- Ferrocene metallopolymers of intrinsic microporosity (MPIMs)
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We show here that non-network metallopolymers can possess intrinsic microporosity stemming from contortion introduced by metallocene building blocks. Metallopolymers constructed from ferrocenyl building blocks linked by phenyldiacetylene bridges are synth
- Ambrose, Kenson,Feldblyum, Jeremy I.,Nyayachavadi, Audithya,Rondeau-Gagné, Simon,Walter, Kelly G.,Zhai, Tianran
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supporting information
p. 238 - 241
(2022/01/06)
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- A study on the synthesis, characterization, structural optimization, and conformational behaviors of bromo-substituted pyromelliticdiimide-based [2+2] macrocycle as structural units of covalently linked molecular tubes
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Synthesis and structural, photo physical, and conformational behaviors at variable temperature and structural optimization of the pyromelliticdiimide-based bromo-substituted [2 + 2] macrocycles are described. Cyclization of the diamine (3) with dianhydride (4) in THF, followed by dehydration of the resultant amic acids resulted in the isolation of the bromo-substituted [2 + 2] macrocycle 1 (4.5%). The dynamic temperature-dependent 1H NMR spectra and MO calculations revealed the presence of two possible conformers for the [2 + 2] macrocycle 1. The UV/Vis spectrum of 1 reveals the presence of a weak intramolecular CT interaction of electron-withdrawing pyromelliticdiimide moiety with the electron-donating hexyloxy-substituted xylyl moiety. The cyclic voltammetric measurement shows two two-electron reversible reduction processes.
- Bandyopadhyay, Arkasish,Halim, Md. Ershad,Hossain, Md. Elius,Shinmyozu, Teruo
-
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- Tunable optical properties of push-pull chromophores: End group effect
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A series of A-π-D-π-A type symmetrical push-pull chromophores with various end groups (e.g., trifluoroacetone, indanone, dicyano, isoxazolone and pyrazolinone) linked through a symmetric π-conjugated backbone (EDOT-phenylene vinylene-EDOT) was synthesized
- Tonga, Murat
-
supporting information
(2020/07/15)
-
- Supramolecular enantiomeric and structural differentiation of amino acid derivatives with achiral pillar[5]arene homologs
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Complexation of achiral pillar[5]arenes with chiral amines induced strong circular dichroism (CD) signals. The CD responses differed drastically depending on the nature of the amino acid guest, and they significantly varied and part of them even inverted, upon increasing the length of the alkyl chains of the pillar[5]arenes guests. Accordingly, this tactic allowed for the unprecedented simultaneous enantiomeric and structural differentiation of α-amino esters with homologous molecular hosts.
- Ji, Jiecheng,Li, Yizhou,Xiao, Chao,Cheng, Guo,Luo, Kui,Gong, Qiyong,Zhou, Dayang,Chruma, Jason J.,Wu, Wanhua,Yang, Cheng
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supporting information
p. 161 - 164
(2019/12/30)
-
- Linker-Dependent Singlet Fission in Tetracene Dimers
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Separation of triplet excitons produced by singlet fission is crucial for efficient application of singlet fission materials. While earlier works explored the first step of singlet fission, the formation of the correlated triplet pair state, the focus of
- Korovina, Nadezhda V.,Joy, Jimmy,Feng, Xintian,Feltenberger, Cassidy,Krylov, Anna I.,Bradforth, Stephen E.,Thompson, Mark E.
