- An effective and regioselective bromination of 1,4,5,8- naphthalenetetracarboxylic dianhydride using tribromoisocyanuric acid
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A highly efficient and cost-effective reagent for the bromination of 1,4,5,8-naphthalenetetracarboxylic dianhydride under mild reaction conditions is reported. Bromination of 1,4,5,8-naphthalenetetracarboxylic dianhydride using tribromoisocyanuric acid (TBCA) in concentrated H2SO4 is very effective and regioselective. 1,4,5,8-Naphthalenetetracarboxylic dianhydride was brominated smoothly under optimized reaction conditions to give mono-, di- and tetra-brominated products in good to excellent yields using TBCA. As a proof of principle, the potential of this bromination methodology is demonstrated by converting brominated naphthalenetetracarboxylic dianhydrides into N-imide and core functionalized 1,4,5,8-napthalenetetracarboxylic diimides by treating with n-butylamine to yield corresponding mono-, di- and tetra-(n-butylamino)-naphthalene diimides in good yields in one-step reactions.
- Suseela,Sasikumar,Govindaraju
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- Red-Emitting Delayed Fluorescence and Room Temperature Phosphorescence from Core-Substituted Naphthalene Diimides
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Unprecedented ambient triplet-mediated emission in core-substituted naphthalene diimide (cNDI) derivatives is unveiled via delayed fluorescence and room temperature phosphorescence. Carbazole core-substituted cNDIs, with a donor–acceptor design, showed deep-red triplet emission in solution processable films with high quantum yield. This study, with detailed theoretical calculations and time-resolved emission experiments, enables new design insights into the triplet harvesting of cNDIs; an important family of molecules which has been, otherwise, extensively been investigated for its n-type electronic character and tunable singlet fluorescence.
- Kuila, Suman,Ghorai, Anaranya,Samanta, Pralok K.,Siram, Raja B. K.,Pati, Swapan K.,Narayan,George, Subi J.
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- Quinoidization of π-Expanded Aromatic Diimides: Photophysics, Aromaticity, and Stability of the Novel Quinoidal Acenes
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We report the synthesis and photophysical characterization of π-expanded quinoidal triplet chromophores which exhibit attractive light-harvesting properties. The kinetic of the triplet excited state of quinoidal benzotetraphene 2 was found to be one order of magnitude higher than the lifetime of 3(1)* from the less conjugated parent chromophore 1. Furthermore, the evaluation of the optoelectronic properties indicates that π-expansion helps narrow the optoelectronic band gap, but the influence of the additional aromatic rings in the structure of 2 and 3 compromises the stability of the p-quinoidal ring. QDM 2 was isolated and fully characterized; however, it was found to rearomatize to a mixture of uncharacterized radical species.
- Ayitou, A. Jean-Luc,Jockusch, Steffen,Kamatham, Nareshbabu,Li, Jingbai,Rogachev, Andrey Yu.,Shokri, Siamak,Yang, Guang
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- Small bandgap naphthalene diimide copolymers for efficient inorganic-organic hybrid solar cells
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Two low band-gap naphthalene diimide (NDI)-based conjugated polymers have been designed and grafted with benzo[1,2-b:4,5-b′]dithiophene (BDT) or dithieno [3,2-b:2′,3′-d]pyrrole (DTP) by a Stille cross-coupling reaction. Inorganic-organic hybrid solar cells (HSCs) based on the copolymers deliver high performances by suitable molecular design and careful selection of chemical structures with different electronic nature. The well designed copolymers exhibit broader solar light absorption, which is attributed to their smaller band gaps. Density functional theory calculations and cyclic voltammetry characteristics reveal that the copolymers have small band gaps and deep HOMO and LUMO energy levels. Moreover, after introducing the copolymers, the energy level formation of the bulk-heterojunction become more matched, thus giving rise to excellent photovoltaic performances as HSCs. The results showed that an NDI-based copolymer with DTP donor segments exhibits a higher power conversion efficiency of 2.36%. This work highlights the development of bipolar host materials with a focus on molecular design strategies, which benefits the light harvest and enhances the efficiency by well aligned energy level formation. This journal is
- Qin, Yuancheng,Li, Xing,Sun, Weifu,Luo, Xubiao,Li, Mingjun,Tang, Xinghua,Jin, Xiao,Xie, Yu,Ouyang, Xinhua,Li, Qinghua
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- Rod-like oligomers incorporating 2,6-dialkylamino core-substituted naphthalene diimide as acceptors for organic photovoltaic
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Core-substituted naphthalene diimides (core-substituted NDIs) were incorporated into rod-like molecules and oligomers through reaction at the imide nitrogen positions. N,N′-Di(4-bromophenyl)-2,6-di(N-alkylamino)-1,4,5,8- naphthalenetetracarboxydiimide was synthesized in only three steps, and used as a versatile platform to prepare extended structures by reaction with thiophene substrates using Suzuki-coupling conditions. The optoelectronic properties of the new compounds were examined by UV/vis absorption spectroscopy, fluorescence spectroscopy, cyclic voltammetry and theoretical calculations. The imide substituents had little effect on the optical and electrochemical properties of core-substituted NDIs in solution. A bathochromic shift of the absorption was observed upon film formation, accompanied by quenching of fluorescence. These observations are consistent with increased inter-molecular interactions between core-substituted NDI moieties in the solid state. All compounds were tested in organic solar cells by blending with poly(3-hexylthiophene), and several showed a photovoltaic effect, demonstrating their potential as electron acceptors in organic solar cell. The best solar cell was observed for core-substituted NDI with 4-(thiophen-2-yl)phenyl imide substituents (5a), showing a power conversion efficiency of 0.57% and a large open circuit voltage of 0.87 V. This approach allows new structure-property relationship studies of non-fullerene acceptors in organic solar cells, where one can vary the imide substituent to optimize photovoltaic parameters while keeping the optical and electrochemical properties constant.
- Fernando, Roshan,Mao, Zhenghao,Sauvé, Geneviève
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- Fast, sensitive, selective and reversible fluorescence monitoring of TATP in a vapor phase
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The development of sensors for the detection of triacetone triperoxide (TATP) has attracted great attention. Here, we constructed a low-cost, portable, reusable, visible paper-based fluorescent sensor for the sensitive detection of TATP via vapor sampling. Under optimized conditions, the fluorescent film showed a high sensitivity to TATP with a detection limit of lower than 0.5 μg mL-1 in air. The linear range of the response is from 0.5 to 8.0 μg mL-1. In addition, the paper-based sensor exhibited high selectivity to TATP. The presence of potential interferents showed little effect on sensing. Moreover, sensing is fully reversible. Fortunately, the test can also be conducted in a visualized way.
- An, Yanqin,Xu, Xiaojie,Liu, Ke,An, Xuan,Shang, Congdi,Wang, Gang,Liu, Taihong,Li, Hong,Peng, Haonan,Fang, Yu
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- Fabrication of diverse nano-architectures through the self-assembly of a naphthalene diimide derivative bearing four carbamates
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A naphthalene diimide (NDI) derivative bearing four carbamate groups (coded as: W2) was synthesised using a multistep strategy, and utilizing solvophobic effects, the self-assembly of this molecule was studied using solvent mixtures. Self-assembly led to a variety of controllable morphologies of supramolecular structures on both the micro and nanoscale. Nanobelts, nanospheres, nano-corals, microflowers and nanograss-like morphologies were obtained in DMF, MCH, CHCl3, THF, water and MeOH solvent mixtures. UV-vis absorption, fluorescence emission spectroscopy, FT-IR and XRD gave insight into the mode of aggregation of W2 in various solvents. The polarity of the solvent mixtures used directed the self-organisation of W2 by driving the π-π stacking interaction between NDI cores, and the H-bonding between the carbamate moieties. Our studies show that the solvent polarity guides the self-assembly process during solvent evaporation leading to the formation of supramolecular nano- and microstructures under ambient conditions.
