Recent advances in the chemistry of isolable carbene analogues with group 13-15 elements (vol 53, pg 3896, 2024)

Fri, 19 Jul 2024 09:31:18 GMT

题名: Recent advances in the chemistry of isolable carbene analogues with group 13-15 elements (vol 53, pg 3896, 2024) 作者: He, Mian; Hu, Chaopeng; Wei, Rui; Wang, Xin-Feng; Liu, Liu Leo 摘要: Correction for 'Recent advances in the chemistry of isolable carbene analogues with group 13-15 elements' by Mian He et al., Chem. Soc. Rev., 2024, https://doi.org/10.1039/D3CS00784G.

General Method to Introduce Ï -Electrons into Oxygen-Doped Porous Carbon Nitride for Photocatalytic Hydrogen Evolution and Toluene Oxidation

Fri, 19 Jul 2024 08:58:23 GMT

题名: General Method to Introduce Ï -Electrons into Oxygen-Doped Porous Carbon Nitride for Photocatalytic Hydrogen Evolution and Toluene Oxidation 作者: Sun, Zongzhao; Tan, Yueyang; Shi, Xinkai; Li, Bingwen; Wang, Xinfang; Wen, Jiangwei; Huang, Limin; Lau, Woon-Ming 摘要: pi-Electrons have been successfully connected to an oxygen-doped porous carbon nitride by one-pot pyrolysis of the mixture of urea, ethanol, and 4-iodobenzaldehyde (IBD) in the atmosphere. The resulting COCN20 exhibits superior photocatalytic hydrogen production up to 6.88 mmol h(-1) g(cat)(-1) with a relatively high apparent quantum efficiency (20.6% at 325 nm) as well as toluene oxidation with an outstanding conversion rate of 3.75 mmol h(-1) g(cat)(-1) under 460 nm irradiation. Other pi-electrons from aromatic heterocycles could also be grafted to the network for the general synthesis, demonstrating higher hydrogen evolution rates (e.g., 9.32 mmol h(-1) g(cat)(-1) with the thiophene-pi-electrons coupling). The enhanced n -> pi* electron transition and activated midgap states are found to extend the light-responsive region and improve the capture of effective electrons, while the novel porous architecture encourages the efficient mass-transfer rate and improves light harvesting. This work showcases a straightforward and scalable approach to fabricate immensely proficient photocatalysts composed of porous carbon nitride. Furthermore, it opens up a novel pathway for the methodical development and production of sophisticated photocatalysts that harness the powerful synergistic effects achieved by simultaneously adjusting and refining the electronic, surface, and molecular structures.