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supporting information
p. 10179 - 10190
(2018/07/30)
-
- Synthesis and characterization of 2,2′-bithiophene end-capped dihexyloxy phenylene pentamer and its application in a solution-processed organic ultraviolet photodetector
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In this work a new solution processable small organic material, namely 2,2′-bithiophene end-capped dihexyloxy phenylene pentamer (BHBT2) was synthesized, characterized and applied in the fabrication of an organic ultraviolet photodetector. The
- Lim, Lih Wei,Teh, Chin Hoong,Daik, Rusli,Sarih, Norazilawati Muhamad,Mat Teridi, Mohd Asri,Muhammad, Fahmi Fariq,Sulaiman, Khaulah
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p. 61848 - 61859
(2016/07/11)
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- Simultaneously enhancement of quantum efficiency and color purity by molecular design in star-shaped solution-processed blue emitters
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A series of fluorene-free bipolar star-shaped molecules, Sn-Cz-OXD (n = 1-5), with increasing conjugated length in branches were synthesized as high efficient blue emitters for OLEDs. With the extension of conjugated branches, the solid PL quantum efficiency and external quantum efficiency of Sn-Cz-OXD significantly increased with longer spacer, while the emission spectrum of these materials exhibited a blue-shift with enhanced color purity due to the unique molecular design. All materials maintained exceptionally high thermal stability after prolonged heat treatment at 150 °C in air. The photophysical, electrochemical, thermal properties of these emitters were studied in relation to the molecular structure. Nondoped device based on S4-Cz-OXD with structure ITO/PEDOT:PSS/EML/TPBI/LiF/Al emitted stable pure blue light with CIE coordinates of (0.157, 0.146). It exhibited high current efficiency and external quantum efficiency of 4.96 cd A-1 and 4.20%, respectively. These values are among the best results for solution-processed non-doped blue device based on fluorene-free materials, indicating its potential for commercial applications.
- He, Xuehan,Chen, Lei,Zhao, Yongbiao,Chen, Hui,Ng, Siu Choon,Wang, Xizu,Sun, Xiaowei,Matthew Hu, Xiao
-
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- Versatile bisethynyl[60]fulleropyrrolidine scaffolds for mimicking artificial light-harvesting photoreaction centers
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Fullerene-based tetrads, triads, and dyads are presented in which [60]fulleropyrrolidine synthons are linked to an oligo(p-phenyleneethynylene) antenna at the nitrogen atom and to electron-donor phenothiazine (PTZ) and/or ferrocene (Fc) moieties at the ?±
- Kremer, Adrian,Bietlot, Emerance,Zanelli, Alberto,Malicka, Joanna M.,Armaroli, Nicola,Bonifazi, Davide
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supporting information
p. 1108 - 1117
(2015/03/05)
-
- Energy-dissipative self-assembly driven in microflow: A time-programmed self-organization and decomposition of metastable nanofibers
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Energy-dissipative self-assembly in microflow enables us to approach an energetically unstable self-assembled structure, which undergoes morphological transition in a cascade manner from fibers, sheets, and finally "running down" to thermodynamically stable dots, with switching intermolecular interactions.
- Numata, Munenori,Sato, Akiko,Nogami, Rie
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supporting information
p. 995 - 997
(2015/08/24)
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- Polytriazole bridged with 2,5-diphenyl-1,3,4-oxadiazole moieties: A highly sensitive and selective fluorescence chemosensor for Ag+
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Fluorescent conjugated polytriazoles (FCP 1-4) containing both 2,5-diphenyl-1,3,5-oxadiazole (OXD) and 1,2,3-triazole moieties in the main chain were synthesized from aromatic diazide (1) and dialkynes (2-5) via click polymerization, respectively. In the polymers, OXDs (fluorophores) and triazole rings (generated via CuAAC acting as metal ion ligands) comprise a fluorescent system. The polytriazoles displayed relatively strong emission with quantum yields in the range of 0.20-0.28 at room temperature in DMF. The study on their ion-responsive properties showed that, although all four FCPs have good selectivity for Ag+, the integration of alkoxy side groups (methoxy for FCP 2, hexyloxy for FCP 3 and 2-ethylhexyloxy for FCP 4) to the main chains of the polytriazoles decreased their sensitivity for Ag+via alteration of the polymer aggregation status and electron density of the main chains. Thus FCP 1 is highly sensitive for Ag+, where its Ksv is as high as 1.44 × 105 M-1 and its lowest detection limit is in the ppb range (4.22 × 10-7 M). This study provides an efficient click approach to the synthesis of a novel fluorescence sensor for Ag+ detection, which could expand the application of click polymerization in designing fluorescence sensors based on the triazole unit. This journal is
- Cao, Shoupeng,Pei, Zhichao,Xu, Yongqian,Zhang, Ruina,Pei, Yuxin
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p. 45888 - 45896
(2015/06/08)
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- Dyes for sensitized solar cells by using [2.2]paracyclophane as a bridging unit
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Organic dyes that consist of a [2.2]paracyclophane moiety between a triphenylamine donor group and a cyanoacrylic acid acceptor group have exhibited considerably high values of open-circuit voltage (Voc) in the range of 0.69-0.74 V. In an exper
- Huang, Chiung Hui,Chang, Yuan Jay
-
supporting information
p. 4938 - 4942
(2014/12/10)
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- Lanthanide loading of luminescent multi-tridentate polymers under thermodynamic control
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This work illustrates the use of basic statistical mechanics for rationalizing the loading of linear multitridentate polymers with trivalent lanthanides, Ln(III), and identifies the specific ionic sizes of europium and yttrium as promising candidates for the further design of organized heterometallic f-f′ materials. Using [Ln(hfac)3] (hfac = hexafluoroacetylacetonate) as lanthanide carriers, the thermodynamically controlled formation of Wolf type-II lanthanidopolymers [{Ln(hfac) 3}m(L4)] is modeled with the help of two simple microscopic descriptors: (i) the intrinsic affinity of Ln(III) for the tridentate binding sites fN3Ln and (ii) the intermetallic interactions δE1-2Ln,Ln operating between two occupied adjacent sites. Selective complexation modulated by anticooperative interactions favors the fixation of Eu(III) in semiorganized lanthanidopolymers [{Eu(hfac)3} m(L4)] displaying exploitable light-downshifting.