- Wagalgave, Sopan M.,Ducla, Duong,Bhosale, Rajesh S.,Kobaisi, Mohammad Al,Jones, Lathe A.,Bhosale, Sidhanath V.,Bhosale, Sheshanath V.
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- Targeting Multiple Effector Pathways in Pancreatic Ductal Adenocarcinoma with a G-Quadruplex-Binding Small Molecule
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Human pancreatic ductal adenocarcinoma (PDAC) involves the dysregulation of multiple signaling pathways. A novel approach to the treatment of PDAC is described, involving the targeting of cancer genes in PDAC pathways having over-representation of G-quadruplexes, using the trisubstituted naphthalene diimide quadruplex-binding compound 2,7-bis(3-morpholinopropyl)-4-((2-(pyrrolidin-1-yl)ethyl)amino)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (CM03). This compound has been designed by computer modeling, is a potent inhibitor of cell growth in PDAC cell lines, and has anticancer activity in PDAC models, with a superior profile compared to gemcitabine, a commonly used therapy. Whole-transcriptome RNA-seq methodology has been used to analyze the effects of this quadruplex-binding small molecule on global gene expression. This has revealed the down-regulation of a large number of genes, rich in putative quadruplex elements and involved in essential pathways of PDAC survival, metastasis, and drug resistance. The changes produced by CM03 represent a global response to the complexity of human PDAC and may be applicable to other currently hard-to-treat cancers.
- Marchetti, Chiara,Zyner, Katherine G.,Ohnmacht, Stephan A.,Robson, Mathew,Haider, Shozeb M.,Morton, Jennifer P.,Marsico, Giovanni,Vo, Tam,Laughlin-Toth, Sarah,Ahmed, Ahmed A.,Di Vita, Gloria,Pazitna, Ingrida,Gunaratnam, Mekala,Besser, Rachael J.,Andrade, Ana C. G.,Diocou, Seckou,Pike, Jeremy A.,Tannahill, David,Pedley, R. Barbara,Evans, T. R. Jeffry,Wilson, W. David,Balasubramanian, Shankar,Neidle, Stephen
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- Naphthalene diimides with improved solubility for visible light photoredox catalysis
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Five core-substituted naphthalene diimides bearing two dialkylamino groups were synthesized as potential visible light photoredox catalysts and characterized by methods of optical spectroscopy and electrochemistry in comparison with one unsubstituted naphthalene diimide as reference. The core-substituted naphthalene diimides differ by the alkyl groups at the imide nitrogens and at the nitrogens of the two substituents at the core in order to enhance their solubility in DMF and thereby enhance their photoredox catalytic potential. The 1-ethylpropyl group as rather short and branched alkyl substituent at the imide nitrogen and the n-propyl group as short and unbranched one at the core amines yielded the best solubilities. The electron-donating diaminoalkyl substituents together with the electron-deficient aromatic core of the naphthalene diimides increase the charge-transfer character of their photoexcited states and thus shift their absorption into the visible light (500-650 nm). The excited state reduction potential was estimated to be approximately +1.0 V (vs SCE) which is sufficient to photocatalyze typical organic reactions. The photoredox catalytic activity in the visible light range was tested by the α-alkylation of 1-octanal as benchmark reaction. Irradiations were performed with LEDs in the visible light range between 520 nm and 640 nm. The irradiation by visible light together with the use of an organic dye instead of a transition metal complex as photoredox catalyst improve the sustainability and make photoredox catalysis “greener”.
- Rei?, Barbara,Wagenknecht, Hans-Achim
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- Red fluorescent zwitterionic naphthalenediimides with di/mono-benzimidazolium and a negatively-charged oxygen substituent
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The C-H/C-X cross-coupling of a benzimidazolium salt with 2Br-NDI afforded two unprecedented zwitterionic NDIs with di/mono-benzimidazolium and an extra negatively-charged oxygen substituent. They exhibited intensified red fluorescence in polar solvents and negative solvatochromism due to an intramolecular charge transfer process, and could specifically label lysosomes and the endoplasmic reticulum in living A549 cells, respectively. They represent a rare case of NDI-derived ionic fluorophores.
- Gao, Ge,Han, Songyan,Liu, Yanhong,Wang, Chunqin,Wang, Tianbao,Zhang, Cheng,Zheng, Xuesong,Zhou, Linsen
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supporting information
p. 9422 - 9425
(2021/09/22)
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- Electronic and assembly properties of a water-soluble blue naphthalene diimide
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Herein we report on the synthesis and characterisation of a water soluble deep blue naphthalene diimide, (iPrNH)2NDI-V. The synthesis is performed under mild conditions and careful consideration of the purification of the precuror materials leads to improved results in final yield and purity. The optoelectronic properties are explored through cyclic voltammetry and UV-vis absorption and emission spectroscopy in multiple solvents and the self-assembling properties as part of a multi-component hydrogel are investigated through rheology and small angle neutron scattering.
- Draper, Emily R.,Matsarskaia, Olga,Schweins, Ralf,Welsh, Thomas A.
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p. 14005 - 14013
(2021/08/16)
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- Organic room-temperature phosphorescence from halogen-bonded organic frameworks: hidden electronic effects in rigidified chromophores
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Development of purely organic materials displaying room-temperature phosphorescence (RTP) will expand the toolbox of inorganic phosphors for imaging, sensing or display applications. While molecular solids were found to suppress non-radiative energy dissipation and make the RTP process kinetically favourable, such an effect should be enhanced by the presence of multivalent directional non-covalent interactions. Here we report phosphorescence of a series of fast triplet-forming tetraethyl naphthalene-1,4,5,8-tetracarboxylates. Various numbers of bromo substituents were introduced to modulate intermolecular halogen-bonding interactions. Bright RTP with quantum yields up to 20% was observed when the molecule is surrounded by a Br?O halogen-bonded network. Spectroscopic and computational analyses revealed that judicious heavy-atom positioning suppresses non-radiative relaxation and enhances intersystem crossing at the same time. The latter effect was found to be facilitated by the orbital angular momentum change, in addition to the conventional heavy-atom effect. Our results suggest the potential of multivalent non-covalent interactions for excited-state conformation and electronic control. This journal is
- Zhou, Jiawang,Stojanovi?, Ljiljana,Berezin, Andrey A.,Battisti, Tommaso,Gill, Abigail,Kariuki, Benson M.,Bonifazi, Davide,Crespo-Otero, Rachel,Wasielewski, Michael R.,Wu, Yi-Lin
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p. 767 - 773
(2021/01/28)
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- Organic small molecule electron transport material based on naphthalimide unit and application thereof
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The invention provides an organic small molecule electron transport material based on a naphthalimide unit and application thereof, belongs to the field of organic photoelectric materials, and solves the problems that in the prior art, the quantum dot light-emitting diode device is few in electron transport material selection and poor in device stability. The chemical structure of the organic small molecule electron transport material contains a naphthalimide unit, and the organic small molecule electron transport material has the advantages that 1) the lowest unoccupied molecular orbital energy level is low, electron injection and transport in a QLED device are facilitated, the highest occupied molecular orbital energy level is low, hole injection in the QLED device can be blocked, and the above two aspects are beneficial for improving the electroluminescent efficiency of the QLED device; (2) the absorption spectrum is mainly not located in a visible light region and does not absorb light emitted by the light-emitting layer in the QLED device; and 3) the material has a rigid configuration, can inhibit crystallization of the material, is beneficial to processing in a QLED, and is beneficial to improving the stability of a QLED device.
