Article
Chemistry, Multidisciplinary
Mingjie Liu, Junnan Liu, Jing Li, Zhenghua Zhao, Kai Zhou, Yueming Li, Peipei He, Jiashu Wu, Zongbi Bao, Qiwei Yang, Yiwen Yang, Qilong Ren, Zhiguo Zhang
Summary: This study demonstrates a novel strategy to address the limitations of aryl-ketone photocatalysts in terms of photostability and photoinduced electron transfer applications. By incorporating symmetric aryl ketones into conjugated covalent organic frameworks, improvements in photostability, electronic transfer efficiency, and structure-performance relationships were observed. This system provides a robust rule of thumb for designing new-generation aryl-ketone photocatalysts.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Xue-Ya Gou, Xin-Yu Zhu, Bo-Sheng Zhang, Yong-Min Liang
Summary: In recent years, the synthesis of C-aryl glycosides through C-H functionalization has gained significant attention due to its efficiency and economy. This review focuses on the synthesis of C-aryl glycosides using C-H arylation of glycosides and C-H glycosylation of arenes, highlighting their regioselectivity and diastereoselectivity. It is observed that newly developed C-H glycosylation reactions exhibit better selectivity than traditional Friedel-Crafts glycosylation, with milder reaction conditions that are compatible with acid-sensitive protective groups. However, remote C-H glycosylation of aromatic hydrocarbons remains a relatively unexplored area that requires further research.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Lea Festersen, Constantin Czekelius
Summary: An efficient metal-free, photoredox-mediated cascade cyclization of aryl 1-haloalk-5-ynyl ketones has been developed. Using catalytic amounts of eosin Y (EY) and EtNMe2 as a reductive quencher, various aryl 1-haloalk-5-ynyl ketones have been transformed into the corresponding cyclization products in up to 98% yield. As a result, synthetic access to differently alpha-functionalized cyclopenta[b]naphthones and direct construction of cyclopenta[b]naphtholes has been developed.
Article
Chemistry, Physical
Sofia Caby, Lydia M. Bouchet, Juan E. Arguello, Roberto A. Rossi, Javier Bardagi
Summary: Both photochemical and electrochemical transformations offer opportunities for environmentally friendly methodologies, with potential for improvement if combined. The research compared pure photochemical and electro-photochemical transformations, identifying a system with potential applications in both approaches and recognizing the excitation of radical anion as a key event. Despite similar yields and reaction rates, differences exist in terms of setup simplicity, catalyst solubility tolerance, selectivity, and optimization possibilities between the two methods.
Article
Chemistry, Organic
Lina Cai, Qihong Lai, Lele Zhang, Guotao Xue, Yirui Zhang, Na He, Mingqiang Huang, Shirong Hu, Shunyou Cai
Summary: This study presents an efficient and practical lanthanum-catalyzed reaction method for continuous epoxy-ring opening and oxidative dehydrogenative lactonization under visible-light irradiation. The lanthanum catalyst acts as both a Lewis acid and a photocatalyst in this reaction, eliminating the need for additional photocatalysts. The method allows for convenient preparation of isochromanones with oxygen-containing spirocyclic structural units.
Article
Chemistry, Organic
Rajesh T. Bhawale, Durgesh Sarothiya, Umesh A. Kshirsagar
Summary: A mild and efficient approach for the synthesis of aryl ketones of pyrido[1,2-a]pyrimidin-4-one has been developed by combining palladium catalysis and photoredox catalysis at room temperature. The method allows for good functional group tolerance and provides the desired products in good to excellent yields.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jun Wu, Nikolaos Kaplaneris, Julia Poehlmann, Takuya Michiyuki, Binbin Yuan, Lutz Ackermann
Summary: The prevalence of C-aryl glycosides in biologically active natural products and approved drugs has motivated the development of efficient synthesis strategies. Palladium catalysts with prefunctionalized substrates have been commonly used, while ruthenium-catalyzed C-aryl glycoside synthesis has been challenging. In this study, a versatile ruthenium(II)-catalyzed meta-C-H glycosylation method was disclosed, allowing for the synthesis of meta-C-aryl glycosides from readily available glycosyl halide donors. The ruthenium catalysis exhibited mild reaction conditions, exceptional levels of anomeric selectivity, and exclusive meta-site-selectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Vincent Desrosiers, Samantha M. Knight, Frederic-Georges Fontaine
Summary: Alkenyl boronates are commonly used reagents in organic synthesis for the formation of crucial bonds. This study introduces a metal-free isodesmic borylation strategy for the C-H borylation of electron-rich olefins, using 2-mercaptoimidazole compounds as efficient catalysts. The borylated compounds can be further functionalized in one-pot transformations, demonstrating the versatility and tolerance of this method.
