214-83-5Relevant academic research and scientific papers
Dynamic Covalent Synthesis of Crystalline Porous Graphitic Frameworks
Cai, Songliang,Chan, Emory M.,Chen, Hao,Ciston, Jim,Dun, Chaochao,Gordon, Madeleine P.,Li, Xinle,Liu, Yawei,Liu, Yi,Mao, Haiyan,Reimer, Jeffrey A.,Sun, Bing,Tan, Tianwei,Urban, Jeffrey J.,Wang, Hongxia,Zhang, Jian,Zhang, Qiubo,Zheng, Haimei,Zheng, Qi
, p. 933 - 944 (2020)
Porous graphitic framework (PGF) is a two-dimensional (2D) material that has emerging energy applications. An archetype contains stacked 2D layers, the structure of which features a fully annulated aromatic skeleton with embedded heteroatoms and periodic pores. Due to the lack of a rational approach in establishing in-plane order under mild synthetic conditions, the structural integrity of PGF has remained elusive and ultimately limited its material performance. Here, we report the discovery of the unusual dynamic character of the C=N bonds in the aromatic pyrazine ring system under basic aqueous conditions, which enables the successful synthesis of a crystalline porous nitrogenous graphitic framework with remarkable in-plane order, as evidenced by powder X-ray diffraction studies and direct visualization using high-resolution transmission electron microscopy. The crystalline framework displays superior performance as a cathode material for lithium-ion batteries, outperforming the amorphous counterparts in terms of capacity and cycle stability. Insertion of well-defined, evenly spaced nanoscale pores into the two-dimensional (2D) layers of graphene invokes exciting properties due to the modulation of its electronic band gaps and surface functionalities. A bottom-up synthesis approach to such porous graphitic frameworks (PGFs) is appealing but also remains a great challenge. The current methods of building covalent organic frameworks rely on a small collection of thermodynamically reversible reactions. Such reactions are, however, inadequate in generating a fully annulated aromatic skeleton in PGFs. With the discovery of dynamic pyrazine formation, we succeeded in applying this linking chemistry to obtain a crystalline PGF material, which has displayed high electrical conductivity and remarkable performance as a cathode material for lithium-ion batteries. We envision that the demonstrated success will open the door to a wide array of fully annulated 2D porous frameworks, which hold immense potential for clean energy applications. We report the unusual dynamic characteristics of the C=N bonds in the pyrazine ring promoted under basic aqueous conditions, which enables the successful synthesis of two-dimensional porous graphitic frameworks (PGFs) featuring fully annulated aromatic skeletons and periodic pores. The PGF displayed high electrical conductivity and remarkable performance as a cathode material for lithium-ion batteries, far outperforming the amorphous counterparts in terms of capacity and cycle stability.
Synthesis, ionisation potentials and electron affinities of hexaazatrinaphthylene derivatives
Barlow, Stephen,Zhang, Qing,Kaafarani, Bilal R.,Risko, Chad,Amy, Fabrice,Chan, Calvin K.,Domercq, Benoit,Starikova, Zoya A.,Antipin,Timofeeva, Tatiana V.,Kippelen, Bernard,Bredas, Jean-Luc,Kahn, Antoine,Marder, Seth R.
, p. 3537 - 3547 (2007)
Several hexaazatrinaphthylene derivatives and a tris-(thieno) hexaazatriphenylene derivative have been synthesised by reaction of the appropriate diamines with hexaketocyclohexane. The crystal structure of 2,3,8,9,14,15-hexachloro-5,6,11,12,17,18-hexaazatrinaphthylene has been determined by X-ray diffraction; this reveals a molecular structure in good agreement with that predicted by density functional theory (DFT) calculations and π-stacking with an average spacing between adjacent molecular planes of 3.18 A. Solid-state ionisation potentials have been measured by using UV photoelectron spectroscopy and fall in the range of 5.99 to 7.76 eV, whereas solid-state electron affinities, measured using inverse photoelectron spectroscopy, vary in the range -2.65 to -4.59 eV. The most easily reduced example is a tris(thieno)hexaazatriphenylene substituted with bis(trifluoro-methyl)phenyl groups; DFT calculations suggest that the highly exothermic electron affinity is due both to the replacement of the outermost phenylene rings of hexaazatrinaphthylene with thieno groups and to the presence of electron-withdrawing bis(trifluoro-methyl)phenyl groups. The rather exothermic electron affinities, the potential for adopting π-stacked structures and the low intramolecular reorganisation energies obtained by DFT calculations suggest that some of these molecules may be useful electron-transport materials.
Electrical and magnetic properties of a radical-based Co(II) coordination complex with C–H?π and π?π supramolecular interactions
Wu, Wen-Hao,Huang, Meng-Jiao,Zeng, Qi,Xian, Wan-Ru,Liao, Wei-Ming,He, Jun
, p. 149 - 153 (2019)
HAN–[rad] radical based supramolecular Co(II) complex, Co-HAN, has been synthesized with reaction of large π-conjugated hexaazatrinaphthylene (HAN), cobalt salt and ethylenediamine reductant through one-pot solvothermal method. In aggregating crystal network of Co-HAN, two kinds of Zig-Zag supramolecular channels are formed by π?π stacking and C–H?π hydrogen-bond interactions, respectively. The supramolecular interactions, especially π?π stacking, help promote the charge transport, leading to an enhanced electrical conductivity (σ = 0.599 × 10?7 S·cm?1). In addition, electron paramagnetic resonance (EPR) measurements indicated of antiferromagnetic interactions between monoradical ligand and Co(II) ion. The temperature-dependent magnetic susceptibility and χmT value suggests that Co-HAN exhibits a normal paramagnetic behavior for an effective spin of 1/2 coming from the unquenched orbit magnetic moment of Co(II) ions.