The Highly Operational Team (HOT) toward f-Block Materials

Fri, 19 Jul 2024 08:52:07 GMT

题名: The Highly Operational Team (HOT) toward f-Block Materials 作者: Park, Kyoung Chul; Kittikhunnatham, Preecha; Lim, Jaewoong; Thaggard, Grace C.; Liu, Yuan; Martin, Corey R.; Leith, Gabrielle A.; Toler, Donald J.; Ta, An T.; Birkner, Nancy; Lehman-Andino, Ingrid; Hernandez-Jimenez, Alejandra; Morrison, Gregory; Amoroso, Jake W.; zur Loye, Hans-Conrad; DiPrete, Dave P.; Smith, Mark D.; Brinkman, Kyle S.; Phillpot, Simon R.; Shustova, Natalia B.; Liu, Peiren; Fang, Fang; Wang, Haochen; Khashab, Niveen M.; Wu, Zhu; Choi, Heekyoung; Hudson, Zachary M.; Goerlich, Tim; Coburger, Peter; Yang, Eric S.; Goicoechea, Jose M.; Gruetzmacher, Hansjorg; Mueller, Christian; Ivanova, Mariya E.; Peters, Ralf; Muller, Martin; Haas, Stefan; Seidler, Martin Florian; Mutschke, Gerd; Eckert, Kerstin; Rose, Philipp; Calnan, Sonya; Bagacki, Rory; Schlatmann, Rutger; Grosselindemann, Cedric; Schafer, Laura-Alena; Menzler, Norbert H.; Weber, Andre; van de Krol, Roel; Liang, Feng; Abdi, Fatwa F.; Brendelberger, Stefan; Neumann, Nicole; Grobbel, Johannes; Roeb, Martin; Sattler, Christian; Duran, Ines; Dietrich, Benjamin; Hofberger, M. E. Christoph; Stoppel, Leonid; Uhlenbruck, Neele; Wetzel, Thomas; Rauner, David; Hecimovic, Ante; Fantz, Ursel; Kulyk, Nadiia; Harting, Jens; Guillon, Olivier; Hu, Qiyu; Chen, Shoushun; Wagberg, Thomas; Zhou, Hongshan; Li, Shujun; Li, Yiding; Tan, Yilan; Hu, Wenqi; Ding, Yong; Han, Xinbao; Behren, Sandra; Yu, Jin; Pett, Christian; Schorlemer, Manuel; Heine, Viktoria; Fischoeder, Thomas; Elling, Lothar; Westerlind, Ulrika; Moorthy, Suresh; Lambert, Hugues; Mohan, Neetha; Schwarzlose, Thomas; Nau, Werner M.; Kalenius, Elina; Lee, Tung-Chun; Cha, Jin Wook; Kim, Min-Seon; Park, Jin-Soo; Hou, Pengfei; Tian, Yumiao; Xie, Yu; Du, Fei; Chen, Gang; Vojvodic, Aleksandra; Wu, Jianzhong; Meng, Xing; Liu, Chengyuan; Qian, Bing; Xiao, Tianci; Lv, Chunchun; Luo, Jinsong; Bao, Jun; Pan, Yang; Pakulski, Dawid; Gorczynski, Adam; Brykczynska, Daria; Montes-Garcia, Veronica; Czepa, Wlodzimierz; Janica, Iwona; Bielejewski, Michal; Kubicki, Maciej; Patroniak, Violetta; Samori, Paolo; Ciesielski, Artur; Zhao, Wengao; Wang, Kuan; Fan, Xinming; Ren, Fucheng; Xu, Xieyu; Liu, Yangyang; Xiong, Shizhao; Liu, Xiangsi; Zhang, Zhengfeng; Si, Mayan; Zhang, Ruizhuo; van den Bergh, Wessel; Yan, Pengfei; Battaglia, Corsin; Brezesinski, Torsten; Yang, Yong; Luo, Zhenli; Li, Zhewei; Zhao, Haoqiang; Yang, Ji; Xu, Lijin; Lei, Ming; Fan, Qinghua; Walsh, Patrick J.; Bartolomei, Beatrice; Corti, Vasco; Prato, Maurizio; Chen, Shiyan; Feng, Lingwei; Peng, Lixia; Gao, Xiang; Zhu, Yongfa; Yang, Liulin; Chen, Dafa; Zhang, Kai; Guo, Xugang; Huang, Fei; Xia, Haiping; Lux, Daniel M.; Aryal, Vivek; Niroula, Doleshwar; Giri, Ramesh; Ma, Junjie; Wang, Zixiao; Jiang, Bo; Wang, Wei; Wang, Hui; Panda, Shibaram; Ghorai, Prasanta; Tan, Chang-Yin; Kim, Minseok; Hong, Sungwoo; Zhang, Hao; Bolshakov, Aleksei; Meena, Raghavendra; Garcia, Gustavo