Article
Chemistry, Physical
Zhiqian Yu, Qianhui Liu, Yudong Yang, Jingsong You
Summary: This study demonstrates that phenolic compounds can serve as effective ligands to control the regioselectivity of ortho-C-H arylation reactions, enabling the synthesis of various biaryl phosphines in a streamlined and practical manner. The phosphine ligand library shows great potential in catalytic coupling reactions and exhibits unique chemoselectivity when compared with commercially available classic phosphine ligands.
Review
Chemistry, Organic
Linhao Liu, Manisha Durai, Henri Doucet
Summary: The metal-catalyzed direct functionalization of two different C-H bonds of the same organic molecule, known as regiodivergent C-H bond functionalization, is an important research topic in organic chemistry. The number of tools to control such functionalizations has significantly increased over the last decades, with different metal sources being the most effective. Ru or Rh catalysts can be used for arylation of the aryl unit, while Pd or Cu catalysts can be used for arylation of the azole unit, allowing for regiodivergent direct arylation of aryl-substituted azoles.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Hang Yu, Zhong-Xia Wang
Summary: The [Ru(p-cymene)Cl-2](2)-catalyzed reaction of 2-arylpyridines with 1-aryl-2-vinylpyrrolidines in CF3CH2OH at 40 ? in the presence of KOAc affords ortho-C-H allylation products of arenes with high yields and Z/E ratios. The protocol is applicable to a wide range of substrates and tolerates various functional groups including alkyl, aryl, MeO, F, Cl, Br, OCF3, and CF3 groups.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Shaodong Kang, Jiaxing Li, Qin Yang, Zhibin Song, Yiyuan Peng
Summary: An efficient method for accessing 2-(2-beta-aryl ketone) substituted 2-arylquinazolinones has been described. 2-Carboxyl allylic alcohols derived from Morita-Baylis-Hillman adducts were used as the building blocks. The reaction between 2-aryl quinazolinones and 3-hydroxy-2-methylene-5-phenylpentanoic acid, catalyzed by [RhCp*Cl-2](2)-CF3COOAg, underwent C-H activation and decarboxylation to provide the desired products in good to excellent yields. Control experiments suggested that the nitrogen atom at the 3-position of the quinazolinone scaffold might serve as the directing group in this C-H activation/functionalization. A plausible mechanistic pathway for the synthesis of the target compounds is proposed.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Yuanyuan Luo, Zheng Liu, Ge Yang, Tianhong Wang, Zhengyang Bin, Jingbo Lan, Di Wu, Jingsong You
Summary: This study demonstrates the potential of multi-aryl spirobifluorenes as PHC hosts and provides a new approach for their synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Organic
Frederic-Georges Fontaine, Vincent Desrosiers
Summary: In recent years, the chemistry of frustrated Lewis pairs (FLP) has enabled various transformations, particularly in C-H bond activation and borylation reactions. A comparison is made between FLP borylation chemistry and early borylation methodologies. The mechanism of C-H borylation using inter- and intramolecular Lewis pairs, along with some applications, is presented.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
Mauro Mato, Paolo Cleto Bruzzese, Fumiya Takahashi, Markus Leutzsch, Edward J. J. Reijerse, Alexander Schnegg, Josep Cornella
Summary: This article reports the ability of a well-defined organobismuth(I) complex to undergo formal oxidative addition with a wide range of aryl electrophiles. This reaction, analogous to the transition metal chemistry and catalysis, has been largely underexplored in the context of main group elements.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Meng Wang, Wei-Hai Fang, Chenyang Li
Summary: In this study, the state-averaged driven similarity renormalization group (SA-DSRG) method was used to compute the vertical transition energies of 280 molecules. The optimal parameters were found and compared with other theoretical methods. The accuracy of SA-DSRG-PT2 was found to be better than level-shifted CASPT2, while SA-DSRG-PT3 and SA-sq-LDSRG(2) were comparable to CASPT3. Additionally, the vertical excitation energies of nucleobases were calculated, with SA-sq-LDSRG(2) performing well for π-* π* excitations and SA-DSRG-PT3 for n-* π* transitions.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Chemistry, Multidisciplinary
