- Restricted diffusion of guest molecules in polymer thin films on solid substrates as revealed by three-dimensional single-molecule tracking
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3D single-molecule tracking revealed that the translational diffusion of guest dyes in poly(2-hydroxyethyl acrylate) thin films on glass substrates was confined in a horizontal layer at a distance longer than 300-700 nm from the surface of the substrate. This peculiar long-range effect suggests that the interaction between the host polymer and the interface could affect the properties of polymers at a much longer distance than conventionally estimated.
- Ito, Syoji,Taga, Yuhei,Hiratsuka, Kengo,Takei, Satoshi,Kitagawa, Daichi,Kobatake, Seiya,Miyasaka, Hiroshi
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- Structural refinement of ladder-type perylenediimide dimers: A classical tale of conformational dynamics
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We have synthesized and thoroughly characterized two representative ladder-type acetylene-bridged perylenediimide dimers bearing long alkyl chain solubilizing groups, bis[1-ethynyl-N,N′-bis(1-hexylheptyl)-perylene-3,4:9, 10-tetracarboxylic diimide] ([PDICC]2, 1) and 1,1′-ethynyl- bis[N,N′-bis(1-hexylheptyl)-perylene-3,4:9,10-tetracarboxylic diimide] ([PDI]2CC, 2). In these dimeric PDI molecules, NMR-based structural characterization became nontrivial because severe 1H spectral broadening and greater than expected numbers of observed 13C resonances substantially complicated the interpretation of traditional 1-D spectra. However, rational two-dimensional NMR approaches based on both homo- and heteronuclear couplings (1H-1H COSY; 1H-13C HSQC), in conjunction with high-level structural DFT calculations (GIAO/B3LYP/6-31G(d,p)/PCM, chloroform), were readily applied to these structures, producing well-defined analytical characterization, and the associated methodology is described in detail. Furthermore, on the basis of dynamic NMR experiments, both 1 and 2 were found to exist in a perylene-centered conformational dynamic equilibrium (ΔG? = 13-17 kcal/mol), which primarily caused the observed ambiguities in conventional 1-D spectra.
- Myahkostupov, Mykhaylo,Prusakova, Valentina,Oblinsky, Daniel G.,Scholes, Gregory D.,Castellano, Felix N.
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- Original Suzuki–Miyaura Coupling Using Nitro Derivatives for the Synthesis of Perylenediimide-Based Multimers
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A series of perylenediimide (PDI)-based multimers were synthesized using an original Suzuki–Miyaura Coupling (SMC) reaction. The new approach considers the reaction between 1-nitroPDI as the electrophilic reagent with a wide variety of boronic esters to reach PDI dimers, trimers and tetramers which are of particular interest as Non-Fullerene Acceptors (NFAs) in organic photovoltaics. In this work, we compared the reactivity of 1-bromoPDI and 1-nitroPDI towards this pallado-catalyzed cross-coupling reaction. Considering that 1-nitroPDI is more accessible in terms of selectivity, time reaction, purification efficiency, atom economy, etc, we have shown that the use of nitroarenes is largely favored in the preparation of these PDI-based multimers. The latter were characterized with determination of their spectroscopic and electrochemical properties. With the aim of extending this SMC reaction to N-annulated PDI analogues, an original and efficient transformation of nitro-PDI into pyrrole-fused PDI was found as an alternative to the well-known reductive Cadogan cyclization. The SMC reaction was applied to bromo and nitro N-annulated PDI derivatives, and DFT calculations were accomplished in order to clarify the oxidative addition step of the cross-coupling and understand the difference of reactivity between the bromo- and nitro-PDI based electrophiles.