- Babel, Lucille,Hoang, Thi Nhu Y.,Nozary, Homayoun,Salamanca, Jasmina,Guenee, Laure,Piguet, Claude
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p. 3568 - 3578
(2014/05/06)
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- Design and synthesis of polymeric chiral bicyclo[3.3.0] diene as reusable ligand for rhodium-catalyzed asymmetric 1,4-addition
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A series of A-B type sterically regular bicyclio[3.3.0] diene-based polymers were designed and synthesized as immobilized chiral diene ligands for asymmetric catalysis. With polymeric diene 6b, good to excellent enantioselectivities can be achieved in Rh-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated ketones. A series of A-B type sterically regular bicyclio[3.3.0] diene-based polymers were designed and synthesized as immobilized chiral diene ligands for asymmetric catalysis. By using polymeric diene, good to excellent enantioselectivities can be achieved in Rh-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated ketones. Copyright
- Yang, Hongyu,Xu, Minghua
-
supporting information
p. 119 - 122
(2013/08/24)
-
- Tuning the moisture and thermal stability of metal-organic frameworks through incorporation of pendant hydrophobic groups
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An isostructural series of NbO-type porous metal-organic frameworks (MOFs) with different dialkoxy-substituents of formula Cu2(TPTC-OR) (TPTC-OR = 2′,5′-di{alkyl}oxy-[1,1′:4′,1″-terphenyl]-3, 3″,5,5″-tetracarboxylate, R = Me, Et, nPr, nHex) has been synthesized and characterized. The moisture stability of the materials has been evaluated, and a new superhydrophobic porous MOF has been identified. The relationship between pendant side chain length and thermal stability has been analyzed by in situ synchrotron powder X-ray diffraction, showing decreased thermal stability as the side chain length is increased, contradictory to thermogravimetric decomposition studies. Additionally, the four materials exhibit moderate Brunauer-Emmett-Teller (BET) and Langmuir surface areas (1127-1396 m2 g-1 and 1414-1658 m2 g -1) and H2 capacity up to 1.9 wt % at 77 K and 1 bar.
