,N-dimethylformamide brought back the original cyan emission, whereas for tetrahydrofuran, ethanol, and methanol, it persisted at an intermediate state. Density functional theory calculations unraveled that, twisting of the OPE phenyl rings generated the red shift in emission.
- Roy, Syamantak,Suresh, Venkata M.,Hazra, Arpan,Bandyopadhyay, Arkamita,Laha, Subhajit,Pati, Swapan. K.,Maji, Tapas Kumar
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- Boron ketoiminate-based conjugated polymers with tunable AIE behaviours and their applications for cell imaging
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Three new boron ketoiminate-based conjugated polymers P1, P2, and P3 were designed and synthesized through the Sonogashira coupling reaction of 4,6-bis(4-bromophenyl)-2,2-difluoro-3-phenyl-2H-1,3,2-oxazaborinin-3-ium-2-uide (M1) with 1,4-diethynyl-2,5-bis
- Dai, Chunhui,Yang, Dongliang,Zhang, Wenjie,Fu, Xiao,Chen, Qingmin,Zhu, Chengjian,Cheng, Yixiang,Wang, Lianhui
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- Highly enantioselective recognition of alaninol via the chiral BINAM-based fluorescence polymer sensor
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A novel chiral polymer P1 was designed and synthesized by the polymerization of (S)-2, 2′-binaphthyladiamine (BINAM) derivative monomer (S-M-1) with 2, 5-diiodo-1, 4-dioctyloxybenzene (M-2) via Pd(II)-catalyzed Sonogashira coupling reaction, and P2 could
- Zhang, Wenjie,Wei, Guo,Wang, Ziyu,Ma, Jing,Zhu, Chengjian,Cheng, Yixiang
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- White light emission from fluorene-EDOT and phenothiazine-hydroquinone based D-π-A conjugated systems in solution, gel and film forms
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Two conjugated D-π-A organic molecules, one fluorene-ethylene dioxythiophene (FL-E) based and another phenothiazine-hydroquinone (PT-Hq) based, were synthesized and observed to form 1-dimensional microstructures in the solid state. These two molecules whe
- Anand, Vivek,Dhamodharan, Raghavachari
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- Functional phenylethynylene side arm poly(arylene ethynylene) conjugated polymers: Optical and electrochemical behavior for enrichment of electronic applications
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The poly(arylene ethynylene) (PAE) conjugated polymers (CPs) with a donor-acceptor (D-A) side arm have been designed and synthesized using Sonogashira cross coupling in the presence of cyano methylene, or cyano thiophene gave diethynyl (A) and alkoxy and alkyl substituted diiodo aryl monomers (D). An interesting electronic response in optical measurements such as UV-visible (UV-vis) and fluorescence (FL) spectra was observed in tetrahydrofuran solvent. From the FL spectra, it was observed that the CP solutions possess an interesting long bathochromic shift when compared with the UV-vis spectra, because of the electron withdrawing, electron releasing and conjugation effects. The electrochemical and thin film UV-vis spectral measurements provided highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) electronic energy levels and their corresponding semiconducting electronic energy gaps (Eg) of the PAE CPs. Among the side arm CPs, polymers P1 and P5 have low Eg of 2.14 eV and 2.17 eV. The new PAE CPs are reliable for use in electronic and photonics applications.
- Arun Kumar,Gomathi Priya,Alagar
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supporting information
p. 5767 - 5773
(2018/04/23)
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- How Large Can We Build a Cyclic Assembly? Impact of Ring Size on Chelate Cooperativity in Noncovalent Macrocyclizations
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Self-assembled systems rely on intramolecular cooperative effects to control their growth and regulate their shape, thus yielding discrete, well-defined structures. However, as the size of the system increases, cooperative effects tend to dissipate. We analyze here this situation by studying a set of oligomers of different lengths capped with guanosine and cytidine nucleosides, which associate in cyclic tetramers by complementary Watson–Crick H-bonding interactions. As the monomer length increases, and thus the number of C(sp)–C(sp2) σ-bonds in the π-conjugated skeleton, the macrocycle stability decreases due to a notable reduction in effective molarity (EM), which has a clear entropic origin. We determined the relationship between EM or ΔS and the number of σ-bonds, which allowed us to predict the maximum monomer lengths at which cyclic species would still assemble quantitatively, or whether the cyclic species would not able to compete at all with linear oligomers over the whole concentration range.