- Rocard, Lou,Hatych, Danylo,Chartier, Thomas,Cauchy, Thomas,Hudhomme, Piétrick
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- New cyclotriphosphazene based nanotweezers bearing perylene and glycol units and their non-covalent interactions with single walled carbon nanotubes
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We report on the design, synthesis and characterization of three new amphiphilic four fragment cyclotriphosphazene nanotweezers based on thermally stable carrier/router cyclotriphosphazene, extended polycyclic aromatic perylene bisimides with hydrophobic aliphatic tail and solvophilic glycol units, suitable for the exfoliation of single-walled carbon nanotubes (SWCNTs). The ultrasonication of SWCNT and new cyclotriphosphazene derivatives provided disentangled and undamaged SWCNTs, which interact with the perylene units through π–π interactions. The newly synthesized perylene-cyclotriphosphazenes were characterized by elemental analysis, mass, 31P, 1H and 13C NMR techniques. The photophyisical behavior of cyclotriphosphazene derivatives and their nanocomposites were investigated via UV– Vis absorption and fluorescence emission spectroscopy. It was found that non-geminal- cis-tris- perylenebisimide substituted compound exhibit an additional fluorescence peak compared with the parent compounds which is consistent with an intramolecular excimer formation. Prepared nanocomposites were also characterized via Raman spectroscopy and the morphological features were analyzed by HR- TEM. The quality of the nanocomposite dispersions in water were evaluated by zeta potential analysis.
- Eserci, Hande,?enkuytu, Elif,Okutan, Elif
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- Self-organized perylene diimide nanofibers
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A propeller-shaped perylene diimide trimer was synthesized and a simple evaporation method was used for the self-organization of trimer molecules into fluorescent nanofibers. The sizes of these fibers-from 4 to 150 nm in diameter - were measured by atomic force microscopy and can be controlled by adjusting the concentration of the initial solution. The aspect ratios (length/height) are around 500. The plane of the trimer was determined by polarized scanning confocal microscopy to be perpendicular to the axis of the fibers, in agreement with molecular mechanics calculations. UV/vis and NMR spectroscopies were used to monitor concentration-dependent π-π stacking in solution. Single-fiber fluorescence imaging and spectroscopy were performed using a total internal reflection fluorescence microscope equipped with a digital color camera and imaging CCD spectrometer. Strongly red-shifted fluorescence from these fibers indicates a high degree of electronic delocalization, and breaking up this delocalization by photobleaching blue-shifts the emission toward that of an isolated noninteracting molecule. The delocalization along these nanofibers and the ability to study the electronic structure using fluorescence make them potentially useful in nanoscale devices, such as field effect transistors and photoconductors.
- Yan, Ping,Chowdhury, Arindam,Holman, Michael W.,Adams, David M.
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- Perylenebisimide-fullerene dyads as heavy atom free triplet photosensitizers with unique singlet oxygen generation efficiencies
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We report the synthesis, characterization, photophysical and photochemical properties of two novel perylenebisimide-fullerene dyads (7 and 8) bearing one or two perylenebisimide (PBI) units as light harvester and a fullerene as spin converter. The molecular structures of all synthesized compounds were elucidated by elemental analyses, mass spectrometry, FT-IR, 1H and 13C NMR techniques. Their optical properties were investigated by UV–vis absorption and 2D/3D fluorescence emission spectroscopies. The photochemical studies via direct and indirect method endorsed PBI-fullerene dyads (7 and 8) as efficient heavy atom free tripletphotosensitizers whereas perylene derivatives did not exhibit any singlet oxygen production. The PBI-fullerene dyads exhibit excellent singlet oxygen quantum yields of 0.93 and 0.95. The PBI-fullerene dyads (7 and 8) are also able to use in the photooxidation of 1,5-dihydroxynaphtalene (DHN) to produce juglone and are recognized as stronger than MB as conventional triplet photosensitizers.
- ?ztürk, Ezel,Eserci, Hande,Okutan, Elif
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- Solvents Effects on Film Morphologies and Memory Behavior of a Perylenediimide-Containing Pendent Polymer
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The large polydispersity index of functional pendant polymers has hindered their application in semiconductors. Herein, a novel pendant polymer with perylenediimide (PDI) in the side chains was successfully synthesized through ring-opening metathesis poly
- Wang, Ming,Zhang, Qi-jian,Li, Zhuang,Li, Hua,Lu, Jian-Mei
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- Control of the molecular geometry and nanoscale morphology in perylene diimide based bulk heterojunctions enables an efficient non-fullerene organic solar cell
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Herein we present the design of three perylene diimide (PDI) derivatives with different molecular geometries; namely the monomeric PDI1, the bay-linked PDI2 dimer, and the bay-linked PDI4 tetramer with a 9,9′-spirobifluorene core that are utilized as electron acceptors in non-fullerene organic solar cells (OSCs). In all cases the PTB7-Th polymer is used as the electron donor. Among the three PTB7-Th:PDI systems, the highest power conversion efficiency (PCE) is obtained by the PDI4-based OSC device that exhibits a maximum PCE = 6.44% followed by the PDI2-based (PCE = 5.32%) and PDI1-based (PCE = 2.48%) devices. The detailed study of the photoluminescence quenching, morphology and temperature-dependent charge transport properties of the three systems reveal that the highest PCE of PTB7-Th:PDI4 is a consequence of the three-dimensional (3D) molecular architecture of PDI4 that tunes energetic disorder in the PDI phase and contributes to the improvement of electron transport. Transient photovoltage characterization experiments further identify that the actual effect coming from the 3D molecular geometry of the PDI4 acceptor on PCE is the minimization of non-geminate charge recombination losses. This study provides updated guidelines for optimizing further the molecular structure of 3D small molecular electron acceptors that can be used in highly efficient non-fullerene OSCs.