A.; Dugulan, A. Iulian; Parastaev, Alexander; Li, Guanna; Hensen, Emiel J. M.; Kosinov, Nikolay; Huang, Feng; Fan, Xiao-Chun; Cheng, Ying-Chun; Wu, Hao; Xiong, Xin; Yu, Jia; Wang, Kai; Zhang, Xiao-Hong; Zhan, Wenjun; Xu, Lingling; Liu, Zhiyu; Liu, Xiaoyang; Gao, Ge; Xia, Tiantian; Cheng, Xiaotong; Sun, Xianbao; Wu, Fu-Gen; Yu, Qian; Liang, Gaolin; Li, Linfei; Schultz, Jeremy F.; Mahapatra, Sayantan; Liu, Xiaolong; Zhang, Xu; Hersam, Mark C.; Jiang, Nan; Fan, Qianqian; Si, Yubing; Zhu, Fulong; Guo, Wei; Fu, Yongzhu; Ohtani, Ryo; Xu, Jianeng; Yanagisawa, Junichi; Iwai, Yuudai; Ehara, Takumi; Miyata, Kiyoshi; Onda, Ken; Pirillo, Jenny; Hijikata, Yuh; Hiraoka, Tomoaki; Hayami, Shinya; Le Ouay, Benjamin; Ohba, Masaaki; Mubarok, Hanif; Amin, Al; Lee, Taehwan; Jung, Jaehoon; Lee, Jeong-Hwan; Lee, Min Hyung; Liu, Yujia; Yuan, Liuzhong; Guo, Jiaxiang; Sun, Wenting; Wang, Yue; Dou, Chuandong; Xu, Jing; Zhang, Qiang; Gao, Xin; Wang, Peifang; Che, Huinan; Tang, Chunmei; Ao, Yanhui; Guan, Qianwen; Zhu, Tingting; Zhu, Zeng-Kui; Ye, Huang; You, Shihai; Xu, Peng; Wu, Jianbo; Niu, Xinyi; Zhang, Chengshu; Liu, Xitao; Luo, Junhua; Jose Tarrio, Juan; Rodriguez, Rafael; Crassous, Jeanne; Quinoa, Emilio; Freire, Felix; Wang, Kaixuan; Yang, Longqing; Li, Yi; Li, Hongye; Liu, Zhili; Ning, Lichao; Liu, Xiaohua; Feng, Xiaoming; Yu, Jie; He, Shasha; Zhang, Chi; Xu, Cheng; Huang, Jingsheng; Xu, Mengke; Pu, Kanyi; Ge, Jian-Fei; Zou, Xi-Zhang; Liu, Xin-Ru; Ji, Chong-Lei; Zhu, Xin-Yuan; Gao, De-Wei; Meng, Xin-Yu; Li, Jin-Jin; Liu, Peng; Duan, Mingyu; Wang, Jing; Zhou, Yin-Ning; Xie, Yongbing; Luo, Zheng-Hong; Pan, Yun-Xiang; Cao, Yun-Dong; Yin, Di; Li, Si; Dong, Xi-Yan; Feng, Y.; Liu, Hong; Fan, Lin-Lin; Gao, Guang-Gang; Zang, Shuang-Quan; Yu, Le; Abedi, Syed Ali Abbas; Lee, Jeongjin; Xu, Yunjie; Son, Subin; Chi, Weijie; Li, Mingle; Liu, Xiaogang; Park, Jae Hyung; Kim, Jong Seung; Kobayashi, Toi; Kumagai, Naoya; Yan, Rui; Mishra, Bikash; Traxler, Michael; Roeser, Jerome; Chaoui, Nicolas; Kumbhakar, Bidhan; Schmidt, Johannes; Li, Shuang; Thomas, Arne; Pachfule, Pradip; Zhao, Chuan; Yan, Zhongfu; Zhou, Bo; Pan, Yu; Hu, Anjun; He, Miao; Liu, Jing; Long, Jianping; Zhang, Bo; Xu, Jun; Li, Chang-Tai; Huang, Hong-Liang; Chen, Ming-Xing; Yu, Mei-Hui; Chang, Ze; Bu, Xian-He; Berrocal, David A. Perez; Vishwanatha, Thimmalapura M.; Horn-Ghetko, Daniel; Botsch, J. Josephine; Hehl, Laura A.; Kostrhon, Sebastian; Misra, Mohit; Dikic, Ivan; Geurink, Paul P.; van Dam, Hans; Schulman, Brenda A.; Mulder, Monique P. C.; Si, Xu-Ge; Feng, Shi-Xiong; Wang, Zhuo-Yan; Chen, Xiaoyu; Xu, Meng-Meng; Zhang, Yu-Zhen; He, Jun-Xiong; Yang, Limin; Cai, Quan; Liu, Haipei; Liu, Zhaowei; Santos, Mariana Sa; Nash, Michael A.; Eaby, Alan C.; Loots, Leigh; Basson, Jeanice L.; Esterhuysen, Catharine; Barbour, Leonard J.; Wakpal, Joseph; Pathiranage, Vishaka; Walker, Alice R.; Nguyen, Hien