- 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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- 1,4,5,8-Naphthalenetetracarboxylic acid cyclic 1,8-anhydride bis(dimethyl sulfoxide) solvate and 1,4,5,8-naphthalene-tetracarboxylic 1,8:4,5-dianhydride
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1,4,5,8-Naphthalenetetracarboxylic acid cyclic 1,8-anhydride crystallized from dimethyl sulfoxide (DMSO) as the solvate, C14H6O7.2C2H6OS, in the centrosymmetric space group P1. Two O-H...O hydrogen bonds with O...O distances of 2.592(3) and 2.598 (3) A are formed, with the two carboxylic acid OH groups as donors and the O atoms of the two inequivalent DMSO molecules as acceptors. The carboxylic H atoms are ordered, as are the carboxylic O atoms. In addition to the conventional hydrogen bonds, there are numerous C-H...O interactions consistent with the large number of potential CH donors and O-atom acceptors. 1,4,5,8-Naphthalenetetracarboxylic 1,8:4,5-dianhydride, C14H4O6, crystallized in the centrosymmetric space group P21/c with half the molecule as the asymmetric unit. Each molecule is involved in four significant C-H...O interactions as a donor and in an additional four as an acceptor. These eight interactions link each molecule to six neighboring molecules, forming a three-dimensional network. Geometric parameters of both substances are in general agreement with analogous parameters for naphthalic anhydride, monosodium 1,4,5,8-naphthalenetetracarboxylic acid cyclic 1,8-anhydride monohydrate and 1,4,5,8-naphthalenetetracarboxylic 1,8:4,5-dianhydride, as reported previously.
- Blackburn, Anthony C.,Fitzgerald, Lawrence J.,Gerkin, Roger E.
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- Conformationally rigid molecular and polymeric naphthalene-diimides containing C6H6N2constitutional isomers
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Organic thin films based on naphthalenediimides (NDIs) bearing alkyl substituents have shown interesting properties for application in OLEDs, thermoelectrics, solar cells, sensors and organic electronics. However, the polymorphic versatility attributed to the flexibility of alkyl chains remains a challenging issue, with detrimental implications on the performances. Aryl analogues containing C6H6N2 constitutional isomers are herein investigated as one of the possible way-out strategies. The synthesis of molecular and polymeric species is described, starting from naphthaleneteracarboxyldianhydride with isomeric aromatic amines and hydrazine. The materials are fully characterized by spectroscopy, thermal and structural X-ray diffraction methods, both as bulk powders and thin films, revealing a rich structural landscape. Depending on the stereochemistry of the branching aryls, the compounds show a variety of parallel stacking of the NDI cores, and high structural stability upon heating, up to 560 °C in the polymeric form. Thin films prepared by spin coating from organic solvent solutions and studied by grazing-incidence X-ray diffraction exhibit a high degree of crystallinity indicating the intrinsic tendency of these molecules to self-assemble in an ordered fashion without the need for any post-processing technique. In line with other NDI-based diimides, UV-vis spectroscopy indicates the optical band gaps falling in the visible region (2.87-3.02 eV). DFT calculations reveal a significant lowering of the frontier orbital energies of the hydrazido derivative. Beyond solution processing, the high thermal stability and the absence of polymorphic forms of these materials suggest that sublimation-based routes for films and device preparation can also be followed. This journal is
- Abbinante, Vincenzo Mirco,Barba, Luisa,Calabrese, Gabriele,García-Espejo, Gonzalo,Giannici, Francesco,Guagliardi, Antonietta,Marini, Diego,Masciocchi, Norberto,Milita, Silvia,Pipitone, Candida
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p. 10875 - 10888
(2021/09/02)
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- METHOD FOR PRODUCING CARBOXYLIC ACID ANHYDRIDE, METHOD FOR PRODUCING CARBOXYLIC IMIDE, AND METHOD FOR MANUFACTURING ELECTROPHOTOGRAPHIC PHOTOSENSITIVE MEMBER
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A method for producing a carboxylic acid anhydride includes heating a composition containing a specific compound in a solvent to yield the carboxylic acid anhydride. The solvent is an aprotic polar solvent having a boiling point of 50° C. or more.
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Paragraph 0110
(2017/01/19)
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- Mechanism of 1,4,5,8-naphthalene tetracarboxylic acid dianhydride hydrolysis and formation in aqueous solution
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The study of highly conjugated, carbonyl-containing molecules such as 1,4,5,8-naphthalene tetracarboxylic dianhydride, III, is of interest since reactivity differences and transmission of electronic effects through the conjugated framework can be evidenced. The kinetics of hydrolysis of III in aqueous solution were determined from 5 M acid to pH 10. In basic solution hydrolysis of III yields, sequentially, 1,4,5,8-naphthalene diacid monoanhydride, II, and 1,4,5,8-naphthalene tetracarboxylic acid, I. The second order rate constant for alkaline hydrolysis is 200 fold higher for the first ring opening. The water-catalyzed hydrolysis of III yields a pH-dependent mixture of ionic forms of I and II. The rate constant for water-catalyzed hydrolysis of III is 25 fold higher than that for II. In concentrated acid the rates for reaching equilibrium (I, II and III) increase and III is the major product. The pKas of I (3.24, 5.13 and 6.25) and II (3.05, 5.90) were determined by potentiometric, fluorescence and UV spectroscopy titrations and by quantitative fit of the kinetic and equilibrium data. The apparent, pH-dependent, equilibrium constants, KEqII, for anhydride formation between I and II were obtained from the UV spectra. The quantitative fit of kinetic and equilibrium data are consistent with the assumption that anhydride formation only proceeds with the fully protonated species for both I and II and permitted the estimation of the equilibrium constants for anhydride formation, KEqII. The value of KEqII (I II) between pH 1 and 6 was ca. 5. Geometry optimization calculations in the gas phase of the reactions of III in alkaline, neutral and acid conditions, at the DFT level of theory, gave electronic distributions that were qualitatively consistent with the experimental results. The Royal Society of Chemistry 2006.
- Barros,Cuccovia,Farah,Masini,Chaimovich,Politi
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- DERIVATIVES OF 1,4,5,8-NAPHTHALENETETRACARBOXYLIC ACID. IV. SOME RELATIONSHIPS GOVERNING THE OXIDATION OF 1,6- AND 1,8-PYRENEQUINONES BY ALKALI-METAL HYPOCHLORITES
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The oxidation of 1,6- and 1,8-pyrenequinones by alkali-metal hypochlorites to 1,4,5,8-naphthalenetetracarboxylic acid is preceded by the entry of not less than two hydroxyl groups into the molecule of the quinones. 1,3,6-Pyrenetrione is oxidized by hypochlorites with transfer of the reaction center to position 2.The 1,6- and 1,8-pyrenequinones and their monohalogen and 3-methoxy-substituted derivatives are converted into 1,4,5,8-naphthalenetetracarboxylic acid with yields of 50percent, but the corresponding quinones disubstituted at positions 3 and 8 do not react under these conditions.Quantum-chemical calculations of the electronic strucutre by the Hueckel method were used in the interpretation of the results.
- Shigalevskii, V. A.,Chesnovskii, V. S.,Filippov, M. P.,Solomatin, G. G.
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p. 1373 - 1379
(2007/10/02)
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