- Singh,Lee,Kim,Keivanidis,Cho
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- PDI-based heteroacenes as acceptors for fullerene-free solar cells: Importance of their twisted geometry
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Two perylenediimide (PDI) derivatives (FP4TT2T and FP43T) with extended conjugation have been successfully synthesized. Due to their long fused D-A (D: donor and A: acceptor) molecular structures, PDI-based heteroacenes have rigid backbones and exhibit strong light absorption in the 300-600 nm range. With the contribution from the PDI moiety with strong electron affinity, the molecules possess low energy levels of LUMOs (ca. -3.7 eV), fitting well as acceptors for fullerene-free organic solar cells (OSCs). OSC devices containing FP4TT2T and FP43T were fabricated and fully characterized. It is found that the geometric twist in PDI-based heteroacenes as acceptors could enhance the performance of OSC devices. OSCs based on FP43T with a more twisted geometry achieved a power conversion efficiency of 6.05%, which is higher than those based on the FP4TT2T counterpart.
- Chen, Huaqing,Wang, Ling,Sun, Hua,Liu, Qian,Tan, Xiao,Sang, Shenglong,Wu, Bo,Zhang, Cong,Chen, Fei,Hang, Xiao-Chun,Chen, Zhi-Kuan
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- Encapsulation induced aggregation: a self-assembly strategy for weakly pi-stacking chromophores
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Molecular assembly of weakly pi-stacking core-substituted naphthalene diimides (cNDIs) requires the participation of strong side-group interactions. Spatial confinement within a micellar core leads to locally elevated concentrations and reduced entropy that drives a rapid aggregation, often followed by a slower aggregate reorganization. Fast aggregation kinetics leads to self-sorting of aggregates.
- Sao, Soumik,Mukherjee, Ishita,De, Priyadarsi,Chaudhuri, Debangshu
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- New perylenebisimide decorated cyclotriphosphazene heavy atom free conjugate as singlet oxygen generator
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Perylenebisimide-cyclotriphosphazene based inorganic-organic system was synthesized by a multistep procedure. The substitution reaction of asymmetric perylenebisimide (PBI) derivative with the hexachloroyclotriphosphazene (trimer) resulted in the formation of fully PBI decorated cyclotriphosphazene (5). The identity of newly synthesized compound (5) was confirmed by using 31P, 1H and 13C NMR spectroscopies and mass spectrometry. The photophysical (UV- Vis absorption, fluorescence emission, fluorescence lifetime and fluorescence quantum yield) and photochemical (the singlet oxygen generation, and photostability) properties of this conjugate were investigated as novel heavy atom free triplet photosensitizer. The singlet oxygen quantum yield of the PBI-cyclotriphosphazene (5) was calculated to be 0.86 which is good for a heavy atom free triplet photosensitizer. These results will add to the development of cyclotriphosphazene based heavy atom free singlet oxygen triplet photosensitizer systems for applications in organic oxygenation reactions.
- Okutan, Elif,Eserci, Hande,?enkuytu, Elif
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- Energy transfer in pendant perylene diimide copolymers
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We report the synthesis, characterisation and polymerisation of two novel asymmetric perylene diimide acrylate monomers. The novel monomers form a sensitiser-acceptor pair capable of undergoing F?rster resonance energy transfer, and were incorporated as copolymers with tert-butyl acrylate. The tert-butyl acrylate units act as spacers along the polymer chain allowing high concentrations of dye while mitigating aggregate quenching, leading to persistent fluorescence in the solid state at high concentrations of up to 0.3 M. Analysis of fluorescence kinetics showed efficient energy transfer between the optically dense sensitiser and the lower concentration acceptor luminophores within the polymer. This reduced reabsorption within the material demonstrates that the copolymer-scaffold energy transfer system has potential for use in luminescent solar concentrators.