- Makal, Trevor A.,Wang, Xuan,Zhou, Hong-Cai
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p. 4760 - 4768
(2013/12/04)
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- Heterogeneous palladium-catalyzed synthesis of aromatic ethers by solvent-free dehydrogenative aromatization: Mechanism, scope, and limitations under aerobic and non-aerobic conditions
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Starting from cyclohexanone derivatives and alcohols, both non-aromatic precursors, aryl ethers could be synthesized in good yields and with good selectivities in the presence of a catalytic amount of Pd/C, in one step, without added solvent, in a reaction vessel open to air. For less reactive substrates, the addition of 1-octene in a closed system under non-aerobic conditions improved the conversion. In addition, the catalyst could be recycled several times with no decrease in the yield of the aryl ether. The process was also used with tetralone derivatives and polyols. Several reactions were performed to propose a mechanism for this transformation. The formation of an enol ether followed by a dehydrogenation reaction seem to be the key steps of this reaction. Aryl ethers were prepared in good yields and with good selectivities in a solvent-free and heterogeneous catalytic dehydrogenative alkylation of cyclohexanones with various alcohols. Three different complementary routes were used, and for the first time, non-aerobic, safe conditions could be used. Moreover, the catalyst could be recycled several times with no decrease in the yield of the aryl ether. Copyright
- Sutter, Marc,Lafon, Romain,Raoul, Yann,Metay, Estelle,Lemaire, Marc
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supporting information
p. 5902 - 5916
(2013/09/23)
-
- Alkyloxy substituted organic dyes for high voltage dye-sensitized solar cell: Effect of alkyloxy chain length on open-circuit voltage
-
Three novel organic dyes (SB1, SB2, and SB3) containing 4-(hexyloxy)-N-(4-(hexyloxy)phenyl)-N-phenylaniline as electron donor and cyanoacrylic acid as electron acceptor bridged by alkyloxy (methyl = SB1, propyl = SB2 and hexyl = SB3) substituted p-phenylenevinylene linkers have been synthesized. Density functional theory (DFT) has employed to study electron distribution and intramolecular charge transfer. Increase in alkyl chain length in alkyloxy substituent leads to increase in open-circuit voltage (V OC), which is found to be related to the increased electron lifetime at open-circuit condition. Under AM 1.5 G 1 sun light illumination (100 mW/cm2), an optimized SB3-sensitized cell show a short-circuit photocurrent density (JSC) of 12.83 mA/cm2, an open-circuit voltage (VOC) of 0.745 V and a fill factor (FF) of 0.64, corresponding to an overall conversion efficiency (η) of 6.12%. Little degradation in η observed over 40 days is indicative of long-term stability of the SB-series dyes.
- Ko, Soo-Byung,Cho, An-Na,Kim, Mi-Jeong,Lee, Chang-Ryul,Park, Nam-Gyu
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experimental part
p. 88 - 98
(2012/04/04)
-
- A facile approach to highly efficient and thermally stable solid-state emitters: Knitting up AIE-active TPE luminogens by aryl linkers
-
A facile approach to thermally stable and efficient solid-state emitters is proposed. By hooking up tetraphenylethene (TPE) units through aryl linkers under Suzuki coupling conditions, a series of arylene bis(tetraphenylethene)s (TPE-Ar-TPE Ar = 2, 5-dime
- Chan, Carrie Yin Kwan,Lam, Jacky Wing Yip,Zhao, Zujin,Deng, Chunmei,Chen, Shuming,Lu, Ping,Sung, Herman H.Y.,Kwok, Hoi Sing,Ma, Yuguang,Williams, Ian D.,Tang, Ben Zhong
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p. 949 - 958
(2013/01/15)
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- A facile approach to highly efficient and thermally stable solid-state emitters: Knitting up aie-active tpe luminogens by aryl linkers
-
A facile approach to thermally stable and efficient solid-state emitters is proposed. By hooking up tetraphenylethene (TPE) units through aryl linkers under Suzuki coupling conditions, a series of arylene bis(tetraphenylethene)s (TPE-Ar-TPE Ar=2,5- dimeth
- Chan, Carrie Yin Kwan,Lam, Jacky Wing Yip,Zhao, Zujin,Deng, Chunmei,Chen, Shuming,Lu, Ping,Sung, Herman H. Y.,Kwok, Hoi Sing,Ma, Yuguang,Williams, Ian D.,Tang, Ben Zhong
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p. 949 - 958
(2014/01/17)
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- Self-assembled monolayers of clamped oligo(phenylene-ethynylene- butadiynylene)s
-
Rigid rod oligo(phenylene-ethynylene-butadiynylene)s (oPEBs), "half-rings" of two rigid rods connected via a molecular clamp unit, and shape-persistent macrocycles (cyclic "half-ring dimers") are synthesized and their self-assembled monolayers (SAMs) are
- Jester, Stefan-S.,Schmitz, Daniela,Eberhagen, Friederike,Hoeger, Sigurd
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supporting information; experimental part
p. 8838 - 8840
(2011/09/14)
-
- Synthesis and characterization of a fluorescent polymer containing 2,6-bis(2-thienyl)pyridine moieties as a highly efficient sensor for Pd 2+ detection
-
A novel conjugated polymer chemosensor 1 containing 2,6-bis(2-thienyl) pyridine has been synthesized and exhibits a high sensitivity and selectivity for palladium ion detection based on the fluorescent quenching effect.
