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[专家学者] 杭州师范大学有机硅化学及材料技术教育部重点实验室李志芳

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发表于 2020-6-8 16:34:43 | 显示全部楼层 |阅读模式
李志芳,河南上蔡人,1975年1月生,博士,杭州师范大学研究员,课题组负责人。浙江省高校中青年学科带头人,入选省“双创人才计划”和市“131”培养计划。1998年毕业于河南师范大学,获学士学位;2003年毕业于浙江大学,获理学博士学位;2003-2005年作为日本学术振兴会外国人特别研究员(JSPS)在大阪府立大学从事博士后研究工作;2005年8月加入杭州师范大学有机硅化学及材料技术教育部重点实验室,2010年晋升为研究员。主要从事新型有机硅化合物及其聚合物的合成、性质、反应活性等研究。包括:1)高活性低价有机硅化合物及其过渡金属络合物的合成,结构及其在小分子活化中的应用;2)有机硅单体的合成工艺;3)轻质有机硅灌封材料,具有优异阻燃性、耐候性、疏水性的有机硅发泡材料的研制。近年来在Angew Chem. Int. Ed.; Chem.Commun.; Organometallics 等期刊上发表研究论文80余篇,他引1130多次,获国家授权发明专利9项。先后主持国家自然科学基金,国防军工,浙江省自然科学基金,省“钱江人才计划”,浙江省高校优秀青年教师资助项目和杭州市归国人员择优资助项目等研究课题。


【电  话】:0571-28867825; 13732255097
【电子邮件】:e-mail: zhifanglee@hznu.edu.cn


【主要学学习和工作经历】
2005/08-至今   杭州师范大学有机硅化学及材料技术教育部重点实验室 副研究员(2006),研究员(2010年)
2003/06 – 2005/06大阪府立大学, 奈良女子大学,日本学术振兴会外国人特别研究员(JSPS),Ogawa 实验室
1998/09-2003/04  浙江大学,理学院化学系,获理学博士学位
1994/09-1998/06  河南师范大学,化学系,获学士学位


【主要学术成就、奖励及荣誉】
1)浙江省高校中青年学科带头人(2017)
2)入选江苏省“双创人才计划”(2013)
3)台州市“500精英计划”(2018)
4)“竺可桢奖学金”浙江大学 (2002)


【主要研究方向】
1. 新型硅烯化合物的合成及其在小分子活化中的应用
研究包括新型硅烯(R2Si:)化合物的构造,反应活性研究,及硅烯在小分子活化中的应用等。通过这些工作,一是合成一系列列具有优异光电性质的硅基杂环化合物;二是用低价有机硅化合物替代昂贵的贵金属(如,铂,铑、钌等)作为催化剂活化一些小分子,如氢气、一氧化碳、二氧化碳、烷烃和氨气等。


2. 14-族重金属卡宾配位的过渡金属化合物
14-族重金属卡宾不仅具有良好的给电子能力,还具有较强的配电子接受能力。利用其这一特性制备稳定的低价过渡金属配位化合物,应用于氢气的活化、氮气的固定、烯烃或炔烃的硅氢加成反应等。




3.硅基耐高温材料的开发与应用
在合成新型过渡金属配位化合物的基础上,作为高效催化体系应用于高纯硅碳陶瓷前驱体可溶性树枝状聚硅碳烷研制,开发高导热轻质有机硅电子灌封材料,和具有优异阻燃性、耐候性、疏水性的有机硅发泡材料。