- Davis, Nathaniel J.L.K.,Macqueen, Rowan W.,Roberts, Derrick A.,Danos, Andrew,Dehn, Sabrina,Perrier, Sébastien,Schmidt, Timothy W.
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- An unusual β-oxidation of N-functionalized alkyl chains by 1H-imidazole
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The 1H-imidazole-mediated condensation of primary aliphatic amines with perylene-3,4: 9,10-tetracarboxylic bis-anhydride resulted in by-products where the aliphatic group was functionalized in the β-position by imidazole units.
- Langhals, Heinz,Gold, Josef
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- Two asymmetrical perylene diimide derivatives: Synthesis, optical-electrochemical properties and morphologies of self-assembly
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Perylene diimides (PDIs) belong to an important class of photoactive materials due to their excellent electrical and photophysical properties. Highly controlled aggregation and self-assembly attributed to the large π-conjugated aromatic scaffold have led to a variety of optoelectronic applications. In this manuscript, two PDI derivatives PDI-1 and PDI-2 with unsymmetrical N-substitution of amine and ester-bridge were designed and synthesized. These two compounds were characterized by NMR, Fourier transform infrared (FT-IR), and high-resolution mass spectrometry (HRMS). The photophysical properties were studied by UV–Vis absorption and fluorescence spectroscopy. Cyclic voltammograms of PDI-1 and PDI-2 were investigated and HOMO and LUMO energy levels of both two PDIs were estimated as ?6.2 and ?3.9 ?eV, respectively. Thermal properties were also studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). PDI-1 was assembled into nanotubes while PDI-2 was assembled into nanobelts respectively, via a reprecipitation method. PDI-1 and PDI-2 show good potential application in organic devices such as solar cells, organic field-effect transistors (OFETs) and so on.
- Liu, Jian,Song, Yuting,Tao, Jiayu,Xu, Hai-Jun,Zhang, Jiuxuan
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- Supramolecular Nanopatterns of Molecular Spoked Wheels with Orthogonal Pillars: The Observation of a Fullerene Haze
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Molecular spoked wheels with intraannular functionalizable pillars are synthesized in a modular approach. The functionalities at their ends are variable, and a propargyl alcohol, a [6,6]-phenyl-C61-butyrate, and a perylene monoimide are investigated. All compounds form two-dimensional crystals on highly oriented pyrolytic graphite at the solid–liquid interface. As determined by submolecularly resolved scanning tunneling microscopy, the pillars adopt equilibrium distances of 6.0 nm. The fullerene has a residual mobility, limited by the length of the flexible connector unit. The experimental results are supported and rationalized by molecular dynamics simulations. These also show that, in contrast, the more rigidly attached perylene monoimide units remain oriented along the surface normal and maintain a smallest distance of 2 nm above the graphite substrate. The robust packing concept also holds for cocrystals with molecular hexagons that expand the pillar–pillar distances by 15 % and block unspecific intercalation.
- Grimme, Stefan,H?ger, Sigurd,Jester, Stefan-S.,Jochemich, Anna,Keller, Tristan J.,Kr?nert, Anna,Müller, Ute,Poluektov, Georgiy,Spicher, Sebastian
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supporting information
p. 27264 - 27270
(2021/11/30)
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- Methane-perylene diimide-based small molecule acceptors for high efficiency non-fullerene organic solar cells
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We report perylene diimide (PDI) small molecules based on diphenylmethane, triphenylmethane, and tetraphenylmethane cores, named PM-PDI2, PM-PDI3 and PM-PDI4, respectively. The OSC performances of PM-PDI3 and PM-PDI4 are comparable. The PM-PDI3 based device with PDBT-T1 as the donor achieved a highest power conversion efficiency (PCE) of 7.58% along with a high open-circuit voltage (VOC) of 0.98 V, a short-circuit current density (JSC) of 11.02 mA cm-2 and a high fill factor (FF) of 69.9%, a 1.32 times boost in PCE with respect to the PM-PDI2 based control device (3.26%). The high photovoltaic performance of the PM-PDI3 based device can be attributed to its relatively high-lying LUMO level, complementary absorption spectra with the polymer donor material PDBT-T1, relatively favorable morphology and improved exciton dissociation and charge collection efficiency. A PCE of 7.58% is among the highest efficiency of phenyl-methane as core based non-fullerene organic solar cells. Overall, this work provides a new approach to enhance the performance of non-fullerene acceptors.