- Liu, Bin,Bao, Yinyin,Du, Fanfan,Wang, Hu,Tian, Jiao,Bai, Ruke
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supporting information; experimental part
p. 1731 - 1733
(2011/03/22)
-
- Aryl trihydroxyborate salts: Thermally unstable species with unusual gelation abilities
-
A series of aryl trihydroxyborate salts were synthesized and found to form gels in benzene. The compounds were thermally unstable and readily underwent protodeboronation in solution and the solid state. Gelation could be induced without decomposition via sonication. Subsequent characterization studies revealed an unusual dependence of gel properties on alkyl chain length.
- Moy, Cheryl L.,Kaliappan, Raja,McNeil, Anne J.
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experimental part
p. 8501 - 8507
(2011/12/04)
-
- Synthesis and optical properties of molecular rods comprising a central core-substituted naphthalenediimide chromophore for carbon nanotube junctions
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The synthesis of a series of molecular rods 1-5, designed to bridge the gap of a carbon nanotube junction in order to emit light as a characteristic signal of integrated molecules, is reported. The molecular rods consist of a central naphthalenediimide (NDI) core, which itself is substituted with benzylamino and benzylsulfanyl groups, providing distinct absorption and emission properties. The NDI core is embedded in an oligo(phenylene ethynylene) (OPE) system providing the rod-like structure required to bridge gaps between nanoelectrodes. The number of repeating units of the OPE is varied to adjust the length of the target compounds between 2.3 and 6.6 nm. The OPE parts are terminally functionalized with polyaromatic hydrocarbon groups (naphthalene, phenanthrene, anthracene or pyrene), which possess affinity with the surface of the carbon nanotubes due to van der Waals interactions. Synthetic protocols based on Sonogashira-Hagihara couplings were developed to build up the OPE backbone. Bifunctional iodophenyl acetylene derivative 33 served as a key building block in a coupling-deprotecting-coupling sequence. The NDI building block was synthesized by an aromatic nucleophilic substitution reaction of 2,6-dichloro-1,4,5,8-tetracarboxylic acid naphthalenediimide derivative 9 and the corresponding amine and sulfide (i.e., 11, 12), respectively. The convergent synthesis allows modular assembly of the NDI and OPE parts in a final Sonogashira-Hagihara coupling reaction. The target structures were fully characterized by NMR spectroscopy and mass spectrometry. Further, the optical properties of compounds 3-5 in solution, and on a graphene surface were qualitatively investigated. A Dexter-type energy transfer from the OPE unit to the NDI unit was observed. The studies of target structures 3-5 revealed that diamino-functionalized compound 3 is ideally suited for the envisaged single molecule electroluminescence experiments. The synthesis of a series of over 6-nm long modular rods with a central decoupled naphthalenediimide (NDI) chromophore isreported. Their spectroscopic properties are adjusted by varying the substituents of the NDI core
- Grunder, Sergio,Munoz Torres, David,Marquardt, Christoph,Balaszczyk, Alfred,Krupke, Ralph,Mayor, Marcel
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supporting information; experimental part
p. 478 - 496
(2011/03/22)
-
- Iterative synthesis of heterotelechelic oligo(phenylene-vinylene)s by olefin cross-metathesis
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A novel iterative synthesis of heterotelechelic oligo(phenylene-vinylene)s using olefin cross-metathesis is reported. The metathesis homologation proceeds in good yields and allows for further functionalization, including the facile formation of donor-acceptor complexes and repeating sequence copolymers.
- Norris, Benjamin N.,Pan, Tianqi,Meyer, Tara Y.
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supporting information; experimental part
p. 5514 - 5517
(2011/03/18)
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- Directional hydrogen bonding controlled 2D self-organization of phenyleneethynylenes: From linear assembly to rectangular network
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The effect of the carboxylic acid substituent position of phenyleneethynylene systems on the 2D self-organization is revealed by scanning tunneling microscopy.
- Ramesh,Thomas, K. George
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supporting information; experimental part
p. 3457 - 3459
(2010/07/16)
-
- Metal ion detection by luminescent 1,3-bis(dimethylaminomethyl) phenyl receptor-modified chromophores and cruciforms
-
Chromophores ranging from simple small molecule π-conjugated systems comprised of phenylene ethynylene or fluorenylethynyl units to cross-conjugated Bunz-type cruciforms have been derivatized to include 1,3- bis(dimethylaminomethyl)phenyl moieties. The photophysical responsiveness of these diamino-substituted chromophores to metal ions has been examined. Both emission enhancement (turn-on) and ratiometric fluorescence detection of Cu 2+ and Zn2+ ions have been achieved in THF.