【主要科研项目】
1. 新型硅烯化合物的合成及其在小分子活化中的应用(21472032),国家自然科学基金,86万,2015.1-2018.12,项目负责人,已结题。
2. 新型硅基路易斯酸碱对的合成及其在小分子活化中的应用(LY19B020007),浙江省自然科学基金,10万元,2019.1-2021.12,项目负责人,在研。
3. 新型储存材料-光学活性聚硅烷的研制(6001007),10万,杭州市科技计划项目,2013.1-2014.12,项目负责人,已结题。
4. 新型硅稀的制备及其在特种有机硅化合物合成中的应用 (2009R50016), 浙江省“有机硅创新团队”子课题,30万,2011.1-2014.6,项目负责人,已结题。
5. DMC处理二氧化硅技术研究(2010HSN074),横向课题,150万,2010.5-2014.12,项目负责人,已结题。
6. 低价稀土金属催化光学活性聚硅烷的合成研究(20802014),国家自然科学基金,18万,2009,1-2011,12,项目负责人,已结题。
7. 新型碳硅(C/Si)陶瓷先驱体—可溶性聚硅烷的研制(2008R10018),浙江省科技厅,30万,2008,6-2010, 9项目负责人,已结题。
8. 亚洲硅化学学术交流项目(S4100004),浙江省自然科学基金,4万,2010.1-2010.12项目负责人,已结题。
9. 低价金属钐催化光学活性聚硅烷的合成研究(Y4080380), 浙江省自然科学基金, 5万,2008,11-2010,12,项目负责人,已结题。