- Montoro-García, Carlos,Mayoral, María J.,Chamorro, Raquel,González-Rodríguez, David
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p. 15649 - 15653
(2017/12/02)
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- Five-component trigonal nanoprism with six dynamic corners
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The metallo-supramolecular trigonal prism P is based on five different components and three unlike dynamic coordination motifs: the heteroleptic phenanthroline-terpyridine complex [Zn(1)(4)]2+ (HETTAP), the heteroleptic phenanthroline-pyridine
- Gaikwad, Sudhakar,Lal Saha, Manik,Samanta, Debabrata,Schmittel, Michael
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supporting information
p. 8034 - 8037
(2017/07/22)
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- A fishing rod-like conjugated polymer bearing pillar[5]arenes
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A novel diethynyl functionalized pillar[5]arene, that is a pentabenzenacyclodecaphane derivative, has been synthesized and polymerized with p-dihalobenzene to form a fishing rod-like conjugated polymer, where one of the benzenes in the pillar[5]arene ring
- Ma, Yingjie,Chen, Long,Li, Chen,Müllen, Klaus
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supporting information
p. 6662 - 6664
(2016/06/01)
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- Polymer-based fluorescence sensor incorporating thiazole moiety for direct and visual detection of Hg2+ and Ag+
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A thiazole-based conjugated polymer was synthesized by the polymerization reaction of 4,7-dibromo-2-methylbenzo[d]thiazole with 1,4-diethynyl-2,5-bis(octyloxy)benzene via Pd-catalyzed Sonogashira coupling reaction. The conjugated polymer emits bright green fluorescence and exhibits 'turn-off' fluorescent quenching responses towards both Hg2+ and Ag+ over other cations, such as Li+, K+, Ca2+, Mg2+, Ba2+, Zn2+, Cd2+, Co2+, Ni2+, Pb2+, Cu2+, Al3+ and Fe3+. More importantly, the color change of this polymer solution could be clearly observed by the naked eyes upon the addition of Hg2+ (green to colorless) and Ag+ (green to yellow), indicating that this thiazole-based conjugated polymer material could be used as a colorimetric sensor for directly visual detection of Hg2+ and Ag+.
- Li, Fei,Meng, Fandian,Wang, Yuxiang,Zhu, Chengjian,Cheng, Yixiang
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p. 1700 - 1704
(2015/03/31)
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- Comprehensive analysis of fragment orbital interactions to build highly π-conjugated thienylene-substituted phenylene oligomers
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π-Conjugated thienylene-phenylene oligomers with fluorinated and dialkoxylated phenylene fragments have been designed and prepared to understand the interactions in fragment orbitals, the influence of the substituents (F, OMe) on the HOMO-LUMO gap, and th
- Florès, Jean-Charles,Lacour, Marie-Agnès,Sallenave, Xavier,Serein-Spirau, Fran?oise,Lère-Porte, Jean-Pierre,Moreau, Jo?l J. E.,Miqueu, Karinne,Sotiropoulos, Jean-Marc,Flot, David
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p. 7532 - 7546
(2013/06/27)
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- Controlled dealkylation by BBr3: Efficient synthesis of para-alkoxy-phenols
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Controlled dealkylation of dialkyl-aryl-ethers by substoichiometric BBr3 has been developed as a general tool for the differentiation of the oxygen functions in hydroquinone derivatives. The reaction proceeds smoothly at rt either on linear or branched al
- Pasquini, Chiara,Coniglio, Alessandra,Bassetti, Mauro
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supporting information
p. 6191 - 6194,4
(2012/12/11)
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- Variable-gap conjugated oligomers grafted to CdSe nanocrystals
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Three linear asymmetrically functionalized conjugated molecules composed of five or six aromatic rings were synthesized, bearing a terminal phosphonic acid group, with the objective of enabling their grafting onto inorganic CdSe nanocrystals. These chromo
- Stalder, Romain,Xie, Dongping,Zhou, Renjia,Xue, Jiangeng,Reynolds, John R.,Schanze, Kirk S.