- Mangalum, Anshuman,Gilliard Jr., Robert J.,Hanley, Jessica M.,Parker, Austa Marie,Smith, Rhett C.
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supporting information; experimental part
p. 5620 - 5627
(2011/02/18)
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- Synthesis of linear and V-shaped oligo(phenylene ethynylene) derivatives: Geometric effects on photophysical properties
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A series of linear and V-shaped oligo(phenylene ethynylene) derivatives 1-3 were synthesized through sequent Sonogashira coupling and propargyl alcohol deprotection reaction in high yields. The alkoxy chains (i.e., n-hexyloxy groups) were introduced to as
- Yuan, Si Chun,Han, Shu Liang,Ge, Xing,Wang, Hui Chuan
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scheme or table
p. 97 - 100
(2010/11/17)
-
- Substituted poly(p-phenylene) thin films via Surface-Initiated Kumada-Type catalyst transfer polycondensation
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Conjugated polymer films of unsubstituted and alkoxy-substituted poly(p-phenylene) have been prepared via a Kumada-type catalyst-transfer polycondensation in a grafting-from configuration. A surface-bound external initiator was formed by reacting a Ni(O) complex with a thienyl bromide monolayer, and this surface-bound initiator was used to polymerize several Grignard monomers prepared from the corresponding 1,4-dihalobenzenes resulting in surface-bound, conjugated polymer chains with thickness up to 30 nm. A series of 1,4-diodo monomers with alkoxy side chains ranging from unsubstituted 1,4-diiodobenzene to 1,4-diiodo-2,5-dihexyloxybenzene were polymerized in order to explore the influence of steric bulk on the surface-initiated polymerization process. Within the series of molecules, it was observed that monomers with smaller, less bulky side chains were more easily polymerized from the surface, resulting in smooth, regular films for unsubstituted and methoxy-substituted polyphenylene. Islands of polymer growth were observed with the ethoxy-substituted material and only sparse, irregular growth for the hexyloxysubstituted polymer. The resulting films were characterized by AFM., infrared spectroscopy, ellipsometry, and UV-vis spectroscopy.
- Marshall, Nicholas,Sontag, S. Kyle,Locklin, Jason
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experimental part
p. 2137 - 2144
(2011/10/08)
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- Mechanistic studies on Ni(dppe)Cl2-catalyzed chain-growth polymerizations: Evidence for rate-determining reductive elimination
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The mechanisms for Ni(dppe)Cl2-catalyzed chain-growth polymerization of 4-bromo-2,5-bis-(hexyloxy)phenylmagnesium chloride and 5-bromo-4-hexylthiophen-2-ylmagnesium chloride were investigated. Rate studies utilizing IR spectroscopy and gas chromatography revealed that both polymerizations exhibit a first-order dependence on the catalyst concentration but a zeroth-order dependence on the monomer concentration. 31P NMR spectroscopic studies of the reactive organometallic intermediates suggest that the resting states are unsymmetrical NiII-biaryl and Ni II-bithiophene complexes. In combination, the data implicate reductive elimination as the rate-determining step for both monomers. Additionally, LiCl was found to have no effect on the rate-determining step or molecular weight distribution in the arene polymerization.
- Lanni, Erica L.,McNeil, Anne J.
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supporting information; experimental part
p. 16573 - 16579
(2010/02/16)
-
- P-phenyleneethynylene molecular wires: Influence of structure on photoinduced electron-transfer properties
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A series of donor-acceptor arrays (exTTF-oPPE-C60) containing π-conjugated oligo(phenyleneethynylene) wires (oPPE) of different length between π-extended tetrathiafulvalene (exTTF) as electron donor and fullerene (C60) as electron acceptor has been prepared by following a convergent synthesis. The key reaction in these approaches is the bromo-iodo selectivity of the Hagihara-Sonogashira reaction and the deprotecting of acetylenes with different silyl groups to afford the corresponding donor-acceptor conjugates in moderate yields. The electronic interactions between the three electroactive species were determined by using UV-visible spectroscopy and cyclic voltammetry. Our studies clearly confirm that, although the C60 units are connected to the exTTF donor through π-conjugated oPPE frameworks, no significant electronic interactions are observed in the ground state. Theoretical calculations predict how a simple exchange from C=C double bonds (i.e., oligo(p-phenylenevinylene) to C≡C triple bonds (i.e., oPPE) in the electron donor-acceptor conjugates considerably alters long-range electron transfer. Photoexcitation of exTTF-oPPE-C 60 leads to the following features: a transient photoproduct with maxima at 660 and 1000 nm, which are unambiguously attributed to the photolytically generated radical-ion-pair state, [exTTF+-oPPE- C60-]. Both charge-separation and charge-recombination processes give rise to a molecular-wire behaviour of the oPPE moiety with an attenuation factor (β) of (0.2 ±0.05) A-1.