【代表性论著】(SCI收录研究论文)
61. A Stable Cyclic (R2SnAu)3 Anion Having In-Plane σ-Möbius Aromaticity, Liliang Wang, Jian Xu, Mitsuo Kira*, Liping Yan, Xu-Qiong Xiao, Zhifang Li*, Angew. Chem. Int. Ed. 2020, 59, 1980-1984. (Highlight by Chemistry World, Trigold anion is first example of strange twisted aromaticity).
60. Exceptionally Long C−C Single Bonds in Diamino -o- carborane as Induced by Negative Hyperconjugation, Junxia Li, Ronglin Pang, Zhifang Li*, Guoqiao Lai, Xu-Qiong Xiao, Thomas Mϋller*, Angew. Chem. Int. Ed. 2019, 58, 1397-1401. (Highlight by C&EN News, ACS OMEGA, The fight over the longest carbon-carbon bond is redefining what a bond is: Why chemists are pushing C-C bonds to their limits).
59. Reactions of an Isolable Dialkylgermylene with Acyl Chlorides Forming Acyl(chloro)germanes and Diacylgermanes,Huaiyuan Zhu, Ningka Wei, Zhifang Li*, Qian Yang, Xu-Qiong Xiao, Guoqiao Lai, Mitsuo Kira*,Organometallics, 2019, 38, 1955-1962.
58. Reaction of an Isolable Dialkylstannylene with Propynoates and Benzyne, Jian Xu, Xu-Qiong Xiao, Chenting Yan, Zhifang Li*, Qiong Lu, Qian Yang, Guoqiao Lai, Mitsuo Kira*, Organometallics, 2018, 37, 2399-2404.
57. Cation-Triggered Stannate (II)/Stannylenoid/Stannylene Convrsion, Hui Zhao, Junxia Li, Xu-Qiong Xiao*, Mitsuo Kira, Zhifang Li*, Thomas Mϋller*, Chem. Eur. J. 2018, 24, 5967-5973.
56. Dihydrogen Splitting Using Dialkylsilylene-Based Frustrated Lewis Pairs, Zhaowen Dong, Zhifang Li,* Xupeng Liu, Chenting Yan, Ningka Wei, and Mitsuo Kira* Thomas Mϋller*, Chem. Asian J. 2017, 12, 1204-1207.
55. Insertion of an Isolable Dialkylstannylene into C-Cl Bonds of Acyl Chlorides Giving Acyl(chloro)stannanes, Qiong Lu, Chengting Yan, Xu-Qiong Xiao, Zhifang Li,* Ningka Wei, Guoqiao Lai and Mitsuo Kira*, Organometallics, 2017, 36, 3633-3637.
54 Silyl- and Disilanyl-BODIPYs: Synthesis via Catalytic Dehalosilylation and Spectroscopic Properties, Sisi Wang, Hua Lu*, Yanping Wu, Xuqiong Xiao, Zhifang Li, Mitsuo Kira, and Zhen Shen, Chem. Asian J. 2017, 12, 561-567.
53. Reversible Stannylenoid Formation from the Corresponding Stannylene and Cesium Fluoride, Chenting Yan, Zhifang Li,* Xu-Qiong Xiao, Ningka Wei, Qiong Lu, and Mitsuo Kira*, Angew. Chem. Int. Ed. 2016, 55, 14784-14787.
52. 1,3-Diazasilabicyclo[1.1.0]butane with Extremely Long N—N Bridge Bond, Xu-Qiong Xiao, Zhaowen Dong, Zhifang Li,* Chenting Yan, Guoqiao Lai and Mitsuo Kira*, Angew. Chem. Int. Ed. 2016, 55, 3758-3762.
51.  Reactions of an Isolable Dialkylsilylene with Aroyl Chlorides. A New Route to Aroylsilanes, Xu-Qiong Xiao, Xupeng Liu, Qiong Lu, Zhifang Li, Guoqiao Lai, Mitsuo Kira, Molecules, 2016, 21, 1376-1385.
50.  Reactions of an Isolable Dialkylstannylene with Carbon Disulfide and Related Heterocumulenes, Chengting Yan, Zheng Xu, Xu-Qiong Xiao, Zhifang Li,* Qiong Lu, Guoqiao Lai and Mitsuo Kira*, Organometallics, 2016, 35, 1323-1328.
49. Synthesis, Structure and Reactivity of Sterically Demanding Oligosilanylmagnesium Compounds, Jun Luo, En-Hui Yan, Hui Zhao, Xu-Qiong Xiao, Zhifang Li*, Polyhedron, 2015, 102, 233-238.
48. Elusive 2H-1,2-Oxasiletes Through  Reactions of an Isolable Dialkylsilylene with Diazocarbonyl Compounds, Zhaowen Dong, Xu-Qiong Xiao, Zhifang Li,* Qiong Lu, Guoqiao Lai and Mitsuo Kira*, Org. Biomol. Chem. 2015, 13, 9471-9476.
47. Organosilicon compounds as fluorescent chemosensors for fluoride anion recognition, Lizhi Gai, Mack John, Hua Lu*, Nyokong Tebello,  Zhifang Li, Kobayashi Nagao, Zhen Shen, Coord. Chem. Rev. 2015, 285, 24-51.
46. Asymmetric core-expanded aza-BODIPY analogues: facile synthesis and optical properties, Hui Liu, Hua, Lu, Zhikuan Zhou, Shimuzi Soki, Zhifang Li, Kobayashi Nagao, Zhen Shen, Chem. Commun. 2015, 1713-1716.
45. Boron-pyridyl-imino-isoindoline dyes: facile synthesis and photophysical properties, Hui Liu, Hua, Lu, Jing Xu, Zhipeng Liu, Zhifang Li, Mack John, Zhen Shen, Chem. Commun. 2014, 1074-1076.
44. A new aza-BODIPY based NIR region colorimetric and fluorescent chemodosimeter for fluoride, Bin Zou, Mack John, Sisi Wang, Jianwei Tian, Zhifang Li, Sen, Zhen, RCS Advances, 2014, 4, 53864-53869.
43. Reactions of an Isolable Dialkylsilylene with Carbon Dioxide and Related Heterocumulenes, Xupeng Liu, Xu-Qiong Xiao, Zheng Xu, Xuemin Yang, Zhifang Li,* Zhaowen Dong, Chenting Yan, Guoqiao Lai and Mitsuo Kira*,  Organometallics, 2014, 33,5434-5439.
42. Chiral Diamine Catalyzed Induction of Helical Chirality in Polysilanes, Zhifang Li, Weifeng Chen, Hua Lu, Qiuhong Wang and Guoqiao Lai*, J. Organomet. Chem. 2014, 772-773, 143-146.
41. New 2,6-Distyryl-Substituted BODIPY Isomers: Synthesis, Photophysical Properties, and Theoretical Calculations, Lizhi Gai, Mack John, Hua Lu*, Yamada, Hiroko, Kuzukara Daiki, Guoqiao Lai, Zhifang Li*, Zhen Shen*, Chem. Eur. J. 2014, 20, 1091-1102.
40. Reactions of an Isolable Dialkylsilylene with Aromatic Nitriles Providing a New Type of Hetereosilole, Liliang Wang, Weifeng Chen, Zhifang Li,* Xuqiong Xiao, Guoqiao Lai,*  Xupeng Liu, Zheng Xu, Mitsuo Kira*, Chem. Commun. 2013, 9776-9778.