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p. 3143 - 3152
(2015/03/18)
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- In situ generated 1:1 Zn(II)-containing polymer complex sensor for highly enantioselective recognition of N-Boc-protected alanine
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A novel chiral (S)-BINAM-based fluorescence polymer sensor was designed and synthesized by the polymerization of 5,5′-((2,5-dioctyloxy-1,4-phenylene) bis(ethyne-2,1-diyl)bis(2-hydroxy-3-(piperidin-1-ylmethyl)benzaldehyde (M-1) with (S)-2,2′-binaphthyldiamine (S-BINAM, M-2) via Schiffs base formation. The resulting chiral polymer sensor shows very weak fluorescence but exhibits the obvious fluorescence enhancement response toward Zn2+. The in situ generated 1:1 Zn(II)-containing complex of chiral polymer can serve as a fluorescence sensor for highly enantioselective recognition of N-Boc-protected alanine, and the value of enantiomeric fluorescence difference ratio (ef) can reach as high as 6.90. This is the first report on the in situ generated chiral polymer complex used as a fluorescence sensor for highly enantioselective recognition of N-Boc-protected alanine.
- Hou, Jiali,Song, Fengyan,Wang, Lu,Wei, Guo,Cheng, Yixiang,Zhu, Chengjian
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p. 7835 - 7842,8
(2020/09/15)
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- Two-photon absorption properties of proquinoidal D-A-D and A-D-A quadrupolar chromophores
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We report the synthesis, one- and two-photon absorption spectroscopy, fluorescence, and electrochemical properties of a series of quadrupolar molecules that feature proquinoidal p-aromatic acceptors. These quadrupolar molecules possess either donoracceptor donor (D-A-D) or acceptordonoracceptor (A-D-A) electronic motifs, and feature 4-N,N-dihexylaminophenyl, 4-dodecyloxyphenyl, 4-(N,N-dihexylamino)benzo[c][1,2,5]thiadiazolyl or 2,5-dioctyloxyphenyl electron donor moieties and benzo[c][1,2,5]thiadiazole (BTD) or 6,7-bis(30,70-dimethyloctyl)[1,2,5]thiadiazolo[3,4-g]quinoxaline (TDQ) electron acceptor units. These conjugated structures are highly emissive in nonpolar solvents and exhibit large spectral red-shifts of their respective lowest energy absorption bands relative to analogous reference compounds that incorporate phenylene components in place of BTD and TDQ moieties. BTD-based D-A-D and A-D-A chromophores exhibit increasing fluorescence emission redshifts, and a concomitant decrease of the fluorescence quantum yield (Ff) with increasing solvent polarity; these data indicate that electronic excitation augments benzothiadiazole electron density via an internal charge transfer mechanism. The BTD- and TDQcontaining structures exhibit blue-shifted two-photon absorption (TPA) spectra relative to their corresponding one-photon absorption (OPA) spectra, and display high TPA cross sections (>100 GM) within these spectral windows. D-A-D and A-D-A structures that feature more extensive conjugation within this series of compounds exhibit larger TPA cross sections consistent with computational simulation. Factors governing TPA properties of these quadrupolar chromophores are discussed within the context of a three-state model.
- Susumu, Kimihiro,Fisher, Jonathan A.N.,Zheng, Jieru,Beratan, David N.,Yodh, Arjun G.,Therien, Michael J.