- Li, Gang,Yang, Wenbin,Wang, Shuaihua,Liu, Tao,Yan, Cenqi,Zhang, Yu,Li, Dandan,Wang, Xinyu,Hao, Pin,Li, Jiewei,Huo, Lijun,Yan, He,Tang, Bo
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supporting information
p. 10901 - 10907
(2019/09/19)
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- Novel multi-dimensional electron-transporting material
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The invention provides a preparation method of a novel multi-dimensional electron-transporting material. A multi-site core with a two-dimensional or three-dimensional space structure is subjected to a modular splicing reaction with a group structure with electron-withdrawing capacity, by means of change of the core and groups, molecular energy level is further regulated, electron delocalization is enhanced, absorption of visible light is increased, electron mobility is improved, and furthermore, morphology beneficial to exciton dissociation and transportation is obtained during matching with an electron donor material; finally, the electron-transporting material applied to different organic electronic devices can be obtained through optimization.
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Paragraph 0014; 0015
(2017/06/19)
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- Supramolecular Organization of Dye Molecules in Zeolite L Channels: Synthesis, Properties, and Composite Materials
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Sequential insertion of different dyes into the 1D channels of zeolite L (ZL) leads to supramolecular sandwich structures and allows the formation of sophisticated antenna composites for light harvesting, transport, and trapping. The synthesis and properties of dye molecules, host materials, composites, and composites embedded in polymer matrices, including two- and three-color antenna systems, are described. Perylene diimide (PDI) dyes are an important class of chromophores and are of great interest for the synthesis of artificial antenna systems. They are especially well suited to advancing our understanding of the structure-transport relationship in ZL because their core fits tightly through the 12-ring channel opening. The substituents at both ends of the PDIs can be varied to a large extent without influencing their electronic absorption and fluorescence spectra. The intercalation/insertion of 17 PDIs, 2 terrylenes, and 1 quaterrylene into ZL are compared and their interactions with the inner surface of the ZL nanochannels discussed. ZL crystals of about 500 nm in size have been used because they meet the criteria that must be respected for the preparation of antenna composites for light harvesting, transport, and trapping. The photostability of dyes is considerably improved by inserting them into the ZL channels because the guests are protected by being confined. Plugging the channel entrances, so that the guests cannot escape into the environment is a prerequisite for achieving long-term stability of composites embedded in an organic matrix. Successful methods to achieve this goal are described. Finally, the embedding of dye-ZL composites in polymer matrices, while maintaining optical transparency, is reported. These results facilitate the rational design of advanced dye-zeolite composite materials and provide powerful tools for further developing and understanding artificial antenna systems, which are among the most fascinating subjects of current photochemistry and photophysics. Rylenes in nanochannels: The synthesis and properties of organic dyes incorporated into zeolite L (ZL) crystals are described. The intercalation/insertion of 17 perylene diimides, two terrylene diimides, and one quaterrylene diimide into ZL is compared and their interactions with the inner surface of the ZL nanochannels are discussed (see figure).