39. Reduction of the dihalocyclopentasilanes. Quest for a homocyclic silylene, Xu-Qiong Xiao, Hui Zhao, Zheng Xu, Guoqiao Lai*, Xiao-Lin He and Zhifang Li*, Chem. Commun. 2013, 2706-2708.
38. Diverse reactivity of an isolable dialkylsilylene toward imines, Weifeng Chen, Liliang Wang, Zhifang Li*, Aiqin Lin, Guoqiao Lai*, Xuqiong Xiao, Yuan Deng, Mitsuo Kira*, Dalton Trans. 2013, 42, 1872-1878.
37. Synthesis and characterization of heterocyclic disilylchalcogenides, Xu-Qiong Xiao, Hui Zhao, Zheng Xu, Guo-Qiao Lai*, Mitsuo Kira and Zhifang Li*, Dalton Trans. 2013, 42, 3994-4001.
36. A BODIPY fluorescent probe with selective response for hypochlorous acid and its application in cell imaging, Lizhi Gai, Mack John, Hui Liu, Zheng Xu, Hua Lu*, Zhifang Li*, Sensors and Actuators B 2013, 182, 1-6.
35. Tuning the solid-state luminescence of BODIPY derivatives with bulky arysilyl group: synthesis and spectroscopic properties, Hua Lu, Qiuhong Wang, Lizhi Gai, Zhifang Li*, Yuan Deng, Xuqiong Xiao, Guoqiao Lai, Zhen Shen*, Chem. Eur. J. 2012, 18, 7852-7861.
34. Reaction-based pyrene derivatives and its monomer/excimer emission ratio for sensing analyte and application in living cell, Lizhi Gai, Huachao Chen, Bin Zou, Hua Lu, * Gaoqiao Lai, Zhifang Li*, Zhen Shen *, Chem. Commun. 2012, 10721-10723.
33. Emission of Boron Dipyrromethene (BDP) Dyes through Energy Transfer to Their S2 State from Polysilane S1 State, Qiuhong Wang, Hua Lu, Lizhi Gai, Guoqiao Lai, Zhifang Li*, Dyes and Pigments 2012, 94, 183-186.
32. Synthesis and Spectroscopic Properties of BODIPY Dimers with Effective Solid-State Emission, Lizhi Gai, Hua Lu,* Bin Zou, Guoqiao Lai, Zhen Shen * and Zhifang Li *, RCS Advances, 2012, 2, 8840-8846.
31. A specific chemodosimeter for fluoride ion based on a pyrene derivative with trimethylsilylethynyl groups, Hua Lu, Qiuhong Wang, Zhifang Li*, Guoqiao Lai, Jianxiong Jiang,  and Zhen Shen*, Org. Biomol. Chem. 2011, 9, 4558-4562.
30. Investigation on the Se-Acylation with N-Acylbenzotriazoles, Junyuan Jiang, Wencun Wang, Xiaoxia Wang*, Xiangming Zhu, Zhifang Li*, Phosphorus, Sulfur, and Silicon, 2011, 186, 1-8.
29. Utility of Dysprosium as a Reductant in Coupling Reactions of Acyl Chlorides: the Synthesis of Amides and Diaryl-Substituted Acetylenes, Weifeng Chen, Kebin Li, Ziqiang Hu, Liliang Wang, Guoqiao Lai* and Zhifang Li*, Organometallics, 2011, 30, 2026-2031.
28. Facile Hg2+ detection in water using fluorescent self-assembled monolayers of a rhodamine –based turn-on chemodosimeter formed via a “click” reaction, Hua Lu, Shulin Qi, John Mack, Zhifang Li, Jianping Lei, Nagao Kobayashi, Zhen Shen*, J. Mater. Chem. 2011, 21, 10878-10882.
27. Insertion of Silylenes into Si-H and Si-Cl Bonds.  Comparison of Mechanism and Substituent Effects, Zheng Xu, Juan Jin, Haixia Zhang, Zhifang Li, Jianxiong Jiang, Guoqiao Lai,* and  Mitsuo Kira, Organometallics, 2011, 30, 3311-3317.
26. Self-assembly of novel fluorescent silole derivatives into different supramolecular aggregates, Junhua Wan, Linyan Mao, Y. Li, Zhifang Li, Huayue Qiu, Cheng, Wang, Guoqiao Lai, Soft. Matter, 2011, 6, 3195-3201.
25. Remarkable Substituent Effects on the Activation Energy of Silylene Insertion into Silicon-Chlorine Bonds, Zheng, Xu, Juan Jin, Zhifang Li, Huayu Qiu, Jianxiong Jiang,  Guoqiao Lai,  Mitsuo Kira, Chem. Eur. J. 2009, 15, 8605-9612.
24. Stereoelectronic Substituent Effects on Silylene Insertion into the Si-Cl Bond, Guoqiao Lai, Zheng, Xu, Zhifang Li, Jianxiong Jiang, Mitsuo Kira, Huayu Qiu, Organometallics, 2009, 28, 3591-3593.
23. Photoaccelerated Reductive Coupling of Acid Chlorides with Conjugate Dienes and Styrenes by Use of Neodymium Metal in N,N-Dimethylacetamide, Zhifang Li, Yuri Tomisaka, Akihiro Nomoto, Yongmin Zhang, Akiya Ogawa, Chem. Lett, 2009, 38, 16-17.
22. Selective Mono- and Di-allylation and Allenylation of Chlorosilanes Using Indium, Zhifang Li, Chenjun, Yang, Hongfang Zheng, Huayu Qiu and Guoqiao Lai, J. Organomet. Chem.  2008, 693, 3771-3779.
21. The Synthesis of Si-H Functional Poly(phenylsilane) and Organosilane Copolymers: The Low-Valent Titanium Induced  Polymerization  of Organodichlorosilanes, Zhifang Li, Jiabang Huang, Guoqiao Lai, Jianxiong Jiang, Yongmin Zhang, Chin. J. Chem. 2008, 26, 1693-1696.
20. Features and Applications of reactions of α, β-Unsaturated N- Acylbenzotriazoles with Amino Compounds, Xiaoxia Wang, Zhifang Li, Xiangming Zhu, Hui Mao, Xuefei Zou, Lichun Kong, Xinsheng Li, Tetrahedron, 2008, 64, 6510-6521.
19. A New Entry to the Construction of Si-Si Linkage: Sm/SmI2-Induced Efficient Reductive Coupling of Organochlorosilanes, Zhifang Li, Koichiro Iida, Yuri Tomisaka, Aya Yoshimura, Toshikazu Hirao, Akihiro Nomoto, Akiya Ogawa, Organometallics, 2007, 26, 1212-1216.
18. Direct Construction of Silicon-Silicon Bond by Using the Low-Valent Titanium Guoqiao Lai, Zhifang Li, Jiabang Huang, Jianxiong Jiang, Huayu Qiu, Yongjia Shen, J. Organomet. Chem. 2007, 692, 3559-3562.
17. Controlled Introduction of Allylic Group to Chlorosilanes, Zhifang Li, Xiaojun Cao, Guoqiao Lai, Jinhua Liu, Yong Ni, Jirong Wu, Huayu Qiu, J. Organomet. Chem. 2006, 691, 4740-4746.