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Paragraph 0121-0126; 0134-0139; 0146-0151; 0159-0164
(2021/07/17)
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- Molecular Encapsulation of Naphthalene Diimide (NDI) Based π-Conjugated Polymers: A Tool for Understanding Photoluminescence
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Conjugated polymers are an important class of chromophores for optoelectronic devices. Understanding and controlling their excited state properties, in particular, radiative and non-radiative recombination processes are among the greatest challenges that must be overcome. We report the synthesis and characterization of a molecularly encapsulated naphthalene diimide-based polymer, one of the most successfully used motifs, and explore its structural and optical properties. The molecular encapsulation enables a detailed understanding of the effect of interpolymer interactions. We reveal that the non-encapsulated analogue P(NDI-2OD-T) undergoes aggregation enhanced emission; an effect that is suppressed upon encapsulation due to an increasing π-interchain stacking distance. This suggests that decreasing π-stacking distances may be an attractive method to enhance the radiative properties of conjugated polymers in contrast to the current paradigm where it is viewed as a source of optical quenching.
- Royakkers, Jeroen,Guo, Kunping,Toolan, Daniel T. W.,Feng, Liang-Wen,Minotto, Alessandro,Congrave, Daniel G.,Danowska, Magda,Zeng, Weixuan,Bond, Andrew D.,Al-Hashimi, Mohammed,Marks, Tobin J.,Facchetti, Antonio,Cacialli, Franco,Bronstein, Hugo
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supporting information
p. 25005 - 25012
(2021/10/20)
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- Influences of the number of 2-ethylhexylamine chain substituents on electron transport characteristics of core-substituted naphthalene diimide analogues
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We designed and synthesized a series of naphthalenediimide (NDI) derivatives through core-substitution (coded as cNDI) with various number of 2-ethyl-hexylamine (EHA) chains at different positions. The molecular structure of cNDI derivatives such as cNDI-1EHA, cNDI-2EHA, cNDI-3EHA and cNDI-4EHA bearing one, two, three and four 2-ethyl-hexylamine chains, respectively, was confirmed by different spectroscopic techniques such as FTIR, 1H-NMR, 13C-NMR spectroscopy and mass spectrometry. Interestingly, the incorporation of different numbers of 2-ethyl-hexylamine on electron-deficient cNDI yields diverse photophysical and electrochemical properties. The change in the number of alkyl chains on the NDI core significantly influences the redox properties and the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels. The changes in the morphology of the spin-coated films before and after annealing are reorganized differently depending on the number of 2-ethyl-hexylamine topology proved by scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques. The electron mobility of cNDIs was examined by following the standard protocol of the space-charge limiting current (SCLC) method. The NDI derivatives bearing various number of 2-ethyl-hexylamine chains at the NDI core after thermal treatment at 170 °C exhibited very good electron mobility of the order of 10-6 to 10-4 cm2 V-1 s-1. The observed electron mobility trends depend not only on the number of 2-ethyl-hexylamine substituents but also on the changes in thin-film morphology.
- Birajdar, Shailesh S.,Naqvi, Samya,More, Kerba S.,Puyad, Avinash L.,Kumar, Rachana,Bhosale, Sidhanath V.,Bhosale, Sheshanath V.
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supporting information
p. 1590 - 1600
(2021/02/06)
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- Near-infrared two-region dye based on naphthalimide derivative as well as preparation and application of near-infrared two-region dye
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The invention relates to a near-infrared two-region dye based on a naphthalimide derivative as well as preparation and an application of the near-infrared two-region dye. The near-infrared two-region dye based on a naphthalimide structure is obtained by carrying out coupling reaction on naphthalimide serving as an acceptor structure unit and different donor units. Then the near-infrared second-region dye and amphiphilic lipid molecules DSPE-PEG5000 are subjected to self-assembly, and the obtained water-soluble nanoparticles have good fluorescence intensity in a near-infrared second region and can be used as a contrast agent to realize imaging application in the near-infrared second region.
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Paragraph 0039-0043
(2021/08/14)
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- Spin-Orbit Charge-Transfer Intersystem Crossing of Compact Naphthalenediimide-Carbazole Electron-Donor-Acceptor Triads
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Compact electron donor-acceptor triads based on carbazole (Cz) and naphthalenediimide (NDI) were prepared to study the spin-orbit charge-transfer intersystem crossing (SOCT-ISC). By variation of the molecular conformation and electron-donating ability of the carbazole moieties, the electronic coupling between the two units was tuned, and as a result charge-transfer (CT) absorption bands with different magnitudes were observed (ε = 4000-18?000 M-1cm-1). Interestingly, the triads with NDI attached at the 3-C position or with a phenyl spacer at theNposition of the Cz moiety, thermally activated delayed fluorescence (TADF) was observed. Femtosecond transient absorption (fs-TA) spectroscopy indicated fast electron transfer (0.8-1.5 ps) from the Cz to NDI unit, followed by population of the triplet state (150-600 ps). Long-lived triplet states (up to τT= 45-50 μs) were observed for the triads. The solvent-polarity-dependent singlet-oxygen quantum yield (ΦΔ) is 0-26%. Time-resolved electron paramagnetic resonance (TREPR) spectral study of TADF molecules indicated the presence of the3CT state forNDI-Cz-Ph(zero-field-splitting parameterD= 21 G) and an3LE state forNDI-Ph-Cz(D= 586 G). The triads were used as triplet photosensitizers in triplet-triplet annihilation upconversion by excitation into the CT absorption band; the upconversion quantum yield was ΦUC= 8.2%, and there was a large anti-Stokes shift of 0.55 eV. Spatially confined photoexcitation is achieved with the upconversion using focusing laser beam excitation, and not the normally used collimated laser beam, i.e., the upconversion was only observed at the focal point of the laser beam. Photo-driven intermolecular electron transfer was demonstrated with reversible formation of the NDI-?radical anion in the presence of the sacrificial electron donor triethanolamine.
- Barbon, Antonio,El-Zohry, Ahmed M.,Hou, Yuqi,Hussain, Mushraf,Mohammed, Omar F.,Toffoletti, Antonio,Zhao, Jianzhang
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p. 10813 - 10831
(2021/10/12)
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- Novel core-substituted naphthalene diimide-based conjugated polymers for electrochromic applications
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A novel core-substituted naphthalene diimide derivative (DPyNDI-TPA) capped with electroactive triphenylamine was employed as an electroactive precursor to prepare p(DPyNDI-TPA) polymer films through in situ electropolymerization on FTO substrates. In contrast to the non-core-substituted NDI-TPA, the introduction of pyrrolidine groups endows the p(DPyNDI-TPA) films with a distinct morphology and a capability of ionization. Under an electric field, the pyrrolidine group could release an electron and combine with counterions in the electrolyte solution. Moreover, compared with the p(NDI-TPA) films, the wrapped counter anions in the p(DPyNDI-TPA) films could serve as balancing charges in electrochromic processes, which provide the film with a much better electrochromic performance (e.g., switching stability, coloring-bleaching speed and coloration efficiency). This meaningful design provides new concepts for the design of organic electrochromic materials and shows great prospects in optoelectrical materials.
- Wang, Kai,Zhu, Lin,Hu, Xuening,Han, Mingxi,Lin, Junyu,Guo, Zhiyong,Zhan, Hongbing
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supporting information
p. 16959 - 16965
(2021/12/20)
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- Asymmetrically Substituted Quadruplex-Binding Naphthalene Diimide Showing Potent Activity in Pancreatic Cancer Models
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Targeting of genomic quadruplexes is an approach to treating complex human cancers. We describe a series of tetra-substituted naphthalene diimide (ND) derivatives with a phenyl substituent directly attached to the ND core. The lead compound (SOP1812) has 10 times superior cellular and in vivo activity compared with previous ND compounds and nanomolar binding to human quadruplexes. The pharmacological properties of SOP1812 indicate good bioavailability, which is consistent with the in vivo activity in xenograft and genetic models for pancreatic cancer. Transcriptome analysis shows that it down-regulates several cancer gene pathways, including Wnt/β-catenin signaling.
