3638-73-1Relevant articles and documents
Heterometallic Actinide-Containing Photoresponsive Metal-Organic Frameworks: Dynamic and Static Tuning of Electronic Properties
Martin, Corey R.,Leith, Gabrielle A.,Kittikhunnatham, Preecha,Park, Kyoung Chul,Ejegbavwo, Otega A.,Mathur, Abhijai,Callahan, Cameron R.,Desmond, Shelby L.,Keener, Myles R.,Ahmed, Fiaz,Pandey, Shubham,Smith, Mark D.,Phillpot, Simon R.,Greytak, Andrew B.,Shustova, Natalia B.
, p. 8072 - 8080 (2021)
Acquiring fundamental knowledge of properties of actinide-based materials is a necessary step to create new possibilities for addressing the current challenges in the nuclear energy and nuclear waste sectors. In this report, we established a photophysics–electronics correlation for actinide-containing metal-organic frameworks (An-MOFs) as a function of excitation wavelength, for the first time. A stepwise approach for dynamically modulating electronic properties was applied for the first time towards actinide-based heterometallic MOFs through integration of photochromic linkers. Optical cycling, modeling of density of states near the Fermi edge, conductivity measurements, and photoisomerization kinetics were employed to shed light on the process of tailoring optoelectronic properties of An-MOFs. Furthermore, the first photochromic MOF-based field-effect transistor, in which the field-effect response could be changed through light exposure, was constructed. As a demonstration, the change in current upon light exposure was sufficient to operate a two-LED fail-safe indicator circuit.
Bicyclic Phenyl–Ethynyl Architectures: Synthesis of a 1,4-Bis(phenylbuta-1,3-diyn-1-yl) Benzene Banister
Bannwart, Linda Maria,Müntener, Thomas,Rickhaus, Michel,Jundt, Lukas,H?ussinger, Daniel,Mayor, Marcel
supporting information, p. 6295 - 6307 (2021/03/08)
The novel diacetylene bridged terphenylic macrocycle 1 is presented and discussed in the context of rotationally restricted “Gel?nder” oligomers. The 1,4-bis(phenylbuta-1,3-diyn-1-yl) benzene bridge of diacetylene 1 is significantly longer than its terphenyl backbone, forcing the bridge to bend around the central pylon. The synthesis of molecule 1 is based to a large extent on acetylene scaffolding strategies, profiting from orthogonal alkyne protection groups to close both macrocyclic subunits by oxidative acetylene coupling sequentially. The spatial arrangement and the dynamic enantiomerization process of the bicyclic target structure 1 are analyzed. In-depth NMR investigations not only reveal an unexpected spatial arrangement with both oligomer strands bent alongside the backbone, but also display the limited stability of the model compound in the presence of molecular oxygen.
A Metal-Free Direct Arene C?H Amination
Wang, Tao,Hoffmann, Marvin,Dreuw, Andreas,Hasagi?, Edina,Hu, Chao,Stein, Philipp M.,Witzel, Sina,Shi, Hongwei,Yang, Yangyang,Rudolph, Matthias,Stuck, Fabian,Rominger, Frank,Kerscher, Marion,Comba, Peter,Hashmi, A. Stephen K.
supporting information, p. 2783 - 2795 (2021/04/05)
The synthesis of aryl amines via the formation of a C?N bond is an essential tool for the preparation of functional materials, active pharmaceutical ingredients and bioactive products. Usually, this chemical connection is only possible by transition metal-catalyzed reactions, photochemistry or electrochemistry. Here, we report a metal-free arene C?H amination using hydroxylamine derivatives under benign conditions. A charge transfer interaction between the aminating reagents TsONHR and the arene substrates enables the chemoselective amination of the arene, even in the presence of various functional groups. Oxygen was crucial for an effective conversion and its accelerating role for the electron transfer step was proven experimentally. In addition, this was rationalized by a theoretical study which indicated the involvement of a dioxygen-bridged complex with a “Sandwich-like” arrangement of the aromatic starting materials and the aminating agents at the dioxygen molecule. (Figure presented.).
Method for reducing aromatic nitro into arylamine
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Paragraph 0109-0112; 0213-0216, (2020/07/15)
The invention relates to a method for reducing aromatic nitro to arylamine. The method comprises the following steps: (1) taking an aromatic nitro compound as a raw material, water as a hydrogen source, a palladium compound, cheap and easy to obtain, as a catalyst and tetrahydroxydiboron as an additive to reduce nitro to obtain a product; (2) taking the aromatic nitro compound as the raw material, a copper salt, cheap and easy to obtain, as the catalyst, the tetrahydroxydiboron as the additive to reduce the nitro to obtain a product; and (3) taking the aromatic nitro compound as the raw material, water as the hydrogen source, and the tetrahydroxydiboron as the additive, without needing a metal catalyst, to reduce the nitro to obtain a product. A preparation method for the arylamine, which is provided by the invention, is mild in reaction condition, low in costs, environment-friendly, high in yield, and suitable for industrial production.