- Wielopolski, Mateusz,Atienza, Carmen,Clark, Timothy,Guldi, Dirk M.,Martin, Nazario
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experimental part
p. 6379 - 6390
(2009/06/18)
-
- New luminescent compositions and their uses
-
High quantum yield luminescent monomers, oligomers, and polymers, comprising benzotriazole repeating units and derivatives thereof have been discovered and utilized in optical devices and components therefor, including electroluminescent devices, light emitting devices, photoluminescent devices, organic light emitting diodes (OLEDs), OLED displays, sensors, and the like.
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-
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- Catalyst-transfer polycondensation for the synthesis of poly(p-phenylene) with controlled molecular weight and low polydispersity
-
To examine whether catalyst-transfer polycondensation, which affords well-defined polythiophenes, has generality for other conjugated polymers, the synthesis of poly(p-phenylene) (PPP) with various Ni catalysts was investigated. Monomer 1, 1-bromo-4-chlor
- Miyakoshi, Ryo,Shimono, Kyohei,Yokoyama, Akihiro,Yokozawa, Tsutomu
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p. 16012 - 16013
(2007/10/03)
-
- The CA.M lattice revisited. Gel formation from a linear bis-isocyanuric acid and 2-amino-4,6-bis-(4-tert-butylphenylamino)-1,3,5-triazine
-
Five bis(isocyanuric) acid dimers have been prepared and characterised. The introduction of flexible alkyl chains was necessary to aid solubility. On mixing with N,N-bis(4-tert-butyphenyl)melamine in THF followed by slow evaporation, a viscous gel can form which is interpreted as evidence for the assembly of an infinite 2-D hydrogen bonded network.
- Plater, M. John,Sinclair, James P.,Aiken, Stuart,Gelbrich, Thomas,Hursthouse, Michael B.
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p. 6385 - 6394
(2007/10/03)
-
- Synthesis, characterization, and physical properties of monodisperse oligo(p-phenyleneethynylene)s
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A new stepwise synthesis method for the preparation of precisely defined oligo(p-phenyleneethynylene)s (OPEs) is described. High-purity monomer, trimer, pentamer, heptamer, and nonamer of OPEs with dihexyloxy side groups and trimethylsilyl (TMS) or thioac
- Zhou, Chuan-Zhen,Liu, Tianxi,Xu, Jing-Mei,Chen, Zhi-Kuan
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p. 1457 - 1464
(2007/10/03)
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- A giant conjugated molecular ring
-
Ever increasing circles? The giant cycle 1 has a diameter of 12 nm making it the largest, shape persistent and monodisperse cyclic molecular structure designed and synthesized to date. A modular approach consisting of a series of subsequent dimerization s
- Mayor, Marcel,Didschies, Claudia
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p. 3176 - 3179
(2007/10/03)
-
- Syntheses and emission properties of novel violet-blue emissive aromatic bis(diazaborole)s
-
Violet-blue emission from novel aromatic bis(diazaborole)s, which were synthesized by the reaction of 2,5-bis(hexyloxy)-1,4-phenylenediboronic acid and 1,2-phenylenediamine derivatives or diaminonaphthalene derivatives, is described. White-blue emission front a 4-methoxy-1,2-phenylenediamine-derived molecule was observed in DMF using 340 nm as the excitation wavelength.