学生阶段论文
16. Synthesis of Enamines Via the Cross-coupling of Thioamides and Diarylketones Promoted by the Sm/SmI2 Mixed Reagent, Weimin Zhu, Zhifang Li, Yongmin Zhang Chin. Chem. Lett. 2006, 17 , 1-4.
15. Novel Cyclization of Dimeric Dianions of Anils or Aldehydes with Triphosgene: A Safe and Efficient Synthesis of Substituted Imidazolidin –2-ones and 4,5-Diaryl-1,3-dioxolan –2-ones, Zhifang Li, Yongmin Zhang, Heteroatom Chem. 2003, 14 , 46-49.
14. Syntheise of trans-Stilbene Utilizing Decarbonylation of α-Chloro Chloroformates Mediated by Samarium Diiodide, Zhifang Li, Yongmin Zhang J. Chem. Res. 2003, 340.
13. Development of New Reaction System Using Low-Valent Rare Earths, Akiya Ogawa, Yuri Tomisaka, Nami Harato, Zhifang Li, Rare Earths 2003, 43, 65-72.
12. Direct construction of quaternary carbon center utilizing an allylsamarium bromide reagent, Zhifang Li, Yongmin Zhang, Tetrahedron 2002, 58 , 5301.
11. Low-Valent Titanium Induced Cyclization of Dimeric Dianions of Anil with Triphosgene: A Safe and Efficient Method for the Synthesis of Substituted Imidazolidine, Zhifang Li, Yongmin Zhang, Synth. Commun. 2002, 32, 2613-2618.
10. The Synthesis of N-(1-allyl-3-butenyl)-N-Aryl Amine by Addition of Organosamarium Reagent to Formanilide, Zhifang Li, Yongmin Zhang J. Chem. Res. 2002, 297-298.
9. Sm/TiCl4 System Induced Reductive Coupling Reactions: Synthesis of Tetraarylfurans, Zhifang Li, Yongmin Zhang Indian J. Chem. Soc. 2002, 79, 188.
8. A One-Pot Synthesis of 2-Aryl-2,3-dihydro-4(1H)-quinazolinones by Use of Samarium Diiodide Guoping Cai, Xiaoliang Xu, Zhifang Li, WP Weber, Ping Lu, J. Heterocyclic Chem. 2002, 79, 1271-1272.
7. Samarium Diiodide Mediated Coupling of Aroyl Chlorides, Zhifang Li, Yongmin Zhang Chin. J. Chem. 2001, 19, 634.
6. Low-Valent Titanium Induced Reductive Coupling of o-Nitrophenylazide with Benzoyl Substituted Ketene Dithioacetals: A Novel Synthesis of 4-Aryl-2-methylthio-3H-1,5-benzodiazepines, Zhifang Li, Yongmin Zhang, Chin. J. Chem. 2001, 19, 996.
5. Low Valent Titanium Induced One - Pot Synthesis of Imidazolidines, Zhifang Li, Yongmin Zhang, Org. Prep. Proc. Int. 2001, 33, 185.
4. Samarium Diiodide Mediated Reductive Addition Reaction of 1-(phenylsulfonylmethyl) benzotriazole and 1-(benzoyloxymethyl) benzotriazole to Aldehydes and Ketones, Zhifang Li, Yongmin Zhang, J. Chem. Res. 2001, 522.
3.  Direct Construction of Quaternary Carbon Centre Utilizing an Organosamarium Reagent, Zhifang Li, Yongmin Zhang, Tetrahedron Lett. 2001, 42, 8507.
2. Samarium (III) Iodide Promoted Preparation of ,'-Bis(Substituted benzylidene)Cyclohexanones from Benzaldehydes and Cyclohexanone, Zhifang Li, Yongmin Zhang, J. Chem. Res. 2000, 580.
1. Facile Synthesis of Amidines Via Intermolecular Reductive Coupling of Nitriles with Azobenzene Promoted by Samarium Diiodide, Zhifang Li, Ping Lu, Yongmin Zhang, J. Chem. Res. 2000, 580.