M.; Zhao, Huisi; Zhao, Chuanqi; Liu, Zhengwei; Yi, Jiadai; Liu, Xuemeng; Ren, Jinsong; Qu, Xiaogang; Basak, Yudhajeet; Jeoung, Jae-Hun; Domnik, Lilith; Dobbek, Holger; Geng, Shubo; Xu, Hang; Cao, Chun-Shuai; Pham, Tony; Zhao, Bin; Zhang, Zhenjie; Hou, Li-Peng; Li, Yuan; Li, Zheng; Zhang, Qian-Kui; Li, Bo-Quan; Bi, Chen-Xi; Chen, Zi-Xian; Su, Li-Ling; Huang, Jia-Qi; Wen, Rui; Zhang, Xue-Qiang; Li, Fengqin; Li, Junru; Yang, Weiqiang; Yang, Shuai; Chen, Congshuo; Du, Ling; Mei, Junyang; Tang, Qianyun; Chen, Xiaojing; Yao, Chi; Yang, Dayong; Zuo, Xiaolei; Liu, Peifeng; Zheng, Wei; Li, XuPing; Baryshnikov, Glib V.; Shan, Xueru; Siddique, Farhan; Qian, Cheng; Zhao, Shengyin; Wu, Hongwei; Schulz, Annika; Kalkuhl, Till L.; Keil, Philip M.; Hadlington, Terrance J.; Tan, Zheng; Chen, Long; Li, Lingyu; Li, Yuzhen; Luo, Yao; Wang, Fei; Dong, Shunxi; Wang, Yunzheng; Han, Jinfeng; Chen, Mengyang; Lv, Wenting; Meng, Pengtong; Gao, Wei; Meng, Xiangju; Fan, Weibin; Yan, Wenfu; Yu, Jihong; Zhang, Yanjie; Zhang, Lu; Wang, Wenjie; Deng, Qingqing; Liu, Mengmeng; Zhu, Zitong; Liu, Hao; Song, Yurou; Ren, Yanhan; Cheng, Huijie; Jiao, Yuye; Shi, Shaobo; Gao, Lihua; Xie, Huimin; Gao, Junfeng; Sun, Licheng; Hou, Jungang; Naveen, Kenkera Rayappa; Oh, Jun Hyeog; Lee, Hyun Seung; Kwon, Jang Hyuk; Liu, Qingxue; Shen, Feiran; Song, Guohui; Liu, Tianfu; Feng, Weicheng; Li, Rongtan; Zhang, Xiaomin; Li, Mingrun; He, Lunhua; Zheng, Xu; Yin, Shuaishuai; Yin, Guangzhi; Song, Yuefeng; Wang, Guoxiong; Bao, Xinhe; Li, Yilin; Yu, Yanyan; Lou, Yuhan; Zeng, Suqing; Sun, Yaxu; Liu, Yongzhuang; Yu, Haipeng; Tan, Boon Beng; Hu, Ming; Ge, Shaozhong; Gu, Binbin; Dickschat, Jeroen S.; Fuchs, Kathleen; Medina Rivero, Samara; Weidlich, Anna; Rominger, Frank; Israel, Noel; Popov, Alexey A.; Dreuw, Andreas; Freudenberg, Jan; Casado, Juan; Bunz, Uwe H. F.; Tay, Gavin; Wayama, Toshiaki; Takezawa, Hiroki; Yoshida, Satoshi; Sato, Sota; Fujita, Makoto; Oguri, Hiroki; Ji, Shuaiyu; Zhao, Lixing; Miao, Bingyang; Xue, Meng; Pan, Tao; Shao, Zhichao; Zhou, Xin; Fu, Aiping; Zhang, Yuexia; Wang, Chong; Tian, Chang-Yi; Zhao, Ya; Jiang, Shuai; Wang, Tiantong; Zheng, Huijun; Yan, Wenhui; Li, Gang; Xie, Hua; Li, Jun; Hu, Han-Shi; Yang, Xueming; Jiang, Ling; Kent, Greggory T.; Morgan, Emily; Albanese, Kaitlin R.; Kallistova, Anna; Brumberg, Alexandra; Kautzsch, Linus; Wu, Guang; Vishnoi, Pratap; Seshadri, Ram; Cheetham, Anthony K.; Wu, Shuo; Schiel, Florian; Melchiorre, Paolo; Zeng, Yaxin; Xia, Ying; Plangger, Immanuel; Pinkert, Tobias; Wurst, Klaus; Magauer, Thomas; Wang, Wang; Brown, M. Kevin; Ramirez, Nieves P.; Waser, Jerome; Genossar-Dan, Nadav; Atlas, Sharona; Fux, Dana; Lavan, Shani Har; Zamir, Uri; Rozenberg, Illya; Nguyen, Thanh Lam; Hemberger, Patrick; Baraban, Joshua H.; Yang, Yuhao; Miraghaee, Seyedesahar; Pace, Renee; Umemoto, Teruo; Hammond, Gerald B.; Yang, Xiuxiu; Kuziola, Jennifer; Beland, Vanessa A.; Busch, Julia; Leutzsch, Markus; Bures, Jordi; Cornella, Josep; Pang, Yue; Leutzsch, Markus; Nothling, Nils; Bauer, Kevin; Kazmaier, Uli