Cheng Cheng, Oleg V. Prezhdo, Run Long, Wei-Hai Fang
Summary: Identifying photolysis and photothermolysis during a photochemical reaction is challenging due to the non-equilibrium and ultrafast nature of the processes. In this study, the authors use advanced ab initio molecular dynamics to investigate the photodissociation of N2O on a TiO2 surface. They establish the detailed mechanism and find that photothermolysis governs the dissociation when N2O- is short-lived, while photolysis becomes dominant as the N2O- resonance lifetime increases. The authors also demonstrate that thermal dissociation of N2O can be achieved by choosing appropriate metal dopants. Overall, this study provides a fundamental understanding of the competition and synergy between photocatalytic and photothermocatalytic dissociation of N2O and has implications for designing high-performance transition-metal oxide catalysts.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Yanting Yang, Jing Liang, Weijia Li, Wenjing Yang, Chu Wang, Xiaorui Zhang, Wei-Hai Fang, Zhen Guo, Xuebo Chen
Summary: This study focuses on the photolysis of disubstituted tetrazoles, and theoretical calculations reveal the mechanistic understanding and reactivity analyses. The combination of space and electronic effects is found in maximum-absorption excitation. The results indicate that tetrazoles exhibit reactivity characteristics of bond-breaking selectivity in their photolysis reactions.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Xiuli Hu, Neil Qiang Su, Wei-Hai Fang
Summary: Direct electrochemical ammonia synthesis from nitric oxide is an attractive strategy, but the lack of efficient and durable electrocatalysts hinders its applications. This study comprehensively investigates the transition metal 1,3,5-triethynylbenzene frameworks and identifies Cr-TEB as a promising electrocatalyst for the NO reduction reaction to NH3. The work demonstrates the potential of TM-TEB as electrocatalysts for the NORR to NH3 and provides descriptors for the catalytic activity.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Yun-Hua Zhu, Xin-Xin Liu, Qiu Fang, Xiang-Yang Liu, Wei-Hai Fang, Ganglong Cui
Summary: In this study, a combined CASPT2//CASSCF approach within the QM/MM framework was used to investigate the early time photoisomerization of rsEGFP2 starting from its two OFF trans states, Trans1 and Trans2. The results showed similar vertical excitation energies in the Franck-Condon regions. By considering rotations of the C11-C9 bond, four pairs of excited-state minima and low-lying conical intersections were optimized, leading to the determination of four barrierless photoisomerization paths to efficient excited state deactivation. This work identified multiple photoisomerization and excited-state decay paths, providing significant insights for the understanding of GFP-like RSFPs and the design of novel GFP-like fluorescent proteins.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Zhong Yuan You, Xin Wang, Fuqi Lu, Shuting Wang, Bingxi Hu, Lian Li, Weihai Fang, Ying Liu
Summary: In this study, a miniature windmill generator based on dynamic semiconductor/metal Schottky triboelectric nanogenerators was designed and fabricated to generate DC electrical power by harvesting wind energy. The device achieved optimal output performance with a maximum open-circuit voltage of 0.6 V and a maximum short-circuit current of 3.6 muA at a wind speed of 7 m/s and a friction layer area of 2.5 cm2. The introduction of a lubricating material, Polyalphaolefin 4, improved the wear resistance as well as the open-circuit voltage and short-circuit current of the device. This work presents a possible strategy for fabricating miniature windmill DC-TENGs and offers a potential supplement to traditional electromagnetic windmills.
