- Structure-property relationships for tailoring phenoxazines as reducing photoredox catalysts
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Through the study of structure-property relationships using a combination of experimental and computational analyses, a number of phenoxazine derivatives have been developed as visible light absorbing, organic photoredox catalysts (PCs) with excited state reduction potentials rivaling those of highly reducing transition metal PCs. Time-dependent density functional theory (TD-DFT) computational modeling of the photoexcitation of N-aryl and core modified phenoxazines guided the design of PCs with absorption profiles in the visible regime. In accordance with our previous work with N,N-diaryl dihydrophenazines, characterization of noncore modified N-aryl phenoxazines in the excited state demonstrated that the nature of the N-aryl substituent dictates the ability of the PC to access a charge transfer excited state. However, our current analysis of core modified phenoxazines revealed that these molecules can access a different type of CT excited state which we posit involves a core substituent as the electron acceptor. Modification of the core of phenoxazine derivatives with electron-donating and electron-withdrawing substituents was used to alter triplet energies, excited state reduction potentials, and oxidation potentials of the phenoxazine derivatives. The catalytic activity of these molecules was explored using organocatalyzed atom transfer radical polymerization (O-ATRP) for the synthesis of poly(methyl methacrylate) (PMMA) using white light irradiation. All of the derivatives were determined to be suitable PCs for O-ATRP as indicated by a linear growth of polymer molecular weight as a function of monomer conversion and the ability to synthesize PMMA with moderate to low dispersity (dispersity less than or equal to 1.5) and initiator efficiencies typically greater than 70% at high conversions. However, only PCs that exhibit strong absorption of visible light and strong triplet excited state reduction potentials maintain control over the polymerization during the entire course of the reaction. The structure-property relationships established here will enable the application of these organic PCs for O-ATRP and other photoredox-catalyzed small molecule and polymer syntheses.
- McCarthy, Blaine G.,Pearson, Ryan M.,Lim, Chern-Hooi,Sartor, Steven M.,Damrauer, Niels H.,Miyake, Garret M.
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- BENZOXAZOLE DERIVATIVES AND FLUORESCENT MATERIAL COMPRISING THE SAME
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A benzoxazole derivative represented by Structural Formula 1 is provided. Thus, the present invention is not limited thereto. A fluorescent material is provided to remarkably improve fluorescence yield, to have excellent dyeing property and dispersibility, to minimize environmental pollution and to improve economic feasibility. Structural 1.
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Paragraph 0226-0230
(2021/07/13)
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- Photoactivated novel organic small-molecular matrixes and preparation method thereof, and application of photoactivated novel organic small-molecular matrixes in MALDI mass spectrometric detection
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The invention provides photoactivated novel organic small-molecular matrixes and a preparation method thereof, and application of the photoactivated novel organic small-molecular matrixes in MALDI mass spectrometric detection. According to the invention,
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Paragraph 0038; 0104-0106
(2021/04/10)
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- COMPOSITIONS AND METHODS OF PROMOTING ORGANIC PHOTOCATALYSIS
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The invention provides novel compounds and methods that are useful in promoting reactions that proceed through an oxidative quenching pathway. In certain embodiments, the reactions comprise atom transfer radical polymerization.
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Paragraph 0131
(2018/09/12)
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- Organic micromolecule material based on 2,6-dimethyl-4-cyanophenyl receptor unit, preparation and application
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The invention belongs to the technical field of organic photoelectric materials, and discloses an organic micromolecule material based on a 2,6-dimethyl-4-cyanophenyl receptor unit, preparation and application. The organic micromolecule material has a structural formula as shown in formula (I), and Ar in the formula shows a phenyl aromatic amine heterocycle or phenyl aromatic amine donor unit. Thematerial has a weak intramolecular charge transfer state, and thus, fluorescence emission of a zone from dark blue to ultraviolet can be realized. Meanwhile, because the molecules have quite short effective conjugated length, the material has high triplet state energy level. In the application of an organic electroluminescent device, the problem of unbalanced charge carriers of a unipolar organicphotoelectric material can be solved effectively, therefore, the structure of the device is simplified, and the performance of the device is improved.
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Paragraph 0028; 0030; 0031
(2018/10/19)
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- Pd-Catalyzed double N-arylation of primary amines to synthesize phenoxazines and phenothiazines
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An efficient and versatile Pd-catalyzed tandem C-N bond formation between aryl halides and primary amines is developed. The transformation allows a one-pot synthesis of phenoxazine and phenothiazine derivatives with a broad range of substitution patterns from readily available precursors.