- Ahmed, Ahmed A.,Angell, Richard,Barton, Naomi,Fowler, Thomas G.,Karim, Saadia A.,McConville, Matthew,Morton, Jennifer P.,Neidle, Stephen,O'Flynn, Daniel E.,Oxenford, Sally,Sunose, Mihiro,Vo, Tam,Williams, Nicole,Wilson, W. David,Worthington, Jenny
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p. 1634 - 1644
(2020/09/18)
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- Naphthalene Diimide-Based Molecules for Efficient and Stable Perovskite Solar Cells
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Naphthalene-diimide (NDI)-based molecules have shown an interesting behaviour within the field of perovskite solar cells, thanks to their promising application as electron transporting materials. In this paper, three novel NDI-containing molecules are synthesized and fully characterized, more specifically two polymers and an analogue small molecule. Each one of the NDI units contains an amine, either tertiary or quaternary, which is a moiety known for improving the conductivity. The newly synthesized compounds are suitable for the use as n-type buffer layers on the top of PC61BM, thanks to their appropriate energy levels and their solubility in polar solvents. The photovoltaic performances of the NDI-containing cells are highly comparable to those of the reference cells, which contain bathocuproine (BCP) as buffer layer. Furthermore, the stability of the NDI-containing cells is higher than that of the BCP reference.
- Cabrera-Espinoza, Andrea,Collavini, Silvia,Delgado, Juan Luis,Kosta, Ivet,Marinova, Nevena,Pascual, Jorge,Valero, Silvia
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supporting information
(2020/08/24)
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- REDOX FLOW BATTERY AND NEW COMPOUNDS USEFUL THEREIN
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The present invention relates to a redox flow battery comprising: a positive compartment containing a positive electrode in contact with a first aqueous-based electrolyte solution comprising a positive electrolyte dissolved in a first aqueous-based solvent; a negative compartment containing a negative electrode in contact with a second aqueous-based electrolyte solution comprising a negative electrolyte being an organic redox-active molecule dissolved in a second aqueous-based solvent; means for establishing electrical conduction between said positive electrode and said negative electrode, and an external load for directing electrical energy into or out of the redox flow battery; a separator component that separates the first aqueous-based electrolyte solution in the positive compartment from the second aqueous-based electrolyte solution in the negative compartment and substantially prevents the positive electrolyte in the positive compartment and the negative electrolyte in the negative compartment from intermingling with each other, while permitting the passage of non-redox-active species between the electrolyte solutions in the positive and negative compartments; and means capable of establishing flow of the electrolyte solutions past said positive and negative electrodes, respectively, and wherein the organic redox-active molecule is a naphthalene diimide (NDI); and a modified NDI.
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Page/Page column 32-33
(2020/10/20)
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- Peptide Stapling with Anion-π Catalysts
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We report design, synthesis and evaluation of a series of naphthalenediimides (NDIs) that are bridged with short peptides. Reminiscent of peptide stapling technologies, the macrocycles are conveniently accessible by a chromogenic nucleophilic aromatic substitution of two bromides in the NDI core with two thiols from cysteine sidechains. The dimension of core-bridged NDIs matches that of one turn of an α helix. NDI-stapled peptides exist as two, often separable atropisomers. Introduction of tertiary amine bases in amino-acid sidechains above the π-acidic NDI surface affords operational anion-π catalysts. According to an enolate chemistry benchmark reaction, anion-π catalysis next to peptides occurs with record chemoselectivity but weak enantioselectivity. Catalytic activity drops with increasing distance of the amine base to the NDI surface, looser homocysteine bridges, mismatched, shortened and elongated α-helix turns, and acyclic peptide controls. Elongation of isolated turns into short α helices significantly increases activity. This increase is consistent with remote control of anion-π catalysis from the α-helix macrodipole.
- Matile, Stefan,Pham, Anh-Tuan
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supporting information
(2020/04/28)
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- NARROW ABSORPTION POLYMER NANOPARTICLES AND RELATED METHODS
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Polymers, monomers, narrow-band absorbing polymers, narrow-band absorbing monomers, absorbing units, polymer dots, and related methods are provided. Bright, luminescent polymer nanoparticles with narrow-band absorptions are provided. Methods for synthesizing absorbing monomers, methods for synthesizing the polymers, preparation methods for forming the polymer nanoparticles, and applications for using the polymer nanoparticles are also provided.
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Page/Page column 182
(2020/04/25)
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- Controlling intermolecular redox-doping of naphthalene diimides
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Naphthalene diimide (NDI) with tertiary amine side chains is used to n-dope a series of NDI derivatives of varying energy levels. We demonstrate a photoinduced, intermolecular redox-doping process in which a dimethylpropyl amine side chain attached to one NDI reduces another NDI derivative to form radical anions. The influence of the aromatic core substituents on energy levels, doping efficacy and radical anion stability is studied by cyclic voltammetry, UV-Vis and electron paramagnetic resonance (EPR) spectroscopy. In general, the HOMO energy level of the NDI is responsible for the doping process and the LUMO for air stability of the resulting radical anion. The most electron deficient NDI derivative having two cyano substituents displays the highest doping yield and yields air stable radical anions for both light- and thermally-induced doping. Thermal doping is further accompanied by morphologic changes that stabilize radical anions in air.
- Schmidt, Simon B.,Biskup, Till,Jiao, Xuechen,McNeill, Christopher R.,Sommer, Michael
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supporting information
p. 4466 - 4474
(2019/04/25)
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- Naphthalimide derivatives and preparing method and application thereof
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The invention belongs to the technical field of organic electroluminescence materials, and particularly relates to naphthalimide derivatives having low LUMO energy levels and a preparing method and application thereof. Through molecular design on the derivatives, the LUMO energy levels of materials can be effectively reduced (between -4.6 and -6 eV). The energy levels of the derivatives can matchthose of HOMO of a hole transporting material well, thus meeting application requirements. In addition, through accurate control on the molecular structures, the derivatives have good stability, low volatility, and high decomposition temperature reaching 306 DEG C or above, and is stabler. The derivatives when applied into organic electroluminescence devices as n-type doping materials can effectively increase the hole concentration and the hole migration speed, thus reducing the cut-in voltage of the devices and increasing the current efficiency.
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Paragraph 0074; 0078; 0080
(2019/06/07)
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- Anthracene-Naphthalenediimide Compact Electron Donor/Acceptor Dyads: Electronic Coupling, Electron Transfer, and Intersystem Crossing
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We attached different electron donors of phenyl, anthryl, and alkylamino moieties, to electron acceptor naphthalenediimide (NDI) to construct compact electron donor/acceptor dyads. The purpose is to study the effect of electron coupling (the magnitude is the matrix element, VDA) on the photophysical properties of UV-vis absorption, fluorescence emission, especially spin-orbit charge transfer intersystem crossing. We found that the magnitude of VDA depends on the electron donating strength of the aryl moieties (VDA = 0.22-0.55 eV), as well as the molecular conformation, based on steady state and time-resolved transient absorption spectroscopies. We also found that electron coupling does not show the add-up (or synergetic) effect. Solvent polarity-dependent intersystem crossing (ISC) was observed for the dyad/triads and singlet oxygen quantum yield decreases in polar solvents. Femtosecond transient absorption results indicate that the charge separation (CS) for 9-An-NDI-NH occurs on time scale of 0.83 ps (in toluene) or 0.71 ps (in acetonitrile). The charge recombination (CR) process (50 ps in toluene) produces triplet state with ωISC = 19%. The triplet state lifetime is up to 22 μs. This result indicates that orthogonal geometry for a compact electron donor/acceptor does not lead to efficient ISC via CR. Other factors such as the energy gap between the CS state and triplet state also determine the ISC efficiency.