【授权专利】
1. 有机聚硅烷的制备方法, 李志芳,来国桥,邱化玉,毛建江,盛春荠, 发明专利,专利号:ZL 200510061322.8。
2. 烯丙基氯硅烷的制备方法, 李志芳,来国桥,邱化玉,蒋可志,曹肖君, 发明专利,专利号:ZL 200610050555.2。
3. 一种Si-H硅官能化聚硅烷的制备方法, 李志芳,邱化玉,黄家榜,伍 川,邓 元,罗蒙贤,发明专利,专利号:ZL2007 1 0070022.5。
4. 碳官能化氯硅烷的制备方法, 李志芳,杨成军,来国桥,发明专利,专利号:ZL200710156444.4。
5. 格氏法利用四氯化硅制备苯基三氯硅烷和二苯基二氯硅烷的方法,来国桥,李志芳,彭家建,蒋剑雄,华西林,发明专利,专利号:ZL200910307018.5。
6. 光学活性聚烷基芳基硅烷的制备方法, 陈巍峰,来国桥,蒋剑雄,李志芳,王秋红,发明专利,专利号:ZL201110195314.8。
7. 一种光学活性聚硅烷的制备方法, 李志芳,来国桥,陈巍峰,蒋剑雄,王秋红,发明专利,专利号:ZL2012102575004。
8. 一种聚碳硅烷的制备方法,李志芳,刘旭鹏,发明专利,专利号:ZL201611005653.4。
9. 一种一锅法制备含硫硅烷偶联剂的方法,李志芳,刘旭鹏,倪勇,蒋剑雄吴连斌,发明专利,专利号:ZL2016100422021。