- Zhang, Lu,Huang, Xin,Zhen, Shan,Zhao, Jing,Li, Heng,Yuan, Bingxin,Yang, Guanyu
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p. 6306 - 6309
(2017/08/10)
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- A phenoxazine compound or a phenothiazine compound synthesis method (by machine translation)
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The present invention discloses a series of novel OLEDs (phenothiazine) compound and its new synthetic method in under the nitrogen atmosphere, will be double-halide compound, primary amine, palladium compound, phosphine, alkali may be dissolved in the organic solvent, heating and stirring the reaction, extraction, drying, concentration, purification, to prepare a series of phenoxazine or phenothiazine compound. The invention involves the oxygen (sulfur) nitrogen compound synthesis technology field, in particular to a phenoxazine (phenothiazine) the preparation method of compound. The invention through palladium-catalyzed double-halide compound with the primary amine N-position and double-aromatise synthetic OLEDs (phenothiazine) compound, simple synthesis steps, mild reaction conditions, operation is simple and easy, the product yield as high as 99%, but also the applicable substrate a wide range, for the OLEDs (phenothiazine) compound synthesis provides a new train of thought, in the organic synthesis methodologically has great significance. (by machine translation)
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Paragraph 0029; 0030; 0031; 0032; 0033; 0034
(2017/07/21)
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- Stereoelectronic control of oxidation potentials of 3,7-bis(diarylamino)phenothiazines
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The influence of diarylamino (Ar2N-) substituents on the oxidation potential of 3,7-bis(diarylamino)phenothiazines (Ar2N)2-PTZ (1a-f, a: carbazolyl; b: dihydrodibenzoazepinyl; c: dibenzoazepinyl; d: diphenylamino; e: phenothiazinyl; and f: phenoxazinyl) is investigated, where the Ar2N-substituent sequence a→f is aligned in the increasing order of their electron-donating ability. Interestingly, a different sequence of electron-donating ability for Ar2N-substituents was observed for the oxidation potentials of (Ar2N)2-PTZ: 1a (Eox1 = +0.35 V vs. Fc/Fc+) > 1f (+0.30 V) > 1e (+0.15 V) > 1d (-0.05 V) > 1c (-0.19 V) > 1b (-0.22 V). The observed sequence can be explained by the stereoelectronic effect of the Ar2N-substituents to stabilize (Ar2N)2-PTZ+. Clear-cut examples are observed in the crystal structure of 1c+ and 1e+, for which coplanar conformation is observed between the PTZ+-plane and the planes of the sp2-hybridized nitrogen atoms in Ar2N-substituents through a large conformational change during the oxidation process of (Ar2N)2-PTZ.
- Karimata, Ayumu,Suzuki, Shuichi,Kozaki, Masatoshi,Okada, Keiji
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p. 56144 - 56152
(2017/12/26)
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- Organic small molecule luminescent material and organic electroluminescent device prepared from same
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The invention belongs to the field of organic photoelectric material technology, and discloses an organic small molecule luminescent material and an organic electroluminescent device prepared from same. The organic small molecule luminescent material uses
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Paragraph 0019; 0020; 0121; 0124
(2016/10/07)
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- Organocatalyzed Atom Transfer Radical Polymerization Using N-Aryl Phenoxazines as Photoredox Catalysts
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N-Aryl phenoxazines have been synthesized and introduced as strongly reducing metal-free photoredox catalysts in organocatalyzed atom transfer radical polymerization for the synthesis of well-defined polymers. Experiments confirmed quantum chemical predictions that, like their dihydrophenazine analogs, the photoexcited states of phenoxazine photoredox catalysts are strongly reducing and achieve superior performance when they possess charge transfer character. We compare phenoxazines to previously reported dihydrophenazines and phenothiazines as photoredox catalysts to gain insight into the performance of these catalysts and establish principles for catalyst design. A key finding reveals that maintenance of a planar conformation of the phenoxazine catalyst during the catalytic cycle encourages the synthesis of well-defined macromolecules. Using these principles, we realized a core substituted phenoxazine as a visible light photoredox catalyst that performed superior to UV-absorbing phenoxazines as well as previously reported organic photocatalysts in organocatalyzed atom transfer radical polymerization. Using this catalyst and irradiating with white LEDs resulted in the production of polymers with targeted molecular weights through achieving quantitative initiator efficiencies, which possess dispersities ranging from 1.13 to 1.31.
- Pearson, Ryan M.,Lim, Chern-Hooi,McCarthy, Blaine G.,Musgrave, Charles B.,Miyake, Garret M.
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supporting information
p. 11399 - 11407
(2016/11/05)
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- COMPOUND FOR ORGANIC OPTOELECTRONIC DEVICE, ORGANIC LIGHT EMITTING DIODE INCLUDING THE SAME AND DISPLAY INCLUDING THE ORGANIC LIGHT EMITTING DIODE
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Compound for organic optoelectronic devices, including organic luminous person element and same said device relates to display including organic light emitting device, an organic optoelectronic device represented by formula 1 a provided is a compound for the, excellent electrochemical and thermal stability and and excellent life characteristics, low, even under a low drive voltage optoelectronic devices additive is soluble in the organic monomer a high luminous efficiency can be produced. [Formula 1] Specification the present definition of said formula 1 is described.
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Paragraph 0787-0790
(2016/10/10)
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- Compound For Organic Optoelectronic Device, Organic Light Emitting Diode Including The Same and Display Including The Organic Light Emitting Diode
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Compound for organic optoelectronic devices, including organic luminous person element and same said device relates to display including organic light emitting device, an organic optoelectronic device represented by formula 1 a provided is a compound for the, excellent electrochemical and thermal stability and and excellent life characteristics, low, even under a low drive voltage optoelectronic devices additive is soluble in the organic monomer a high luminous efficiency can be produced. [Formula 1] Specification the present definition of said formula 1 is described.
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Paragraph 0794-0798
(2016/11/24)
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- A general route for synthesis of N-aryl phenoxazines via copper(i)-catalyzed N-, N-, and O-arylations of 2-aminophenols
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A novel copper(i)-catalyzed tandem reaction of N- and O-arylations of 2-[N-(2-chlorophenyl)amino]phenols was developed, by which a series of structurally novel N-aryl phenoxazines were synthesized efficiently. This success owes much to the discovery of hi
- Liu, Nan,Wang, Bo,Chen, Wenwen,Liu, Chulong,Wang, Xinyan,Hu, Yuefei
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p. 51133 - 51139
(2014/12/10)
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