CO-free, aqueous mediated, instant and selective reduction of nitrobenzeneviarobustly stable chalcogen stabilised iron carbonyl clusters (Fe3E2(CO)9, E = S, Se, Te)
Joshi, Raj Kumar,Kumari, Sangeeta,Sharma, Charu,Soni, Aditi,Srivastava, Avinash Kumar
, p. 32516 - 32521 (2020/09/17)
Highly stable and thermally robust iron chalcogenide carbonyl clusters Fe3E2(CO)9(E = S, Se or Te) have been explored for the reduction of nitrobenzene. A 15 min thermal heating of an aqueous solution of nitrobenzene and hydrazine hydrate in the catalytic presence of Fe3E2(CO)9(E = S, Se or Te) clusters yield average to excellent aniline transformations. Among the S, Se and Te based iron chalcogenised carbonyl clusters, the diselenide cluster was found to be most efficient and produce almost 90% yield of the desired amino product, the disulfide cluster was also found to be significantly active, produce the 85% yield of amino product, while the ditelluride cluster was not found to be active and produced only 49% yield of the desired product. The catalyst can be reused up to three catalytic cycles and it needs to be dried in an oven for one hour prior to reuse for the best results. The developed method is inexpensive, environmentally benign, does not require any precious metal or a high pressure of toxic CO gas and exclusively brings the selective reduction of the nitro group under feasible and inert free conditions.
Method for synthesizing dibromobenzene -2,5- 1,4- diiodo benzene (by machine translation)
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Page/Page column 6-8, (2020/01/12)
The synthetic method disclosed by the invention comprises 1,4 - the following steps: the, synthesis method disclosed by. the, invention has a good industrial production prospect, 1,4 - in the prior, art that, the raw materials are firstly, 2,5 - subjected to a nitrification step and then subjected to 2,5 - an iodine, generation step to generate 2,5 - the second bromo,4-diiodo benzene 1,4 . (by machine translation)
Aromatic C-H amination in hexafluoroisopropanol
D'Amato, Erica M.,B?rgel, Jonas,Ritter, Tobias
, p. 2424 - 2428 (2019/02/28)
We report a direct radical aromatic amination reaction that provides unprotected anilines with an improvement in the substrate scope compared to prior art. Hydrogen bonding by the solvent hexafluoroisopropanol to anions of cationic species is responsible for increased reactivity and can rationalize the enhancement in substrate scope. Our findings may have bearings on radical additions to arenes for direct C-H functionalization in general.
Cu-catalyzed reduction of azaarenes and nitroaromatics with diboronic acid as reductant
Pi, Danwei,Zhou, Haifeng,Zhou, Yanmei,Liu, Qixing,He, Renke,Shen, Guanshuo,Uozumi, Yasuhiro
, p. 2121 - 2129 (2018/03/23)
A ligand-free copper-catalyzed reduction of azaarenes with diboronic acid as reductant in an aprotic solvent under mild conditions has been developed. Most interestingly, the nitroazaarenes could be reduced exclusively to give the corresponding amines without touching the azaarene moieties. Furthermore, the reductive amination of aromatic nitro compounds and aromatic aldehydes has also been realized. A series of hydrogenated azaarenes and secondary amines were obtained with good functional group tolerance.
Functional phenylethynylene side arm poly(arylene ethynylene) conjugated polymers: Optical and electrochemical behavior for enrichment of electronic applications
Arun Kumar,Gomathi Priya,Alagar
supporting information, p. 5767 - 5773 (2018/04/23)
The poly(arylene ethynylene) (PAE) conjugated polymers (CPs) with a donor-acceptor (D-A) side arm have been designed and synthesized using Sonogashira cross coupling in the presence of cyano methylene, or cyano thiophene gave diethynyl (A) and alkoxy and alkyl substituted diiodo aryl monomers (D). An interesting electronic response in optical measurements such as UV-visible (UV-vis) and fluorescence (FL) spectra was observed in tetrahydrofuran solvent. From the FL spectra, it was observed that the CP solutions possess an interesting long bathochromic shift when compared with the UV-vis spectra, because of the electron withdrawing, electron releasing and conjugation effects. The electrochemical and thin film UV-vis spectral measurements provided highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) electronic energy levels and their corresponding semiconducting electronic energy gaps (Eg) of the PAE CPs. Among the side arm CPs, polymers P1 and P5 have low Eg of 2.14 eV and 2.17 eV. The new PAE CPs are reliable for use in electronic and photonics applications.
Synthetic method of 2,5-dibromo-p-phenylenediamine
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Paragraph 0090-0095; 0113; 0122-0124; 0151-0156; 0183-0185, (2018/10/26)
The invention discloses a synthetic method of 2,5-dibromo-p-phenylenediamine. According to the method, the 2,5-dibromo-p-phenylenediamine is synthesized from a compound shown as I, namely, p-dibromobenzene serving as a starting material. By adopting the synthetic method of the 2,5-dibromo-p-phenylenediamine disclosed by the invention, the 2,5-dibromo-p-phenylenediamine can be effectively synthesized. Moreover, the synthetic method has the advantages of high synthesis efficiency, safe production, simple process operation, short production period and the like, so that the method is more suitablefor large-scale and industrialized production of the 2,5-dibromo-p-phenylenediamine.