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 楼主| 发表于 2020-6-8 16:37:16 | 显示全部楼层
有机硅实验室李志芳团队的研究成果被英国皇家化学学会出版的《CHEMISTRYWORLD》以“Trigold anion is first example of strange twisted aromaticity”为题做了亮点评述(https://www.chemistryworld.com/n ... ity/4010757.article

蓝色纳米簇

蓝色纳米簇
        三个金原子构成的蓝色纳米簇,是首例具备σ-莫比乌斯芳香性的化合物,也是第一例稳定的三元环金负离子化合物。
        包括苯在内的传统意义的π芳香体系,基本特征是相邻的π轨道彼此重叠,允许电子可以在芳环上自由地运动。当然,相互重叠的σ轨道本质上也具备传导电子的能力,形成具有σ芳香性的化合物,只是具备σ芳香性的例子还比较有限。如下图所示:第一例具备双重芳香性的六苯硒基取代苯双阳离子,内层具有6个π电子,外层具有10个σ电子,均满足休克尔规则;并且相互重叠的σ轨道形成一个闭环的圆柱形。
李志芳教授课题组合成的锡金环簇阴离子是首例满足σ-莫比乌斯体系的稳定化合物,它的σ轨道重叠的相位差在节点处如同莫比乌斯带一样发生了扭转,只有一个面,而且只有一半的面发生扭曲。因此形成了具有σ-莫比乌斯芳香性金三元环阴离子化合物。也是首次报道合成具有σ-莫比乌斯芳香性的化合物。
        该金簇阴离子也是首例被合成出来的稳定环状三金阴离子化合物,在以往报道中该类化合物只存在于气相中。金原子间形成正三角形,锡原子在金三元环外围共同组成一个六边形结构。深蓝色环状三金阴离子稳定性极好,甚至可以在惰性气氛中可以稳定存在数周。作者也对三金负离子化合物的反应性进行研究,筛选出一些特征反应性和催化活性。


References
1)Z Liet al, Angew. Chem. Int. Ed., 2020, 59, 1980.
2)S Furukawa et al, Comms. Chem., 2018, 1, 60.

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