- Chen, Kepeng,Zhao, Jianzhang,Li, Xiaoxin,Gurzadyan, Gagik G.
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p. 2503 - 2516
(2019/03/29)
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- A fluorescent naphthalenediimide-alkoxyfuroxan photoinduced nitric oxide donor
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We describe the design and facile synthesis of a fluorescent alkoxyfuroxan naphthalenediimide (NDI) hybrid nitric oxide (NO) donor molecule which releases NO under spatiotemporal control when irradiated with visible light (420600 nm). The hybrid also demonstrates cellular uptake made possible by its fluorescence capability. This research consolidates our recent work into visible light absorbing photosensitised furoxan NO release by addressing the limitations of previous designs. Key points of photoinduced nitric oxide donors are highlighted such as water solubility, NO release, cellular uptake, fluorescence, and longer absorption wavelengths.
- Seymour, Christopher Peter,Nakata, Akito,Tsubaki, Motonari,Hayashi, Masahiko,Matsubara, Ryosuke
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p. 162 - 169
(2019/01/28)
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- Aqueous Phase Phosphorescence: Ambient Triplet Harvesting of Purely Organic Phosphors via Supramolecular Scaffolding
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Ambient solution and amorphous state room temperature phosphorescence (RTP) from purely organic chromophores is rarely achieved. Remarkable stabilization of triplet excitons is realized to obtain deep red phosphorescence in water and in amorphous film state under ambient conditions by a unique supramolecular hybrid assembly between inorganic laponite clay and heavy atom core substituted naphthalene diimide (NDI) phosphor. Structural rigidity and oxygen tolerance of the inorganic template along with controlled molecular organization via supramolecular scaffolding are envisaged to alleviate the unprecedented aqueous phase phosphorescence.
- Kuila, Suman,Rao, K. Venkata,Garain, Swadhin,Samanta, Pralok K.,Das, Shubhajit,Pati, Swapan K.,Eswaramoorthy, Muthusamy,George, Subi J.
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supporting information
p. 17115 - 17119
(2018/12/11)
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- An Electron Transport Layer Material and the Application Thereof
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The present invention belongs to the technical field of optoelectronic devices, and discloses an electron transport layer material and its application. This material has the following structure: wherein n is a natural number of 1 to 10000, B is a strongly polar group, A1 and A2 are the same or different aromatic ring derivatives or conjugated units containing carbon-carbon double bonds and carbon-nitrogen bonds, M is a connection unit between A2 and B and is an alkyl group containing 1 to 20 carbon atoms, or is an alkyl group in which one or more carbon atoms are replaced by one or more functional groups selected from oxygen atoms, alkenyl groups, alkynyl groups, aryl groups or ester groups, and the hydrogen atom is replaced by a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the above-mentioned functional groups.
- -
-
Paragraph 0031; 0032
(2018/02/28)
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- Core-substituted naphthalenediimides anchored on BiVO4 for visible light-driven water splitting
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In this work, a novel catalytic system for the sunlight-driven water splitting reaction, which exploits the photocatalytic ability of BiVO4 coupled to a new kind of noble-metal-free organic dye molecules, is proposed. Hence, mono- and di-substituted naphthalenediimides (NDIs) were designed to have different functional groups that provide to them both tunable optical properties and adjustable HOMO/LUMO levels, and were selectively prepared (starting from 1,4,5,8-naphthalenetetracarboxylic acid) achieving yields >69%. Smart anchoring groups (i.e. carboxylates or aromatic amines) were added to the dyes in order to allow them to covalently bond to acidic -OH groups present on the BiVO4 surface. An easy and low-cost room temperature dip-coating technique was used to dye-sensitize both BiVO4 powders and thin films. NMR, MS, FT-IR, TG, FESEM, XRD, XPS and optical analyses confirmed the successful organic synthetic routes and good dyes/BiVO4 linkages. Photochemical and photoelectrochemical water oxidation reaction tests, together with DFT calculations, demonstrated that a proper alignment of the semiconductor/NDI-based dye energy levels is fundamental for enhancing the photocatalyst performance through a Z-scheme mechanism. The ability of the NDI organic molecules to delocalize the electronic charges was also a key factor for minimizing recombination processes and achieving more than a ten-fold increase in the photocurrent density of a 6 cm2 BiVO4 photo-electrode. The here reported results open new perspectives for the utilization of this new series of core-substituted NDIs, which are able to improve the activity of photocatalysts for different sunlight-driven applications, e.g. waste water treatment and organic contaminants' degradation, other than the production of solar fuels by water splitting mechanisms.
- Hernández, Simelys,Ottone, Carminna,Proto, Stefano,Tolod, Kristhine,Díaz De Los Bernardos, Miriam,Solé-Daura, Albert,Carbó, Jorge J.,Godard, Cyril,Castillón, Sergio,Russo, Nunzio,Saracco, Guido,Claver, Carmen
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p. 2448 - 2462
(2017/07/12)
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- Visualization of Stereoselective Supramolecular Polymers by Chirality-Controlled Energy Transfer
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Chirality-driven self-sorting is envisaged to efficiently control functional properties in supramolecular materials. However, the challenge arises because of a lack of analytical methods to directly monitor the enantioselectivity of the resulting supramolecular assemblies. Presented herein are two fluorescent core-substituted naphthalene-diimide-based donor and acceptor molecules with minimal structural mismatch and they comprise strong self-recognizing chiral motifs to determine the self-sorting process. As a consequence, stereoselective supramolecular polymerization with an unprecedented chirality control over energy transfer has been achieved. This chirality-controlled energy transfer has been further exploited as an efficient probe to visualize microscopically the chirality driven self-sorting.
- Sarkar, Aritra,Dhiman, Shikha,Chalishazar, Aditya,George, Subi J.
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supporting information
p. 13767 - 13771
(2017/10/09)
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- Excitonically Coupled States in Crystalline Coordination Networks
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When chromophores are brought into close proximity, noncovalent interactions (π–π/CH–π) can lead to the formation of excitonically coupled states, which bestow new photophysical properties upon the aggregates. Because the properties of the new states not only depend on the strength of intermolecular interactions, but also on the relative orientation, supramolecular assemblies, where these parameters can be varied in a deliberate fashion, provide novel possibilities for the control of photophysical properties. This work reports that core-substituted naphthalene diimides (cNDIs) can be incorporated into surface-mounted metal– organic structures/frameworks (SURMOFs) to yield optical properties strikingly different from conventional aggregates of such molecules, for example, formed in solution or by crystallization. Organic linkers are used, based on cNDIs, well-known organic chromophores with numerous applications in different optoelectronic devices, to fabricate MOF thin films on transparent substrates. A thorough characterization of the properties of these highly ordered chromophoric assemblies reveals the presence of non-emissive excited states in the crystalline material. Structural modulations provide further insights into the nature of the coupling that gives rise to an excited-state energy level in the periodic structure.