- Maruyama, Sumio,Kawanishi, Yuji
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p. 2245 - 2249
(2007/10/03)
-
- Tuning of photo- and electroluminescence of new soluble, PPV-analogous short-chain compounds with naphthalene moieties
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A series of oligomers analogous to poly(p-phenylenevinylene) (PPV), combining naphthalene and benzene as aromatic units, have been synthesized by a Knoevenagel reaction. By measuring UV/Vis spectra, photoluminescence (PL) and electroluminescence (EL), we
- Martinez-Ruiz,Behnisch,Schweikart,Hanack,Lueer,Oelkrug
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p. 1294 - 1301
(2007/10/03)
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- Reactivity of silyl monomers for the oxidative polymerization of phenylene units
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Oxidative coupling of silyl monomers containing phenylene units was performed electrochemically and chemically using FeCl3 as oxidant. 2,5-Trimethylsilyl-1,4-dihexoxybenzene led to poly (2.5-dihexoxyparaphenylene) with a degree of polymerization higher than the one obtained upon oxdative coupling of non silyl monomers. The coupling reaction was however moderately improved in the case of 3,6-bis-dimethylsilyl(N-n-butylcarbazole). The role of the silyl substituents during the oxidative polymerization is dicussed.
- Bouachrine, Mohammed,Lere-Porte, Jean-Pierre,Moreau, Joel J. E.
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p. 265 - 278
(2007/10/03)
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- Functionalized major-groove and minor-groove chiral polybinaphthyls: Application in the asymmetric reaction of aldehydes with diethylzinc
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A series of functionalized and optically active major-groove polybinaphthyls and minor-groove polybinaphthyls have been synthesized by using the Suzuki coupling reaction and have been spectroscopically characterized. The application of these chiral polymers in the asymmetric addition of diethylzinc to aldehydes has been studied. A minor-groove polybinaphthyl is found to be an excellent catalyst for the asymmetric reaction of diethylzinc with a number of aldehydes. The molecular weight and the molecular weight distribution of the polymer have little effects on the catalytic process. The chiral polymer can be easily recovered and reused without loss of catalytic activity as well as enantioselectivity. These rigid and sterically regular chiral polybinaphthyls represent a new generation of enantioselective polymeric catalysts. The reaction of the polybinaphthyls as well as certain monomeric binaphthyl molecules with diethylzinc has been investigated which has provided further information on the novel polymeric catalysts.
- Hu, Qiao-Sheng,Huang, Wei-Sheng,Vitharana, Dilrukshi,Zheng, Xiao-Fan,Pu, Lin
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p. 12454 - 12464
(2007/10/03)
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- Alkoxylated p-phenylenevinylene oligomers: Synthesis and spectroscopic and electrochemical properties
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Twenty-one n-alkoxy substituted phenylenevinylene oligomers were synthesized, varying in size, number and position of the OR groups. IR,MS and solubility data are presented. NMR measurements provided the molecular structure as well as information about conformations and molecular dynamics. UV and of cyclic voltammetric data give correlations of chemical structure (number and position of OR substituents) with separate HOMO and LUMO energies.
- Ndayikengurukiye, Henri,Jacobs, Sven,Tachelet, Wim,Van Der Looy, Johan,Pollaris, Anne,Geise, Herman J.,Claeys, Magda,Kauffmann, Jean M.,Janietz, Silvia
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p. 13811 - 13828
(2007/10/03)
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- Effects of side arm length and structure of para-substituted phenyl derivatives on their binding to the host cyclobis(paraquat-p-phenylene)
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The binding constants with the host cyclobis(paraquat-p-phenylene), 14+, have been determined in CH3CN by UV-vis spectrophotometry for a series of p-phenylene guests, symmetrically substituted with side arms of varying length and fun
- Castro, René,Nixon, Kendric R.,Evanseck, Jeffrey D.,Kaifer, Angel E.
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p. 7298 - 7303
(2007/10/03)
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- Selective etherification of polyhydroxybenzenes using PEG 200 as solvent or cosolvent
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The monoalkylation of hydroquinone is performed using PEG 200 as a solvent or a cosolvent.The effect on the selectivity of the base strength, the temperature, and the percentage of cosolvent are discussed.The substituted phenols were found to behave differently upon etherification.When a carboxylic function is present in the ring, the hydroxybenzoic acids were selectively etherified using pure PEG and sodium hydroxyde as a base.Substituted diphenols were selectively etherified using a mixture of PEG and dioxan and potassium hydrogencarbonate as a base.Keywords - etherification / selectivity / polyhydroxybenzenes / polyethylene glycol
- Berdague, P.,Perez, F.,Courtieu, J.,Bayle, J. P.
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p. 475 - 480
(2007/10/02)
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