- Cao, Pengpeng,Khorev, Oleg,Devaux, André,S?gesser, Lucie,Kunzmann, Andreas,Ecker, Achim,H?ner, Robert,Brühwiler, Dominik,Calzaferri, Gion,Belser, Peter
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supporting information
p. 4046 - 4060
(2016/03/16)
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- Tetrahedral rigid core antenna chromophores bearing bay-substituted perylenediimides
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Two new representative methane- and adamantane-centered 'antenna' tetramers bearing bay-substituted π-conjugated phenylethynyl-perylenediimides (PDICCPh) as chromophoric subunits, tetrakis-[1-(4-ethynylphenyl)-N,N′-bis(1-hexylheptyl)-perylene-3,4:9,10-tetracarboxylic diimide]-methane (1) and tetrakis-1,3,5,7-[1-(4-ethynylphenyl)-N,N′-bis(1-hexylheptyl)-perylene-3,4:9,10-tetracarboxylic diimide]-adamantane (2), have been synthesized and their structural aspects have been thoroughly investigated by NMR spectroscopy. These PDI tetramers (1 and 2) represent the first successful example of incorporating the bay-substituted phenylethynyl-perylenediimides into the large rigid core tetrahedral frameworks. In these PDI tetramers, dynamic NMR experiments revealed the existence of perylene-centered conformational dynamic equilibrium (ΔG≠=15-17 kcal/mol), the primary cause of the observed spectral broadening in conventional 1H NMR spectra (295 K). In addition, PDI tetramers 1 and 2 were found to possess exceptional (photo)chemical stability, and their corresponding photophysical properties (εmax~180,000; τFL=6.9 ns; ΦFL~60%) make them viable candidates for various photonic applications and are in good agreement with other related multichromophoric PDI-based systems.
- Myahkostupov, Mykhaylo,Castellano, Felix N.
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supporting information
p. 9519 - 9527
(2015/12/01)
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- Modulating helicity through amphiphilicity - Tuning supramolecular interactions for the controlled assembly of perylenes
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Here we show that it is possible to modulate the supramolecular assembly of designed H-bonding amphiphilic perylene-based materials through simple solvent interactions. These modulated supramolecular interactions have been translated to and observed in macroscopic properties, and provide new pathways to the preparation of switchable interfaces based on designed supramolecular interactions.
- Huang, Yongwei,Hu, Jianchen,Kuang, Wenfeng,Wei, Zhixiang,Faul, Charl F. J.
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supporting information; experimental part
p. 5554 - 5556
(2011/06/23)
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- Room-temperature columnar liquid-crystalline perylene imido-diesters by a homogeneous one-pot imidification-esterification of perylene-3,4,9,10- tetracarboxylic dianhydride
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The reaction of PTCDA (perylene-3,4,9,10-tetracarboxylic dianhydride) with an alcohol, a bromoalkane, and an alkylamine in the presence of DBU in DMF yields imido-diester-substituted perylenes. The reaction is limited to polar alcohols such as propanol, but longer alkyl chains are efficiently introduced in a second step by alkyl group exchange by using selective acidic ester hydrolysis that leaves the imide group intact. This amine-efficient approach to imido-diesters is used to obtain acceptor-type self-assembling dyes that form a hexagonal columnar liquid crystalline phase at room temperature. Perylenetetracarboxylic monoimide-diesters were synthesized by an amine-efficient, one-pot procedure. Alkyl group exchange of the ester moieties leads, through the use of the monoimido-monoanhydride, to room-temperature hexagonal columnar liquid crystals with potential as self-assembling electron acceptors for organic electronics.
- Kelber, Julien,Bock, Harald,Thiebaut, Olivier,Grelet, Eric,Langhals, Heinz
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p. 707 - 712
(2011/04/22)
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- Evidence of preferential π-stacking: A study of intermolecular and intramolecular charge transfer complexes
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Nine combinations of π-electron donors and acceptors were examined by UV-vis, fluorescence and 1H-NMR spectroscopy to identify π-stacked charge transfer complexes in macromolecular and supramolecular constructs. The high association constant of pyrene and naphthalene diimide suggests a preferentially π-stacking pair rationalized by frontier orbital congruence. The Royal Society of Chemistry 2010.
- Kumar, N. S. Saleesh,Gujrati, Maneesh D.,Wilson, James N.
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supporting information; scheme or table
p. 5464 - 5466
(2010/10/04)
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- "Helter-skelter-like" perylene polyisocyanopeptides
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We report on a combined experimental and computational investigation on the synthesis and thorough characterization of the structure of perylene-functionalized polyisocyanides. Spectroscopic analyses and extensive molecular dynamics studies revealed a well defined 4) helix in which the perylene molecules form four "helter skelter-like" overlapping pathways along which excitons and electrons can rapidly migrate. The well-defined polymer scaffold stabilized by hydrogen bonding, to which the chromophores are attached, accounts for the precise architectural definition, and molecular stiffness observed for these molecules. Molecular-dynamics studies showed that the chirality present in these polymers is expressed in the formation of stable right-handed helices. The formation of chiral supramolecular structures is further supported by the measured and calculated bisignated Cotton effect. The structural definition of the chromophores aligned in one direction along the backbone is highlighted by the extremely efficient exciton migration rates and charge densities measured with Transient Absorption Spectroscopy.