Article
Chemistry, Physical
Weijia Li, Juanjuan Wang, Weihai Fang, Liangliang Wu, Xuebo Chen
Summary: This study aims to settle the controversy regarding the role of chlorine versus alkoxy radicals in cerium photocatalysis by employing the theoretical frameworks of Marcus electron transfer and transition state theory. Co-function mechanisms and kinetic evaluations are proposed to explain the ternary dynamic competition among photolysis, back electron transfer, and hydrogen atom transfer (HAT). It is discovered that Cl·-based HAT initially controls the early dynamics of the photocatalytic transformation on the picosecond to nanosecond time scale, which is then taken over by alkoxy radical-mediated HAT in a postnanosecond event. The developed theoretical models offer a coherent understanding of the continuous time dynamics of photogenerated radicals in lanthanide photocatalysis and help address paradoxical arguments.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Xuesong Tian, Qiu Fang, Run Long, Wei-Hai Fang
Summary: Using nonadiabatic molecular dynamics simulations, it is found that slight pressure can accelerate hot electron relaxation and suppress nonradiative electron-hole recombination. Hydrogen/deuterium isotope exchange can mitigate the pressure-caused fast losses of hot electrons and prolong the charge carrier lifetime in semiconducting materials.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Lixin Xiong, Neil Qiang Su, Wei-Hai Fang
Summary: This study systematically investigates the self-catalytic effect of in-situ electrochemical cobalt doping of Li2O2 and reveals its potential mechanism for enhancing the performance of lithium-oxygen batteries. Theoretical calculations show that Co impurities in the discharge products serve as active sites to promote the formation of Li3O4, switching the nucleation mechanism. Through a comprehensive investigation of the properties of Co-doped Li2O2 and Li3O4 compounds, it is found that Li3O4 exhibits better charge/mass transport and lower overpotential, leading to improved battery performance.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Xiao-Ying Xie, Ke-Qin Cheng, Wen-Kai Chen, Wenzuo Li, Qingzhong Li, Juan Han, Wei-Hai Fang, Ganglong Cui
Summary: This study employs DFT and TD-DFT methods to investigate the excited-state properties and dual-emission mechanism of a thiolate-protected Au42 nanocluster. Based on the results, a three-state model (S-0, S-1, and T-1) is proposed and the interactions and transitions between these states are discussed.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Ming Ma, Junjie Song, Yi Dong, Weihai Fang, Lianghui Gao
Summary: In this study, a novel coarse-grained force field was developed to reproduce the structural and thermodynamic properties of triglycerides in bulk phase, as well as at air and water interfaces. The force field accurately reproduced the self-assembled network and diverse molecular conformations of triglycerides in water, and correctly predicted experimental macroscopic thermodynamic properties. This work paves the way for studying complex systems involving triglycerides on a larger scale.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Lishuang Ma, Wenxu Feng, Shidong Zhao, Chuangye Wang, Yanyan Xi, Xufeng Lin
Summary: A simple (BuOK)-Bu-t base-promoted acceptorless dehydrogenation of saturated N-heterocycles has been discovered. This study reveals that the (BuOK)-Bu-t catalyzes the dehydrogenation process of 1,2,3,4-tetrahydroquinoline through a quasi-metal-ligand bifunctional catalytic channel or a base-catalyzed pathway.
Article
Chemistry, Physical
Lin Zhang, Hengwei Qiu, Ran Shi, Jinsong Liu, Guangliu Ran, Wenkai Zhang, Genban Sun, Run Long, Weihai Fang
Summary: This work presents the attractive device performance of perovskite photoconductors based on epitaxial CsPbBr3-Pb4S3Br2 Janus nanocrystals. The carrier relaxation and transfer mechanism of the heterojunction is also investigated. The study demonstrates that the photogenerated holes on CsPbBr3 can be efficiently extracted by Pb4S3Br2, leading to long-range charge separation and transport, resulting in exceptional responsivity and specific detectivity.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Xufeng Lin, Yu Guo, Zhengjian Hou, Hua Chi, Guozeng Ren, Lishuang Ma, Yanjun Ren, Yanyan Xi
Summary: Adsorptive desulfurization (ADS) using alkaline-earth metal-modified Y zeolite (AEY) was studied for deep desulfurization of oil. The AEY adsorbents showed good S adsorption capacity and selectivity, and a new adsorption mechanism was proposed and supported by calculations.
Article
Chemistry, Multidisciplinary
Zhengjian Hou, Xufeng Lin, Ke Wu, Hua Chi, Wumin Zhang, Lishuang Ma, Yanyan Xi
Summary: The adsorption of methanethiol, thiophene, benzothiophene, and dibenzothiophene on hexagonal boron nitride has been investigated using density functional theory. The results show that sulfur compounds prefer to adsorb on the center B atoms of h-BN and thiophene analogues tend to adsorb parallel to the h-BN plane. van der Waals force plays a dominant role in the adsorption process and the adsorption energy is negatively correlated with the number of benzene rings.
