7326-80-9Relevant academic research and scientific papers
Heavily n-dopable π-conjugated redox polymers with ultrafast energy storage capability
Liang, Yanliang,Chen, Zhihua,Jing, Yan,Rong, Yaoguang,Facchetti, Antonio,Yao, Yan
, p. 4956 - 4959 (2015)
We report here the first successful demonstration of a π-conjugated redox polymer simultaneously featuring a π-conjugated backbone and integrated redox sites, which can be stably and reversibly n-doped to a high doping level of 2.0 with significantly enhanced electronic conductivity. The properties of such a heavily n-dopable polymer, poly{[N,N′-bis(2-octyldodecyl)-1,4,5,8-naphthalenedicarboximide-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)} (P(NDI2OD-T2)), were compared vis-à-vis to those of the corresponding backbone-insulated poly{[N,N′-bis(2-octyldodecyl)-1,4,5,8-naphthalenedicarboximide-2,6-diyl]-alt-5,5′-[2,2′-(1,2-ethanediyl)bithiophene]} (P(NDI2OD-TET)). When evaluated as a charge storage material for rechargeable Li batteries, P(NDI2OD-T2) delivers 95% of its theoretical capacity at a high rate of 100C (72 s per charge-discharge cycle) under practical measurement conditions as well as 96% capacity retention after 3000 cycles of deep discharge-charge. Electrochemical, impedance, and charge-transport measurements unambiguously demonstrate that the ultrafast electrode kinetics of P(NDI2OD-T2) are attributed to the high electronic conductivity of the polymer in the heavily n-doped state.
Complementary Semiconducting Polymer Blends: The Influence of Conjugation-Break Spacer Length in Matrix Polymers
Zhao, Xikang,Zhao, Yan,Ge, Qu,Butrouna, Kamal,Diao, Ying,Graham, Kenneth R.,Mei, Jianguo
, p. 2601 - 2608 (2016)
The concept of complementary semiconducting polymer blends (c-SPBs) for efficient charge transport was recently proposed and established by our group. In this study, we aim to reveal the influence of the length of conjugation-break spacers (CBSs) on charge transport properties of the matrix polymers and their corresponding complementary polymer blends. A series of 11 DPP-based semiconducting polymers DPP-Cm (m = 2-12) that incorporate CBSs of 2-12 methylene units along the polymer backbones were prepared and characterized. The UV-vis spectra and the ultraviolet photoelectron spectroscopy (UPS) measurements show that the CBS length has marginal influence on the polymer absorption spectra, energy levels, and band gaps. It also has little impact on polymer decomposition temperatures. However, the CBS length has a profound influence on polymer phase transition and the heat of fusion. As for the melt transitions, an odd-even effect is observed from DPP-C2 to DPP-C7, in which polymers with even-numbered CBSs show higher melting points than their adjacent odd-numbered derivatives. The trend is opposite for heat of fusion. The polymers with odd-numbered CBSs exhibit larger heat of fusion, indicating higher ordering and crystallinity. The odd-even effect is also found in surface morphologies of the polymers by atomic force microscopy (AFM). The polymers with the even CBSs have a more interconnected feature that appear more fibrillar than the polymers with the odd linkages. As far as charge carrier mobility is concerned, the average number drops from 0.023 cm2 V-1 s-1 to 7.9 × 10-6 cm2 V-1 s-1 as the CBS moves from C2 to C12. It is intriguing to observe that even-numbered polymers outperform the adjacent odd-numbered polymers, despite the fact that the latter show higher ordering and crystallinity in thin films. When these polymers are mixed with fully conjugated DPP-C0 (2 wt %, designated as tie chain polymer), the obtained c-SPBs witness a dramatic increase (2-4 orders of magnitude) in charge carrier mobility. Interestingly, the odd-even effect is not found for charge transport in the c-SPBs. This work reveals that the length of CBSs plays a significant role in charge transport properties of the matrix polymers and reconfirms that efficient charge transport properties of the c-SPB result from the interactions between matrix polymers and tie chain polymers. This begins to provide guidelines as to what spacer lengths may be utilized to offer the best balance between processing and charge transport properties.
Synthesis of Dibenzyls by Nickel-Catalyzed Homocoupling of Benzyl Alcohols
Pan, Feng-Feng,Guo, Peng,Huang, Xiaochuang,Shu, Xing-Zhong
, p. 3094 - 3100 (2021/04/23)
Dibenzyls are essential building blocks that are widely used in organic synthesis, and they are typically prepared by the homocoupling of halides, organometallics, and ethers. Herein, we report an approach to this class of compounds using alcohols, which are more stable and readily available. The reaction proceeds via nickel-catalyzed and dimethyl oxalate assisted dynamic kinetic homocoupling of benzyl alcohols. Both primary and secondary alcohols are tolerated.
Silver-Catalyzed Decarboxylative Couplings of Acids and Anhydrides: An Entry to 1,2-Diketones and Aryl-Substituted Ethanes
Zou, Hua-Xu,Li, Yang,Yang, Yuan,Li, Jin-Heng,Xiang, Jiannan
supporting information, p. 1439 - 1443 (2018/02/26)
Silver-catalyzed oxidative decarboxylative couplings of carboxylic acids and anhydrides to produce 1,2-diketones and substituted ethanes were developed. This reaction allows the generation of acyl or alkyl radicals by decarboxylation of the corresponding α-keto acids, alkyl acids and anhydrides, which are sequentially coupled to efficiently construct a new C?C bond. This reaction represents a carboxylic acid decarboxylative alternative that employs a radical termination strategy. (Figure presented.).