- Schwartz, Erik,Palermo, Vincenzo,Finlayson, Chris E.,Huang, Ya-Shih,Otten, Matthijs B. J.,Liscio, Andrea,Trapani, Sara,Gonzalez-Valls, Irene,Brocorens, Patrick,Cornelissen, Jeroen J. L. M.,Peneva, Kalina,Muellen, Klaus,Spano, Frank C.,Yartsev, Arkady,Westenhoff, Sebastian,Friend, Richard H.,Beljonne, David,Nolte, Roeland J. M.,Samori, Paolo,Rowan, Alan E.
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scheme or table
p. 2536 - 2547
(2009/12/03)
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- ORGANIC SEMICONDUCTOR MATERIALS AND METHODS OF PREPARING AND USE THEREOF
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Solution-processable organic n-type semiconductor materials are provided with processes for preparing the same. Composites and electronic devices including the organic n-type semiconductor materials also are provided.
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Page/Page column 26-27
(2008/12/05)
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- New and efficient arrays for photoinduced charge separation based on perylene bisimide and corroles
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The bichromophoric systems C2-PI, C3-PI, and C3-PPI consisiting of corrole and perylene bisimide units and representing one of the rare cases of elaborate structures based on corrole, have been synthesized. Corroles C2 and C3 are, respectively, meso-substituted corroles with 2,6-dichlorophenyl and pentafluorophenyl substituents at the 5 and 15 positions. The three dyads were prepared by divergent strategy with the corrole-forming reaction as the last step of the sequence. C2-PI and C3-PI differ in the nature of the corroles, whereas C3-PI differs from C3-PPI in the presence of a further phenyl unit in the linker between photoactive units. The dyads display spectroscopic properties which are the superposition of the component spectra, indicating a very weak electronic coupling. Excitation of the corrole unit leads to charge separation with a rate which decreases from 2.4 × 1010, to 5.0 × 109, and to 4.9 × 107 s-1 for C2-PI, C3-PI, and C3-PPI, respectively, where the reaction is characterized by a ΔG° > 0. Excitation of the perylene bisimide unit is followed by competing reactions of; 1) energy transfer to the corrole unit, which subsequently deactivates to the charge-separated state and; 2) electron transfer to directly form the charge-separated state. The ratio of electron-to-energy- transfer rates is 9;1 and 1;1 for C3-PI and C3-PPI, respectively. The yield of charge separation is essentially 100% for C2-PI and C3-PI, and approximately 50% (excitation of peryleneimide) or 15% (excitation of the corrole) for C3-PPI. The lifetime of the charge-separated state, observed for the first time in corrole-based structures, is 540 ps for C2-PI, 2.5 ns for C3-PI, and 24 ns for C3-PPI, respectively. This is in agreement with an inverted behavior, according to Marcus theory.
- Flamigni, Lucia,Ventura, Barbara,Tasior, Mariusz,Becherer, Thomas,Langhals, Heinz,Gryko, Daniel T.
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p. 169 - 183
(2008/09/18)
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- Swallow-tailed perylene derivative: A new tool for fluorescent imaging of lipid hydroperoxides
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A swallow-tailed perylene derivative including a triphenylphosphine moiety was synthesized and applied to the detection and the live-cell imaging of lipid hydroperoxides. The novel probe, named Spy-LHP, reacted rapidly and quantitatively with lipid hydroperoxides to form the corresponding oxide, Spy-LHPOx, which emits extremely strong fluorescence (Φ ~ 1) in the visible range (λem = 535 nm, 574 nm). Spy-LHP was highly selective for lipid hydroperoxides, and the addition of other reactive oxygen species (ROS) including hydrogen peroxides, hydroxyl radical, superoxide anion, nitric oxide, peroxynitrite, and alkylperoxyl radical, caused no significant increase in the fluorescence intensity. The probe exhibited good localization to cellular membranes and was successfully applied to the confocal laser scanning microscopy (CLSM) imaging of lipid hydroperoxides in live J774A.1 cells, in which lipid peroxidation was proceeded by the stimulation of 2,2-azobis(2-amidinopropane)dihydrochloride (AAPH). These findings establish Spy-LHP as a promising new tool for investigating the physiology of lipid hydroperoxides. The Royal Society of Chemistry 2007.