- Haldar, Ritesh,Mazel, Antoine,Joseph, Reetu,Adams, Michael,Howard, Ian A.,Richards, Bryce S.,Tsotsalas, Manuel,Redel, Engelbert,Diring, Stéphane,Odobel, Fabrice,W?ll, Christof
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supporting information
p. 14316 - 14322
(2017/09/25)
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- Dual-channel copper ion probe with naphthalimide as core as well as preparation method and application thereof
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The invention discloses a dual-channel fluorescent probe with naphthalimide as a core as well as a preparation method and application thereof. The fluorescent probe has the structural formula shown in the description. According to the invention, the preparation conditions are mild; the prepared probe NDI-Py has excellent photoelectric properties, not only can detect copper ions in an environment through color in a manner of being visible to naked eyes and rapidly detecting the copper ions through change of fluorescence, but also can be adsorbed on a silica gel plate to detect the copper ions with different concentrations in the environment and detect the copper ions in cells.
- -
-
Paragraph 0030; 0032
(2017/04/29)
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- Colorimetric-fluorescent probe taking naphthalimide as core, and preparation method and application of colorimetric-fluorescent probe
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The invention discloses a colorimetric-fluorescent probe taking naphthalimide as a core, and a preparation method of the colorimetric-fluorescent probe. The molecule of the probe has a structure as shown in formula (I) (shown in the description). According to the colorimetric-fluorescent probe and the preparation method, disclosed by the invention, the preparation condition is mild, the prepared colorimetric-fluorescent difunctional probe has good photoelectric characteristics, not only can copper ions in an environment be macroscopically detected, but also mercury ions in the environment can be detected by utilizing variation of fluorescence, and particularly, cyclic detection on the mercury ions can be realized when the colorimetric-fluorescent probe is adsorbed to a test strip.
- -
-
Paragraph 0034
(2017/08/28)
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- Structural insights into the aggregation-induced emission mechanism of naphthalene diimide solids
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Naphthalene diimides (NDIs) are an interesting class of electron-poor organic dyes but with weak emissions that limit their applications. Recently several examples have demonstrated that self-assembly of such weak emissive NDIs into some special aggregates could enhance their emissions. However, a detailed emission mechanism remains unexplored due to the lack of structural evidences. In order to go deep into the emissive mechanism and in turn guide material design, it is necessary to learn the molecular arrangement in the aggregates. For this purpose, in this paper we used a crystal engineering strategy to explore the structure-property relationships between the molecular packing and emissive properties of NDI derivatives in crystalline state, which revealed that the small slipped cofacial π-π stacking of NDI cores in the solid states answered for their enhanced emission behaviors. This observation has an extensive applicability and practical significance for design of NDI based aggregation-induced emission materials.
- Fang, Xin,Ke, Hua,Li, Lei,Lin, Mei-Jin
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p. 469 - 475
(2017/06/27)
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- Core-fluorinated naphthalene diimides: Synthesis, characterization, and application in n-type organic field-effect transistors
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A series of difluoro- and tetrafluoro-substituted naphthalene diimides (NDIs) were synthesized by halogen exchange reactions of corresponding bromo-NDIs with CsF in dioxane. Two strong electron acceptor molecules 6 and 8 with low-lying LUMO energy levels of -4.27 and -4.54 eV were obtained, starting from tetrafluoro-NDI. Organic field-effect transistors (OFETs) based on these fluorinated NDIs were fabricated by vapor deposition, exhibiting n-channel field-effect character under ambient conditions with the highest mobility of 0.1 cm2 V-1 s-1.
- Yuan, Zhongyi,Ma, Yingjie,Ge?ner, Thomas,Li, Mengmeng,Chen, Long,Eustachi, Michael,Weitz, R. Thomas,Li, Chen,Müllen, Klaus
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supporting information
p. 456 - 459
(2016/02/18)
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- N-Type Water/Alcohol-Soluble Naphthalene Diimide-Based Conjugated Polymers for High-Performance Polymer Solar Cells
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With the demonstration of small-area, single-junction polymer solar cells (PSCs) with power conversion efficiencies (PCEs) over the 10% performance milestone, the manufacturing of high-performance large-area PSC modules is becoming the most critical issue for commercial applications. However, materials and processes that are optimized for fabricating small-area devices may not be applicable for the production of high-performance large-area PSC modules. One of the challenges is to develop new conductive interfacial materials that can be easily processed with a wide range of thicknesses without significantly affecting the performance of the PSCs. Toward this goal, we report two novel naphthalene diimide-based, self-doped, n-type water/alcohol-soluble conjugated polymers (WSCPs) that can be processed with a broad thickness range of 5 to 100 nm as efficient electron transporting layers (ETLs) for high-performance PSCs. Space charge limited current and electron spin resonance spectroscopy studies confirm that the presence of amine or ammonium bromide groups on the side chains of the WSCP can n-dope PC71BM at the bulk heterojunction (BHJ)/ETL interface, which improves the electron extraction properties at the cathode. In addition, both amino functional groups can induce self-doping to the WSCPs, although by different doping mechanisms, which leads to highly conductive ETLs with reduced ohmic loss for electron transport and extraction. Ultimately, PSCs based on the self-doped WSCP ETLs exhibit significantly improved device performance, yielding PCEs as high as 9.7% and 10.11% for PTB7-Th/PC71BM and PffBT4T-2OD/PC71BM systems, respectively. More importantly, with PffBT4T-2OD/PC71BM BHJ as an active layer, a prominent PCE of over 8% was achieved even when a thick ETL of 100 nm was used. To the best of our knowledge, this is the highest efficiency demonstrated for PSCs with a thick interlayer and light-harvesting layer, which are important criteria for eventually making organic photovoltaic modules based on roll-to-roll coating processes.
- Wu, Zhihong,Sun, Chen,Dong, Sheng,Jiang, Xiao-Fang,Wu, Siping,Wu, Hongbin,Yip, Hin-Lap,Huang, Fei,Cao, Yong
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p. 2004 - 2013
(2016/03/01)
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- Fluorescent compounds with sensing functions for anilines and o-toluidines, and preparation and application of fluorescent sensing film of fluorescent compounds
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The invention discloses fluorescent compounds with sensing functions for anilines and o-toluidines, and preparation and application of a fluorescent sensing film of the fluorescent compounds. The compounds contain a naphthalene anhydride unit, an alkynyl aniline conjugated segment and a long alkyl chain structure segment. Compared with the perylene anhydride, the naphthalene anhydride has the advantages of higher solubility, abundant photo-physical properties, high photochemical stability and high pi-pi accumulative action. By using the structure units, the prepared fluorescent compounds have supramolecular characteristics, and abundant gelation behaviors and assembly behaviors. Therefore, the sensing film prepared from the fluorescent compounds has the advantages of controllable microscopic shape, favorable stability, high sensitivity and long service life, and is reusable. The fluorescent compounds implement sensitive detection on anilines, and more importantly, the detection is completely reversible, thereby laying a solid foundation for implementing aniline fluorescent sensors.
- -
-
Paragraph 0052; 0088; 0090; 0147; 0149
(2017/02/17)
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- Antioxidants Having Aromatic Structures Reacting with Superoxide
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Disclosed is a method of treating diseases which are: reactive oxygen species mediated, ischemic or reperfusion-related, or T-cell mediated, including autoimmune diseases. The method is administering a therapeutically effective amount of a formulation wherein the active ingredient includes non-phenolic aromatic structures that are electron deficient and are capable of converting the superoxide radical to O2; and/or of converting superoxide radical to oxygen and hydrogen peroxide, or pharmaceutically acceptable salts of said structures. Also disclosed is a method of diagnosing and treating such diseases and conditions.