Total synthesis of natural products containing bicyclo[n.2.2] ring systems

Fri, 19 Jul 2024 08:49:42 GMT

题名: Total synthesis of natural products containing bicyclo[n.2.2] ring systems 作者: Hou, Bao-Long; Liu, Junyang; Qiao, Chuang; Li, Chuang-Chuang 摘要: Bridged bicyclo[m.n.2] ring systems (m >2, n >= 2) are important structural scaffolds, which are widely found in diverse families of natural products. Such natural products are attracting increasing research interests because of their intriguing architectural features and significant biological activities. However, the total synthesis of natural products containing a bridged bicyclo[m.n.2] ring system has proved to be very challenging because there are few efficient approaches to this unique structural motif. In this Minireview, seven representative types of natural products with bridged bicyclo[n.2.2] ring systems are discussed. For each example, we focus on the synthetic routes and highlight the methods and strategies used to prepare bridged bicyclo[n.2.2] ring systems. Lastly, a summary and outlook as well as a discussion of the key features of each strategy applied in the total syntheses are presented. This review demonstrates the creativity and diversity during the synthetic designs of bicyclo[m.n.2] ring systems.

Computational Prediction of Graphdiyne-Supported Three-Atom Single-Cluster Catalysts

Fri, 19 Jul 2024 08:43:42 GMT

题名: Computational Prediction of Graphdiyne-Supported Three-Atom Single-Cluster Catalysts 作者: Liu, Jin-Cheng; Xiao, Hai; Zhao, Xiao-Kun; Zhang, Nan-Nan; Liu, Yuan; Xing, Deng-Hui; Yu, Xiaohu; Hu, Han-Shi; Li, Jun 摘要: ["While heterogeneous single-atom catalysts (SACs) have achieved great success in the past decade, their application is potentially limited by their simplistic single-atom active centers, which make single-cluster catalysts (SCCs) a natural extension in the domain of heterogeneous catalysis. SCCs with precise numbers of atoms and structural configurations possess SAC merits, yet have greater potential for catalyzing complex reactions and/or bulky reactants. Through systematic quantum-chemical studies and computational screening, we report here the rational design of transition metal three-atom clusters anchored on graphdiyne (GDY) as a novel kind of stable SCC with great promise for efficient and atomically precise heterogenous catalysis. By investigating their structure and catalytic performance for the oxygen reduction reaction, the hydrogen evolution reaction, and the CO2 reduction reaction, we have provided theoretical guidelines for their potential applications as heterogeneous catalysts. These GDY-supported three-atom SCCs provide an ideal benchmark scaffold for rational design of atomically precise heterogeneous catalysts for industrially important chemical reactions.","[GRAPHICS]","."]

Catalyst-Controlled Regiodivergent and Enantioselective Formal Hydroamination of N,N-Disubstituted Acrylamides to Î±-Tertiary-Î±-Aminolactam and Î²-Aminoamide Derivatives