- Soh, Nobuaki,Ariyoshi, Tomoyuki,Fukaminato, Tuyoshi,Nakajima, Hizuru,Nakano, Koji,Imato, Toshihiko
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p. 3762 - 3768
(2008/10/09)
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- Single-molecule spectroscopy of interfacial electron transfer
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It is widely appreciated that single-molecule spectroscopy (SMS) can be used to measure properties of individual molecules which would normally be obscured in an ensemble-averaged measurement. In this report we show how SMS can be used to measure photoinduced interfacial electron transfer (IET) and back electron transfer rates in a prototypical chromophore-bridge-electrode nonadiabatic electron transfer system. N-(1-hexylheptyl)-N′ -(12-carboxylicdodecyl)perylene-3,4,9,10-tetracarboxylbisimide was synthesized and incorporated into mixed self-assembled monolayers (SAMs) on an ITO (tin-doped indium oxide, a p-type semiconductor) electrode. Single-molecule fluorescence time trajectories from this system reveals "blinks", momentary losses in fluorescence (>20 ms to seconds in duration), which are attributed to discrete electron transfer events: electron injection from the perylene chromophore into the conduction band of the ITO leads to the loss of fluorescence, and charge recombination (back electron transfer) leads to the return of fluorescence. Such blinks are not observed when an electrode is not present. The fluorescence trajectories were analyzed to obtain the forward and back electron rates; the measured rates are found to lie in the millisecond to second regime. Different rates are observed for different molecules, but the lifetime distributions for the forward or back electron transfer for any given molecule are well fit by single exponential kinetics. The methodology used is applicable to a wide variety of systems and can be used to study the effects of distance, orientation, linker, environment, etc. on electron transfer rates. The results and methodology have implications for molecular electronics, where understanding and controlling the range of possible behaviors inherent to molecular systems will likely be as important as understanding the individual behavior of any given molecule.
- Holman, Michael W.,Liu, Ruchuan,Adams, David M.
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p. 12649 - 12654
(2007/10/03)
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- The Synthesis of Perylenebisimide Monocarboxylic Acids
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The synthesis and properties of perylene-bisimides 4 with one carboxylic acid anchor group are described. The properties of 4 are strongly influenced by the spacer between the carboxylic acid group and the imide moeity. Dyes with aliphatic (4d-4g) and aromatic (4a-4c) spacers have been prepared.
- Langhals, Heinz,Jona, Wolfgang
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p. 847 - 851
(2007/10/03)
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- Synthesis of Perylene-3,4-dicarboximides - Novel Highly Photostable Fluorescent Dyes
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Perylene-3,4-dicarboximides 2 are obtained by a decarboxylizing condensation of moderately sterically hindered primary amines with perylene-3,4,9,10-tetracarboxylic 3,4:9,10-bisanhydride (3) in the presence of water.Perylene-3,4-dicarboxylic anhydride (4) is prepared by hydrolysis of the imides with KOH in tert-butyl alcohol.The anhydride may be condensed with any primary amine to the corresponding imide.The imides are highly fluorescent and very photostable dyes. - Key Words: Fluorescent dyes/Pigments/Perylenes/Carboximides
- Feiler, Leonhard,Langhals, Heinz,Polborn, Kurt
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p. 1229 - 1244
(2007/10/02)
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- Very Soluble and Photostable Perylene Fluorescent Dyes
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The synthesis of perylene dyes 2 with two terminal alkyl groups is described.Long-chain alkyl groups do not increase, but diminish solubility.Cycloalkyl substituents give a minimum of solubility with medium sized rings and a maximum with the cyclotetradecyl derivative (2p).Very high solubility in organic solvents is attained by substitution with secondary alkyl residues having two long chains.One of them, the dye with the 1-hexylheptyl substituent (2v), exhibits a solubility of more than 100g/l in most solvents, a fluorescent quantum yield of about 100 percent, and a very high photostability, thus making it suitable for special applications.
- Demming, Stefan,Langhals, Heinz
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p. 225 - 230
(2007/10/02)
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