Proton Insertion Chemistry of a Zinc–Organic Battery
Deng, Shenzhen,Liu, Luojia,Niu, Zhiqiang,Tie, Zhiwei,Zhao, Dongbing
, p. 4920 - 4924 (2020)
Proton storage in rechargeable aqueous zinc-ion batteries (ZIBs) is attracting extensive attention owing to the fast kinetics of H+ insertion/extraction. However, it has not been achieved in organic materials-based ZIBs with a mild electrolyte. Now, aqueous ZIBs based on diquinoxalino [2,3-a:2′,3′-c] phenazine (HATN) in a mild electrolyte are developed. Electrochemical and structural analysis confirm for the first time that such Zn–HATN batteries experience a H+ uptake/removal behavior with highly reversible structural evolution of HATN. The H+ uptake/removal endows the Zn–HATN batteries with enhanced electrochemical performance. Proton insertion chemistry will broaden the horizons of aqueous Zn–organic batteries and open up new opportunities to construct high-performance ZIBs.
An all-organic symmetric battery based on a triquinoxalinylene derivative with different redox voltage active sites and a large conjugation system
Huang, Weiwei,Kong, Xiangyue,Lin, Yilin,Sun, Zhaopeng,Zhang, Yi
, p. 26208 - 26215 (2021/12/10)
Organic materials are considered to have broad application prospects in energy storage systems due to their strong designability and abundant resources. Here, we report a triquinoxalinylene derivative tribenzoquinoxaline-5,10-dione (3BQ) containing high redox potential functional groups (CO and CN) and a large number of low redox potential functional groups (unsaturated carbon). This paper uses 3BQ as the cathode and anode to assemble all-organic symmetric batteries. Since 3BQ has denser active sites and a larger conjuated system than triquinoxalinylene (3Q), the 3BQ cathode has an initial capacity of 506 mA h g-1 (Ctheo = 515 mA h g-1) at 0.2C, and the capacity of 3BQ and 3Q cathodes is 210 and 107 mA h g-1 after 300 cycles at 1C. The large conjugated system and planar structure of 3BQ inhibit its dissolution in electrolytes and accelerate the charge transfer rate, resulting in good cycle stability and rate performance for batteries. The all-organic symmetric batteries assembled with pre-lithiated 3BQ and pristine 3BQ deliver an initial capacity of 483 mA h g-1 at 0.2C, a capacity of 172 mA h g-1 after 300 cycles and an energy density of 301 W h kg-1. This work provides a strategy for the development of high-performance LIBs using organic materials as the cathode and anode. This journal is
One-pot homo- and cross-coupling of diazanaphthalenes via C-H substitution: Synthesis of Bis- and Tris-diazanaphthalenes
Ucar, Sefa,Dastan, Arif
, p. 4013 - 4022 (2020/09/21)
The transition metal-free coupling reactions of unactivated diazanaphthalenes were studied using only lithium tetramethylpiperidine (LiTMP) reagent. Symmetrical and nonsymmetrical bis-diazanaphthalenes were synthesized in moderate to high yield by homo- and cross-coupling of related monomers. In addition, the single-step synthesis of diquinoxalino [2,3-a: 2', 3'c] phenazine and 2,2': 3', 2″ - terquinoxaline using the appropriate equivalent amount of LiTMP was performed. The products were characterized by means of NMR spectroscopy and HRMS spectrometry.
Hexaazatriphenylene derivatives/GO composites as organic cathodes for lithium ion batteries
Wang, Jinquan,Tee, Kaize,Lee, Yuhang,Riduan, Siti Nurhanna,Zhang, Yugen
, p. 2752 - 2757 (2018/02/19)
Redox active organic molecules as cathode materials for lithium ion batteries are promising. However, these compounds are plagued by their high solubilities in electrolyte solution, leading to capacity decay and a short cycling life. Herein, we report nano-composites of hexaazatriphenylene (HAT) derivatives and graphene oxide (GO) (hexaazatrinaphthalene (HATN)/GO and hexaazatrinaphthalene tricarboxylic acid (HATNTA)/GO) as cathode materials for lithium ion batteries. HAT derivatives demonstrate strong π-π and H-bond interactions with GO, which remarkably suppress their dissolution in electrolyte, leading to significant improvement of their electrochemical performance.
SEMICONDUCTOR MATERIAL
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Paragraph 0050, (2017/08/15)
PROBLEM TO BE SOLVED: To provide a method for simply synthesizing a semiconductor material of which the band gap is comparatively small, and yet which exhibits strong light absorption property. SOLUTION: A semiconductor material is composed of a π-conjugated organic molecule including nitrogen atoms capable of being coordinated to metal ions in its skeleton and copper thiocyanate, in which the π-conjugated organic molecule and the copper ion are coordinately bonded to each other. A molecule having 1,4,5,8,9,12-hexaazatriphenylene (HAT) represented by following formula in its skeleton is desirable as the π-conjugated organic molecule, in the HAT, the nitrogen atoms capable of being coordinated to metal ions are included in its skeleton, and the semiconductor material includes a molecule comprising the HAT with a functional group bonded thereto as the π-conjugated organic molecule. The semiconductor material has a light absorber with a small band gap and being possibly used as an active layer of an organic thin film solar cell. The solar cell uses the semiconductor as the active layer. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
CHARGE-TRANSPORT MATERIALS, METHODS OF FABRICATION THEREOF, AND METHODS OF USE THEREOF
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Page/Page column 77-78, (2008/06/13)
Briefly described, embodiments of this disclosure include charge-transport materials, methods of forming charge-transport materials, and methods of using the charge-transport materials.