- -
-
Sheet 2A; 5A
(2016/07/27)
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- Core substituted naphthalene diimide-metallo bisterpyridine supramolecular polymers: Synthesis, photophysics and morphology
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A series of metallo Ru(ii), Fe(ii), Co(ii) bisterpyridine polymers were prepared with naphthalene diimide (NDI) groups inserted between two 4′-phenyl-2,2:6′,2′′-terpyridine (phtpy) groups. Core-substituted NDIs typically have long-lived excited states with relatively high quantum yields, yet the NDI emission in these metallopolymers was completely quenched, most likely because of efficient electron-transfer from the M(phtpy)22+ groups to the excited NDIs. AFM, TEM and SEM experiments indicate that the regiochemistry of the substitution on the core of the naphthalene diimide, together with coordination of the terpyridine ligand to different metals, strongly influences the morphologies of the resulting metallosupramolecular polymers. The morphologies of spin-coated samples of the para-substituted polymers revealed the formation of long, bundled nanorods. Lengths on the order of ~8 μm were observed for the bundle of the longest polymers (5-Ru) by both AFM and TEM microscopy. The morphologies of the meta substituted polymers, on the other hand, exhibited significantly shorter and less well-defined morphologies. This journal is
- Shokouhi Mehr, Hamideh,Romano, Natalie C.,Altamimi, Rashid,Modarelli, Jody M.,Modarelli, David A.
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p. 3176 - 3184
(2015/03/05)
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- Rational synthesis of Ab-type n -substituted core-functionalized naphthalene diimides (cNDIs)
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Acid-mediated transformation of tetraethyl 2,6-diethoxynaphthalene-1,4,5,8-tetracarboxylate selectively affords the core-substituted naphthalene-anhydride-ester (cNAE) in quantitative yield. This anhydride can be selectively converted into hetero-N-substituted core-functionalized naphthalene diimides (cNDIs) through sequential condensation reactions in the presence of the precursor amine with very high isolated yields over four steps. The approach can be applied to prepare a large variety of heterocyclic, aromatic, and aliphatic heterodiimides.
- Berezin, Andrey A.,Sciutto, Andrea,Demitri, Nicola,Bonifazi, Davide
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supporting information
p. 1870 - 1873
(2015/04/27)
-
- Synergetic effect of CN∧N/C∧N∧N coordination and the arylacetylide ligands on the photophysical properties of cyclometalated platinum complexes
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Six coordinated Pt(II) complexes were prepared, in which the CN∧N or the C∧N∧N ligand were used to form the Pt(II) coordination center. For each coordination profile, three different arylacetylide ligands were used, i.e. naphthalenediimide (NDI), pyrenyl (Py) and naphthaleneimide (NI) acetylides. The electrochemical and the photophysical properties of the complexes were studied with steady-state and time-resolved absorption and emission spectroscopy, cyclic voltammetry and DFT calculations. The photostability and the photoluminescent properties of the complexes are finely tuned by the photoredox and photophysical properties of the arylacetylide ligands and the CN∧N/C∧N∧N Pt(II) coordination center. The triplet excited states of the complexes are an intraligand feature and the lifetime is long (90.1 μs). The photophysical properties of the complexes were rationalized with DFT calculations. The complexes were used as triplet photosensitizer for triplet-triplet annihilation upconversion. The upconversion quantum yield was up to 29.7%. The results are useful for future designing of Pt(II) complexes showing strong visible light-absorption, RT phosphorescence and long-lived triplet excited states.
- Wu, Wenting,Wu, Xueyan,Zhao, Jianzhang,Wu, Mingbo
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supporting information
p. 2291 - 2301
(2015/04/27)
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- Novel electron acceptor -donor-acceptor Naphthalene diimide compound and organic electronic device that contains it
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The present invention relates to an organic semiconductor compound used for manufacturing a novel naphthalene diimide derivative compound in which an electron donor compound is inserted between two naphthalene diimides. Also, a compound is manufactured by synthesizing the organic semiconductor compound of the present invention and substituted or unsubstituted thiophene including a naphthalene diimide derivative and sulfur (S) and accordingly shows a low band gap and, therefore an organic electronic device including the same has a high efficiency. Also, the organic semiconductor compound in the present invention has outstanding thermal stability and physical properties as well as a high interaction between molecules and can be accordingly used as organic semiconductor materials with a high electrical property. The organic semiconductor compound in the present invention can be used in various organic electron devices including an organic thin-film transistor.
- -
-
Paragraph 0047-0049
(2016/11/24)
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- Air-stable ambipolar organic field-effect transistors based on naphthalenediimide-diketopyrrolopyrrole copolymers
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Two air-stable polymeric semiconductors were rationally designed and synthesized, namely PNDI-DPP and PNDI-T(DPP)T, containing naphthalenediimide (NDI) units and diketopyrrolopyrrole (DPP). The coplanar thiophene-substituted DPP moieties act as donors rather than acceptors, even though DPP is an electron-deficient core. In a bottom-gate/top-contact device architecture, the effect of changing the number of thiophene linkers on the performance of the two completely different OFETs was investigated. PNDI-T(DPP)T presented unipolar p-type behaviour with an average hole mobility of 0.02 cm2 V-1 s-1, while PNDI-DPP exhibited ambipolar transport with average electron and hole mobilities of 5.7 × 10-3 and 1.6 × 10-3 cm2 V-1 s-1, respectively. Moreover, OFETs based on the two polymers showed good air-stability with negligible changes after being stored under ambient conditions for over 3 months. This journal is
- Wang, Ping,Li, Hui,Gu, Chunling,Dong, Huanli,Xu, Zhenzhen,Fu, Hongbing
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p. 19520 - 19527
(2015/05/05)
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- Tuning the optoelectronic properties of core-substituted naphthalene diimides by the selective conversion of imides to monothioimides
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Selective sulfur substitution of the distal carbonyls of a core-substituted naphthalene diimide was obtained when a combination of core and imide substituents were used. The substituents appear to inhibit thionation of the proximal carbonyl by steric hindrance. Each thionation caused a 50 nm bathochromic shift of the visible absorption band and an anodic shift of the reduction potentials. The dithionated compound has a λmax in the near-IR at 733 nm and an optical gap of 1.59 eV, which is unusually low for this type of molecule. Thionation of carbonyls offers a useful avenue for tuning optoelectronic properties of NDI-based materials.
- Etheridge,Fernando,Golen,Rheingold,Sauve
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p. 46534 - 46539
(2015/06/16)
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- Naphthalene diimide based materials with adjustable redox potentials: Evaluation for organic lithium-ion batteries
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The promising crystallinity and tunable redox capabilities of naphthalene diimides make them attractive candidates as electroactive materials for organic-based lithium-ion batteries. In this study, a family of naphthalene diimide derivates was synthesized and their redox properties explored with the intent of unveiling structures with reduction potentials that are higher than those encountered in previous organic redox processes. Changes in the electronic characteristics of the aryl substituents resulted in materials with discharge potentials that vary from 2.3 to 2.9 V vs Li/Li+, with discharge capacities as high as 121 mAh/g.
- Vadehra, Geeta S.,Maloney, Ryan P.,Garcia-Garibay, Miguel A.,Dunn, Bruce
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p. 7151 - 7157
(2015/02/19)
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- Phthalimide-based π-conjugated small molecules with tailored electronic energy levels for use as acceptors in organic solar cells
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The design, synthesis, and characterization of seven phthalimide-based organic π-conjugated small molecules are reported. The new materials are based on a phthalimide-thiophene-CORE-thiophene-phthalimide architecture. The CORE units utilized were phthalimide (M2), diketopyrrolopyrrole (M3), isoindigo (M4), naphthalene diimide (M5), perylene diimide (M6), and difluorobenzothiadiazole (M7); they were specifically selected to progressively increase the electron affinity of the resulting compound. A small molecule with no core (M1) was synthesized for comparison. Each material was synthesized through optimized direct heteroarylation cross-coupling procedures using bench top solvents in air. Combinations of UV-visible spectroscopy (UV-vis), cyclic voltammetry (CV), differential scanning calorimetry (DSC), ultraviolet photoelectron spectroscopy (UPS) and density functional theory (DFT) were used to characterize each material. The use of various core acceptor building blocks with differing electron affinities resulted in the series M1-M7 having a range of energetically deep LUMO levels and a range of HOMO-LUMO gap energies. Meanwhile, the melting and crystallization temperatures of the molecules M1-M7 were also found to vary according to the change in central acceptor unit. Compounds M1-M7 were employed as acceptors in combination with either the polymeric donor P3HT or small molecule donor DTS(FBTTh2)2 to understand how the LUMO levels of each acceptor influences the open circuit voltage (Voc). It was found that, in general, Voc was only weakly related to the offset between the HOMO energy level of the donor and LUMO level of the acceptor used, with a Voc of up to 1.2 V being achieved for M1.