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p. 5525 - 5539
(2011/08/06)
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- Synthesis of π-conjugated polymers via regioregular organometallic polymers 2. Transformation of titanacyclopentadienecontaining polymer into poly(ρ-phenylene) derivative
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The transformation of a regioregular organometallic polymer possessing titanacyclopentadiene-2,5-diyl units into a poly(ρ-phenylene) derivative by means of a novel polymer reaction method is described. The organotitianium polymer was prepared by the polymerization of 1,4-diethynyl-2,5- dioctyloxybenzene and a low-valent titanium complex, generated in situ from titanium(IV) isopropoxide and isopropylmagnesium chloride, and was subjected to the reaction with 3-bromo-1-propyne followed by the protonation. Consequently, a polymer consisting of the substituted phenylene-1,4-diyl units could be produced in a high yield,which is soluble in organic solvents such as chloroform. The number-average molecularweight and themolecular weight distribution of the polymer were estimated as 4800 and 1.8, respectively (GPC, polystyrene). The UV-vis absorption spectrum of the polymer exhibited the absorption maximum (λmax) at 329 nm, which was bathochromically shifted by 53 nm compared with that of a model compound, 1,4-bis(2-methoxyphenyl)-2- methylbenzene (λmax = 276 nm). Copyright
- Kino, Tomoko,Nishiyama, Hiroki,Tomita, Ikuyoshi
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experimental part
p. 558 - 562
(2010/11/16)
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- Synthesis, characterization and electroluminescence of polyfluorene copolymers containing t-shaped lsophorone derivatives
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We have successfully synthesized a series of new fluorene-based copolymers, poly[(9,9-bls(4-octyloxy-phenyl)fluorene-2,7-diyl)-co- [2(3{2[4(2{4[bis(bromophenyl-4yl) amino]phenyl}vinyl)-2,5-blsoctyloxyphenyl] vinyl}-5,5-dimethyl-cyclohex-2enylidene)malonon
- Park, Moo-Jin,Jonghee,Hwan Jung,Park, Jong-Hwa,Kong, Hoyoul,Ji-Young,Hwang, D.O.-Hoon,Shim, Hong-K.U.
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experimental part
p. 82 - 90
(2010/11/04)
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- Efficient synthesis of thioamide terminated molecular wires
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Bis-thioamide terminated 'molecular wires' are formed in a high yield under mild conditions from readily synthesised bis-nitrile terminated molecules and aqueous ammonium sulfide in DMF.
- Dixon, Sally,Whitby, Richard J.
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p. 8147 - 8150
(2007/10/03)
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- A new iterative approach for the synthesis of oligo(phenyleneethynediyl) derivatives and its application for the preparation of fullerene- oligo(phenyleneethynediyl) conjugates as active photovoltaic materials
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Disymmetrically substituted oligo(phenyleneethynediyl) (OPE) derivatives were prepared from 2,5-bis(octyloxy)-4-[(triisopropylsilyl)ethynyl]benzaldehyde (5) by an iterative approach using the following reaction sequence: i) Corey - Fuchs dibromoolefinatio
- Nierengarten, Jean-Francois,Gu, Tao,Hadziioannou, Georges,Tsamouras, Dimitris,Krasnikov, Victor
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p. 2948 - 2966
(2007/10/03)
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- Synthesis of fullerene-oligophenyleneethynylene hybrids
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Disymmetrically substituted oligophenyleneethynylene (OPE) derivatives have been prepared by a new iterative method and attached to C60 by a 1,3-dipolar cycloaddition of the azomethine ylides generated in situ from the corresponding OPE aldehyd
- Gu, Tao,Nierengarten, Jean-Fran?ois
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p. 3175 - 3178
(2007/10/03)
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- Synthesis, morphology, and optical properties of tetrahedral oligo(phenylenevinylene) materials