Fri, 19 Jul 2024 08:40:48 GMT

题名: Catalyst-Controlled Regiodivergent and Enantioselective Formal Hydroamination of N,N-Disubstituted Acrylamides to Î±-Tertiary-Î±-Aminolactam and Î²-Aminoamide Derivatives 作者: Wang, Shan; Shi, Lou; Chen, Xiao-Yi; Shu, Wei 摘要: Enantioenriched alpha-tertiary-alpha-aminoacid and alpha-chiral-beta-aminoacid derivatives play an important role in biological science and pharmaceutical chemistry. Thus, the development of methods for their synthesis is highly valuable and yet remains challenging. Herein, an unprecedented catalyst-controlled regiodivergent and enantioselective formal hydroamination of N,N-disubstituted acrylamides with aminating agents has been developed, accessing enantioenriched alpha-tertiary-alpha-aminolactam and alpha-chiral-beta-aminoamide derivatives. Sterically-disfavored and electronically-disfavored enantioselective hydroamination of electron-deficient alkenes have been successfully tuned using different transition metals and chiral ligands. Notably, extremely hindered aliphatic alpha-tertiary-alpha-aminolactam derivatives were synthesized by Cu-H catalyzed asymmetric C-N bond forming with tertiary alkyl species. Enantioenriched achiral-beta-aminoamide derivatives have been accessed by Ni-H catalyzed anti-Markovnikov-selective formal hydroaminations of alkenes. This set of reactions tolerates a wide range of functional groups to deliver diverse alpha-tertiary-alpha-aminolactam and alpha-chiral-beta-aminoamide derivatives in good yields with high levels of enantioselectivity.

Marbofloxacin combined with heavy rare-earth ions makes better candidates for veterinary drugs: crystal structure and bio-activity studies

Fri, 19 Jul 2024 08:40:01 GMT

题名: Marbofloxacin combined with heavy rare-earth ions makes better candidates for veterinary drugs: crystal structure and bio-activity studies 作者: Chen, Zhi-chuan; Liu, Rui-xue; Xie, Yan-jie; Hu, Qin; Huang, Fu-ping; Liu, Yan-cheng; Liang, Hong 摘要: ["Marbofloxacin (MB) is a newly developed fluoroquinolone antibiotic used especially as a veterinary drug. It may be regarded as the improved version of enrofloxacin owing to its antibacterial activity, enhanced bioavailability, and pharmacokinetic-pharmacodynamic (PK-PD) properties. In this study, nine heavy rare-earth ions (Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) were selected in light of their potential antibacterial activity and satisfactory biosafety to afford the corresponding rare-earth metal complexes of MB: the MB-Ln series. Their chemical structures and coordination patterns were characterized using IR spectroscopy, HRMS, TGA, and X-ray single-crystal diffraction analysis. Our results confirmed that all the MB-Ln complexes yielded the coincident coordination modes with four MB ligands coordinating to the Ln(iii) center. In vitro antibacterial screening on five typical bacteria strains revealed that the MB-Ln complexes exhibited antibacterial activities comparable with MB, as indicated by the MIC/MBC values, in which Escherichia coli and Salmonella typhi were the most sensitive ones to MB-Ln. Furthermore, the MB-Ln complexes were found to be much less toxic in vivo than MB, as suggested by the evaluated LD50 (50% lethal dose) values. All the MB-Ln series complexes fell in the LD50 range of 5000-15 000 mg kg-1, while the LD50 value of MB was only 1294 mg kg-1. Furthermore, MB-Lu, as the selected representative of MB-Ln, could effectively inhibit the activity of DNA gyrase, the same as MB, suggesting the primary antibacterial mechanism of the MB-Ln series. The results demonstrated the good prospects and potential of metal-based veterinary drugs with better drug performance.","Marbofloxacin (MB) combined with heavy rare earth ion makes a series of MB-Ln complexes, who exhibit similar antibacterial activity to MB, but much lower in vivo acute toxicity than MB, suggesting their better medicinal prospect as veterinary drugs."]

Enantioselective Recognition of Functional Organic Molecules in Water by Biomimetic Macrocyclic Hosts

Fri, 19 Jul 2024 08:39:03 GMT

题名: Enantioselective Recognition of Functional Organic Molecules in Water by Biomimetic Macrocyclic Hosts 作者: Yang, Xiran; Jiang, Wei 摘要: Enantioselective recognition of functional organic molecules in water is routine in nature but remains a formidable challenge for synthetic hosts. Here, we reported two pairs of chiral naphthotubes with chiral centers located in the neighborhood of the inward-directing amide groups. These naphthotubes, with a chiral twisted cavity, show highly enantioselective recognition in water to a wide scope of organic molecules (90 chiral guests). The highest enantioselectivity of 34 was achieved with neotame. Small differences between all of the noncovalent interactions shielded in the hydrophobic cavity were revealed to be responsible for the enantioselective recognition in water, which is different from the traditional views. Moreover, these hosts can differentiate the analogues of aspartame using fluorescence spectroscopy. These chiral naphthotubes have made unprecedented achievements in enantioselective recognition, providing the basis for their applications in chiral analysis and separations.