- Hendsbee, Arthur D.,McAfee, Seth M.,Sun, Jon-Paul,McCormick, Theresa M.,Hill, Ian G.,Welch, Gregory C.
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supporting information
p. 8904 - 8915
(2015/09/01)
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- Broadband visible-light-harvesting trans-bis(alkylphosphine) platinum(II)-alkynyl complexes with singlet energy transfer between BODIPY and naphthalene diimide ligands
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A heteroleptic bis(tributylphosphine) platinum(II)-alkynyl complex (Pt-1) showing broadband visible-light absorption was prepared. Two different visible-light-absorbing ligands, that is, ethynylated boron-dipyrromethene (BODIPY) and a functionalized naphthalene diimide (NDI) were used in the molecule. Two reference complexes, Pt-2 and Pt-3, which contain only the NDI or BODIPY ligand, respectively, were also prepared. The coordinated BODIPY ligand shows absorption at 503 nm and fluorescence at 516 nm, whereas the coordinated NDI ligand absorbs at 594 nm; the spectral overlap between the two ligands ensures intramolecular resonance energy transfer in Pt-1, with BODIPY as the singlet energy donor and NDI as the energy acceptor. The complex shows strong absorption in the region 450 nm-640 nm, with molar absorption coefficient up to 88 000 m-1 cm-1. Longlived triplet excited states lifetimes were observed for Pt-1-Pt-3 (36.9 μs, 28.3 μs, and 818.6 μs, respectively). Singlet and triplet energy transfer processes were studied by the fluorescence/ phosphorescence excitation spectra, steady-state and time-resolved UV/Vis absorption and luminescence spectra, as well as nanosecond time-resolved transient difference absorption spectra. A triplet-state equilibrium was observed for Pt-1. The complexes were used as triplet photosensitizers for triplet-triplet annihilation upconversion, with upconversion quantum yields up to 18.4% being observed for Pt-1.
- Liu, Lianlian,Guo, Song,Ma, Jie,Xu, Kejing,Zhao, Jianzhang,Zhang, Tierui
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p. 14282 - 14295
(2015/02/05)
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- Anion-π catalysis
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The introduction of new noncovalent interactions to build functional systems is of fundamental importance. We here report experimental and theoretical evidence that anion-π interactions can contribute to catalysis. The Kemp elimination is used as a classical tool to discover conceptually innovative catalysts for reactions with anionic transition states. For anion-π catalysis, a carboxylate base and a solubilizer are covalently attached to the π-acidic surface of naphthalenediimides. On these π-acidic surfaces, transition-state stabilizations up to ΔΔGTS = 31.8 ± 0.4 kJ mol-1 are found. This value corresponds to a transition-state recognition of KTS = 2.7 ± 0.5 μM and a catalytic proficiency of 3.8 × 105 M-1. Significantly increasing transition-state stabilization with increasing π-acidity of the catalyst, observed for two separate series, demonstrates the existence of "anion-π catalysis." In sharp contrast, increasing π-acidity of the best naphthalenediimide catalysts does not influence the more than 12 000-times weaker substrate recognition (KM = 34.5 ± 1.6 μM). Together with the disappearance of Michaelis-Menten kinetics on the expanded π-surfaces of perylenediimides, this finding supports that contributions from π-π interactions are not very important for anion-π catalysis. The linker between the π-acidic surface and the carboxylate base strongly influences activity. Insufficient length and flexibility cause incompatibility with saturation kinetics. Moreover, preorganizing linkers do not improve catalysis much, suggesting that the ideal positioning of the carboxylate base on the π-acidic surface is achieved by intramolecular anion-π interactions rather than by an optimized structure of the linker. Computational simulations are in excellent agreement with experimental results. They confirm, inter alia, that the stabilization of the anionic transition states (but not the neutral ground states) increases with the π-acidity of the catalysts, i.e., the existence of anion-π catalysis. Preliminary results on the general significance of anion-π catalysis beyond the Kemp elimination are briefly discussed.
- Zhao, Yingjie,Beuchat, Cesar,Domoto, Yuya,Gajewy, Jadwiga,Wilson, Adam,Mareda, Jiri,Sakai, Naomi,Matile, Stefan
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supporting information
p. 2101 - 2111
(2014/03/21)
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- DIIMIDE COMPOUNDS
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The invention relates to novel compounds which are naphthalene diimides of general formula (I): The compounds are used in therapy, particularly in cancer treatment.
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-
Paragraph 0036
(2014/09/29)
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- Naphthalenediimide bridged D-A polymers: Design, synthesis and electrochromic properties Dedicated to Professor Eyup Ozdemir.
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We have synthesized two new D-A electrochromic polymers; poly(N,N'-bis(2-hexyl)-2,6-dithiophene-1,4,5,8-naphthalenediimide) (PTNDI) and poly(N,N'-bis(2-hexyl)-2,6-(3,4-ethylenedioxythiophene)-1,4,5, 8-naphthalenedimiide) (PENDI) bearing a naphthalenedimiide chromophore in the backbone. Structural characterization of initial compounds and products were carried out by using FT-IR and 1H-NMR spectroscopies. The optical and electrochemical properties of these polymers were investigated by UV-Vis absorption spectroscopy and cyclic voltammetry, respectively. The results of spectroelectrochemical studies indicate that both polymers reveal various colors due to ambipolar redox behavior at cathodic and anodic regime. Both polymer films have reasonable redox stability (in the range of 75-80% after 1000 cycles), coloration efficiency (in the range of 80-100 cm2 C -1), and response time (approx. 1s). Moreover, it is clearly seen that replacing donor unit from thiophene to EDOT results in change only in neutral state color.
- Sefer, Emre,Baycan Koyuncu, Fatma
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p. 106 - 113
(2014/12/10)
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- Naphthalenediimide bridged D-A polymers: Design, synthesis and electrochromic properties Dedicated to Professor Eyup Ozdemir.
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We have synthesized two new D-A electrochromic polymers; poly(N,N'-bis(2-hexyl)-2,6-dithiophene-1,4,5,8-naphthalenediimide) (PTNDI) and poly(N,N'-bis(2-hexyl)-2,6-(3,4-ethylenedioxythiophene)-1,4,5,8-naphthalenedimiide) (PENDI) bearing a naphthalenedimiide chromophore in the backbone. Structural characterization of initial compounds and products were carried out by using FT-IR and 1H-NMR spectroscopies. The optical and electrochemical properties of these polymers were investigated by UV-Vis absorption spectroscopy and cyclic voltammetry, respectively. The results of spectroelectrochemical studies indicate that both polymers reveal various colors due to ambipolar redox behavior at cathodic and anodic regime. Both polymer films have reasonable redox stability (in the range of 75-80% after 1000 cycles), coloration efficiency (in the range of 80-100 cm2 C-1), and response time (approx. 1s). Moreover, it is clearly seen that replacing donor unit from thiophene to EDOT results in change only in neutral state color.
- Sefer, Emre,Koyuncu, Fatma Baycan
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p. 106 - 113
(2015/02/19)
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