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A novel topological strategy is described for designing amorphous molecular solids suitable for optoelectronic applications. In this approach, chromophores are attached to a tetrahedral point of convergence. Stilbenoid units were covalently linked to tetraphenylmethane, tetraphenyladamantane, or tetraphenylsilane cores using palladium catalyzed coupling methodology. Thus, reaction of E(C6H5X)4 (E = C and adamantane, X = I; E = Si, X = Br) with styrene or 4,4'-tert-butylvinylstilbene under Heck coupling conditions yields the corresponding tetrakis(stilbenyl) (E(STB)4) and tetrakis(4-tert- butylstyrylstilbenyl) (E((t)BuSSB)4) compounds. Similarly, reaction of 1,1- diphenyl-2-(4-dihydroxyboronphenyl)ethene or 2-(4-pinacolatoboronphenyl)-3,3- diphenylacrylonitrile with tetrakis(4-bromophenyl)methane using Suzuki coupling methodology gives tetrakis(4,4'-(2,2-diphenyl-vinyl)-1, 1'- biphenyl)methane (C(DPVBi)4) or tetrakis(4,4'-(3,3-diphenylacrylonitrile)- 1,1'-biphenyl)methane (C(DPAB)4), respectively, in good yields. Compounds with more extended conjugation can also be prepared. Thus, reaction of excess 1-(4'-tert-butylstyryl)-4-(4'-vinylstyryl)benzene with C(C6H4I)4 provides tetrakis(4-(4'-(4''-tert-butylstyryl)styryl)stilbenyl)methane (C(4R-(t)Bu)4) in low yield (~20%). The more soluble analogue, tetrakis(4-(4'-(3,5-di- tert-butylstyryl)styryl)stilbenyl)methane (C(4R-2(t)Bu)4) is prepared similarly using 1-(3',5'-di-tert-butylstyryl)-4-(4'-vinylstyryl)benzene and in better yield (~80%). Alkoxy substituents can also be used to increase solubility. Tetrakis((4-(2',5'-dioctyloxy-4'-styryl)styryl)stilbenyl)methane, C(4R-(OC8H17)2)4, was prepared by treatment of C(C6H4I)4 with excess 2,5-dioctyloxy-1-styryl-4(4'-vinylstyryl)benzene (yield ~73%). The simple stilbenyl-derivatives were found by DSC measurements and powder diffraction experiments to be crystalline compounds. Comparison of single-crystal X-ray diffraction data shows that C(STB)4 and Si(STB)4 form isomorphous crystals. The larger E((t)BuSSB)4, C(DPVBi)4, and C(DPAB)4 compounds readily form amorphous glasses with elevated glass transition temperatures (T(g) = 142190 °C) in the absence of solvent. Extending the conjugation length of the arm leads to more stable glasses. For example, the glass transition temperature of C(4R-(t)Bu)4 was measured at 230 °C. Solution phase optical spectroscopic data of E((t)BuSSB)4 (E = C, adamantane, and Si) are characteristic of the parent distyrylbenzene chromophore. Films, however, show broad and significantly red-shifted emission spectra. In contrast, C(DPVBi)4 gives absorption and emission spectra which are nearly identical between dilute solution phase samples and neat solid films. The emission of C(DPAB)4 is broad and structureless, reminiscent of exciplex or excimer emission. Films of the tetramers with longer arms (C(4R-(t)Bu)4, C(4R- 2(t)Bu)4, and C(4R-(OC8H17)2)4) show emission properties which are dependent on sample history. Annealing the sample at elevated temperature leads to red-shifted emission as a result of better interdigitation between the optically active fragments.
- Wang, Shujun,Oldham Jr., Warren J.,Hudack Jr., Raymond A.,Bazan, Guillermo C.
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p. 5695 - 5709
(2007/10/03)
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- Fluorescence Studies of Poly(p-phenyleneethynylene)s: The Effect of Anthracene Substitution
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The poly(p-phenyleneethynylene) molecules, PI-PIII, synthesized by a palladium-catalyzed cross-coupling reaction of diiodobenzene derivatives and derivatives of 1,4-diethynylbenzene, are highly luminescent materials.The polymers are soluble by virtue of the -OC16H33 groups introduced on the aromatic rings and by controlling their molecular weight.The fluorescent quantum yields are between 0.35 and 0.40 depending on the material.The excited-state lifetimes of the polymers are 1-2 ns, slightly shorter than that of the model compund, 1,4-diphenylethynyl-2,5-dibutoxybenzene, which has a lifetime of 3 ns.Incorporation of anthracene, coupled at the 9,10-positions by using 9,10-dibromoanthracene, into the polymer backbone decreases the quantum yield to between 0.05 and 0.27 depending on the anthracene content.In addition, low-energy electronic transitions and longer wavelength emission bands associated with the anthracene group are produced.The polymers harvest optical energy and transfer it to the anthracene resulting in emission from this chromophore.In the case where only terminal anthracene units, introduced by using 9-bromo-10-phenylethynylanthracene, are present, the process is very efficient with >95percent of the energy being transferred to the end groups.
- Swager, Timothy M.,Gil, Caroline J.,Wrighton, Mark S.
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p. 4886 - 4893
(2007/10/02)
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