Substituent Positioning Effects on the Magnetic Properties of Sandwich-Type Erbium(III) Complexes with Bis(trimethylsilyl)-Substituted Cyclooctatetraenyl Ligands

Fri, 19 Jul 2024 08:38:40 GMT

题名: Substituent Positioning Effects on the Magnetic Properties of Sandwich-Type Erbium(III) Complexes with Bis(trimethylsilyl)-Substituted Cyclooctatetraenyl Ligands 作者: Chen, Qi-Wei; Ding, You-Song; Zhu, Xiao-Fei; Wang, Bing-Wu; Zheng, Zhiping 摘要: Lanthanide complexes with judiciously designed ligands have been extensively studied for their potential applications as single-molecule magnets. With the influence of ligands on their magnetic properties generally established, recent research has unearthed certain effects inherent to site differentiation due to the different types and varying numbers of substituents on the same ligand platform. Using two new sandwich-type Er(III) complexes with cyclooctatetraenyl (COT) ligands featuring two differently positioned trimethylsilyl (TMS) substituents, namely, [Li(DME)Er(COT1,5-TMS2)(2)](n) (Er1) and [Na(DME)(3)][Er(COT1,3-TMS2)(2)] (Er2) [COT1,3-TMS2 and COT1,5-TMS2 donate 1,3- and 1,5-bis(trimethylsilyl)-substituted cyclooctatetraenyl ligands, respectively; DME = 1,2-dimethoxyethane], and with reference to previously reported [Li(DME)(3)][Er(COT1,4-TMS2)(2)] (A) and [K(DME)(2)][Er(COT1,4-TMS2)(2)] (B), any possible substituent position effects have been explored for the first time. The rearrangement of the TMS substituents from the starting COT1,4-TMS2 to COT1,3-TMS2 and COT1,5-TMS2, by way of formal migration of the TMS group, was thermally induced in the case of Er1, while for the formation of Er2, the use of Na+ in the placement of its Li+ and K+ congeners is essential. Both Er1 and Er2 display single-molecule magnetic behaviors with energy barriers of 170(3) and 172(6) K, respectively. Magnetic hysteresis loops, butterfly-shaped for Er1 and wide open for Er2, were observed up to 12 K for Er1 and 13 K for Er2. Studies of magnetic dynamics reveal the different pathways for relaxation of magnetization below 10 K, mainly by the Raman process for Er1 and by quantum tunneling of magnetization for Er2, leading to the order of magnitude difference in magnetic relaxation times and sharply different magnetic hysteresis loops.

Enhanced As-COF nanochannels as a high-capacity anode for K and Ca-ion batteries

Fri, 19 Jul 2024 08:36:57 GMT

题名: Enhanced As-COF nanochannels as a high-capacity anode for K and Ca-ion batteries 作者: Ahmed, Shehzad; Ghani, Awais; Muhammad, Imran; Muhammad, Iltaf; Mehmood, Andleeb; Ullah, Naeem; Hassan, Arzoo; Wang, Yong; Tian, Xiaoqing; Yakobson, Boris 摘要: ["Covalent organic frameworks can be used for next-generation rechargeable metal-ion batteries due to their controllable spatial and chemical architectures and plentiful elemental reserves. In this study, the arsenic-based covalent organic framework (As-COF) is designed by employing the geometrical symmetry of a semiconducting phosphazene-based covalent organic framework that uses p-phenylenediamine as a linker and hexachorocyclotriphosphazene as an As-containing monomer in a C3-like spatial configuration. The As-COF with engineered nanochannels demonstrates exceptional anodic behavior for potassium (K) and calcium (Ca) ion batteries. It exhibits a high storage capacity of about 914(2039) mA h g-1, low diffusion barriers of 0.12(0.26) eV, low open circuit voltage of 0.23(0.18) V, and a minimal volume expansion of 2.41(2.32)% for K (Ca) ions. These attributes collectively suggest that As-COF could significantly advance high-capacity rechargeable batteries.","The first-principles computations show that arsenic-based covalent organic frameworks (As-COF) hold great promise as anode materials for K and Ca ion batteries."]