Thermal Rearrangement of Sulfamoyl Azides: Reactivity and Mechanistic Study
Zou, Xiaodong,Zou, Jiaqi,Yang, Lizheng,Li, Guigen,Lu, Hongjian
, p. 4677 - 4688 (2017/05/12)
The rearrangement of sulfamoyl azides under thermal conditions to form a C-C bond while breaking two C-N bonds is reported. Mechanistic study shows that this reaction goes through a Curtius-type rearrangement to form a 1,1-diazene, then which rearranges possibly through both a concerted rearrangement process and a stepwise radical process. This rearrangement could be used in the synthesis of complex biologically active molecules, such as sterols, and piperine derivatives.
Synthesis and electropolymerization of a series of 2,2′-(ortho-carboranyl)bisthiophenes
Zhao, Ning,Fabre, Bruno,Bobadova-Parvanova, Petia,Fronczek, Frank R.,Vicente, M. Gra?a H.
, p. 157 - 165 (2016/12/18)
A series of 5,5′-functionalized 2,2′-(ortho-carboranyl)bisthiophene with bromo, vinyl, trimethylsilylethyne, N-methylpyrrole or thienyl groups was synthesized and all compounds were characterized by NMR, MS, and X-ray analysis. Electrochemical characterizations of 12a,b and 13a,b were conducted, and the di(thienyl-N-methylpyrrole)-o-carborane 12a and di(bisthienyl)-o-carborane 12b were successfully electropolymerized on a suitable anode to produce the corresponding conducting polymers. DFT calculations are consistent with the electrochemical data.
A 1,2-bis (2-thienyl) ethane method for the synthesis of
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Paragraph 0019; 0020, (2017/02/09)
The invention relates to a synthesis method of 1,2-di(2-thienyl)ethane, and particularly relates to a synthesis method of 1,2-di(2-thienyl)ethane by firstly converting 2-penphene as a raw material into thienyl borane, then reacting with p-toluene sulfonate-2-(2-thienyl)ethyl to generate 1,2--di(2-thienyl)ethane. The 1,2-di(2-thienyl)ethane is synthesized by the following steps: by taking 2-penphene as a raw material, firstly converting into thienyl borane, then reacting with p-toluene sulfonate-2-(2-thienyl)ethyl to generate 1,2--di(2-thienyl)ethane. The invention provides a new method for synthesizing 1,2-di(2-thienyl)ethane, and the synthesis method has the characteristics of being mild in reaction conditions, short in reaction route, and high in reaction yield.
Titania-promoted carboxylic acid alkylations of alkenes and cascade addition-cyclizations
Manley, David W.,McBurney, Roy T.,Miller, Phillip,Walton, John C.,Mills, Andrew,O'Rourke, Christopher
supporting information, p. 1386 - 1398 (2014/03/21)
Photochemical reactions employing TiO2 and carboxylic acids under dry anaerobic conditions led to several types of C-C bond-forming processes with electron-deficient alkenes. The efficiency of alkylation varied appreciably with substituents in the carboxylic acids. The reactions of aryloxyacetic acids with maleimides resulted in a cascade process in which a pyrrolochromene derivative accompanied the alkylated succinimide. The selectivity for one or other of these products could be tuned to some extent by employing the photoredox catalyst under different conditions. Aryloxyacetic acids adapted for intramolecular ring closures by inclusion of 2-alkenyl, 2-aryl, or 2-oximinyl functionality reacted rather poorly. Profiles of reactant consumption and product formation for these systems were obtained by an in situ NMR monitoring technique. An array of different catalyst forms were tested for efficiency and ease of use. The proposed mechanism, involving hole capture at the TiO2 surface by the carboxylates followed by CO2 loss, was supported by EPR spectroscopic evidence of the intermediates. Deuterium labeling indicated that the titania likely donates protons from surface hydroxyl groups as well as supplying electrons and holes, thus acting as both a catalyst and a reaction partner.
A clean and selective radical homocoupling employing carboxylic acids with titania photoredox catalysis
Manley, David W.,Walton, John C.
supporting information, p. 5394 - 5397 (2015/02/19)
A titania photoredox catalysis protocol was developed for the homocoupling of C-centered radicals derived from carboxylic acids. Intermolecular reactions were generally efficient and selective, furnishing the desired dimers in good yields under mild neutral conditions. Selective cross-coupling with two acids proved unsuccessful. An intra-molecular adaptation enabled macrocycles to be prepared, albeit in modest yields. (Chemical Equation Presented).
Unconventional titania photocatalysis: Direct deployment of carboxylic acids in alkylations and annulations
Manley, David W.,McBurney, Roy T.,Miller, Phillip,Howe, Russell F.,Rhydderch, Shona,Walton, John C.
supporting information; experimental part, p. 13580 - 13583 (2012/10/08)
Under dry, anaerobic conditions, TiO2 photocatalysis of carboxylic acid precursors resulted in carbon-carbon bond-forming processes. High yields of dimers were obtained from TiO2 treatment of carboxylic acids alone. On inclusion of electron-deficient alkenes, efficient alkylations were achieved with methoxymethyl and phenoxymethyl radicals. In reactions with maleic anhydride or maleimides, phenoxyacetic acid produced chromenedione derivatives in addition to adducts. These photocatalytic reactions are simple and cheap to perform, and the TiO2 is easily removed by filtration. The anaerobic photocatalysis strategy offers a range of synthetic possibilities.
