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An Isolable Phosphinogermylyne as a Synthon of One-Coordinate GeⅠRadical

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Chinese Journal of Chemistry 2024年第7期42卷 736-742页

作者： Dongmin Wang Haonan Chen Yuhao He Xiaodan Chen Li Zhang Gengwen Tan Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education Guangdong Basic Research Center of Excellence for Functional Molecular EngineeringSchool of ChemistryIGCMESun Yat-Sen UniversityGuangzhouGuangdong 510275China School of Electronic Engineering Guangxi Universityof Science and TechnologyLiuzhouGuangxi 545000China College of Chemistry and Material Jinan UniversityGuangzhouGuangdong 510632China Innovation Center for Chemical Science College of ChemistryChemical Engineering and Materials ScienceSoochow UniversitySuzhouJiangsu 215123China Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education Hangzhou Normal UniversityHangzhouZhejiang 311121China

Reduction of chlorogermylene MsFluindtBu-GeCl 1 with potassium graphite(KC8)afforded putative germylyne radical MsFluindtBu-Ge 2 as confirmed by electron paramagnetic resonance(EPR)spectroscopy.However,it slowly decayed via C—H bond activation at the fluorenyl moiety to yield a bis(germylene)3 at room temperature.By using a Lewis base to stabilize the unoccupied p orbital at the GeⅠradical center,acyclic two-coordinate GeⅠradicals MsFluindtBu-Ge(IMe4)4(IMe4=1,3,4,5-tetramethyl-imidazolin-2-ylidene),MsFluindtBu-Ge(IiPr)5(IiPr=1,3-diisopropyl-4,5-dimethyl-imidazolin-2-ylidene),MsFluindtBu-Ge(PMe3)6 were isolated in crystalline forms.The unpaired electron in 4-6 mainly resides at the Ge 4p orbital as revealed by EPR spectroscopic studies and theoretical calculations.Interestingly,facile ligand exchange of PMe3 in 6 with IMe4 and IiPr was observed to afford 4 and 5,respectively.Moreover,phosphinogermylyne 6 reacted with PhEEPh(E=S,Se),4-tetrabutylphenylacetylene(Ar'CCH),[CpMo(CO)3]2 and nBu3SnH to furnish germylenes MsFluindtBu-GeEPh(E=S 7,Se 8),MsFluindtBu-GeCH=CHAr'9,a germylyne complex MsFluindtBu-Ge≡Mo(CO)2Cp 10 and a Ge(Ⅳ)compound MsFluindtBu-GeH2SnnBu311,respectively.The reactivity studies demonstrate that 6 can act as a synthon of one-coordinate germylyne radical attributing to labile coordination of trimethylphosphine.

关键词： Phosphinogermylyne Germanium radicals Donor-acceptor systems Radical reactions

Organic Synthesis through Radical Innovation:Frustrated Radical Pairs

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Chinese Journal of Chemistry 2024年第10期42卷 1157-1160页

作者： Zhibin Hu Zengrui Cheng Ning Jiao State Key Laboratory of Natural and Biomimetic Drugs School of Pharmaceutical SciencesPeking UniversityBeijing 100191China Shanghai Key Laboratory of Green Chemistry and Chemical Processes East China Normal UniversityShanghai 200062China

Frustrated Lewis Pairs(FLPs)represent a unique class of interactions in Lewis acid-base chemistry,driven by spatial hindrance or incongruent orbital energy levels that hinder the formation of effective coordination bonds.FLPs have received significant attention for their application in activating small molecules and facilitating organic synthesis reactions.Recent developments have led to the emergence of Frustrated Radical Pairs(FRPs)as an extension of the radical family.FRPs are formed from FLPs through Single Electron Transfer(SET)and exhibit the ability to activate a variety of chemical bonds.While research on FLPs is well-established,investigations into FRPs in organic reactions remain limited.This review highlights the current state of FRPs in organic synthesis,delves into mechanistic insights,explores their potential,and underscores the challenges in this emerging field.

关键词： radicals Frustrated Lewis Pairs Frustrated Radical Pairs Methodology and reactions Reaction mechanisms

Planar Blatter radicals through Bu_(3)SnH-and TMS_(3)SiH-assisted cyclization of aryl iodides: azaphilic radical addition

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Organic Chemistry Frontiers 2022年第4期9卷 929-938页

作者： Paulina Bartos Małgorzata Celeda Anna Pietrzak Piotr Kaszynski Faculty of Chemistry University ofŁodz91-403ŁodzPoland Faculty of Chemistry Łodz University of Technology90-924ŁodzPoland Centre of Molecular and Macromolecular Studies Polish Academy of Sciences90-363ŁodzPoland Department of Chemistry Middle Tennessee State UniversityMurfreesboroTennessee 37132USA

Bu_(3)SnH-and TMS_(3)SiH-assisted cyclizations of iodoarene derivatives of benzo[e][1,2,4]triazine lead to the formation of planar Blatter radicals(2-phenyl-3H-[1,2,4]triazino[5,6,1-kl]phenoxazin-3-yls and 2-phenyl-3H... 详细信息

关键词： cyclization radicals

Oxygen vacancies induced narrow band gap of BiOCl for efficient visible-light catalytic performance from double radicals

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Journal of Materials Science & Technology 2022年第19期114卷 240-248页

作者： Changyan Chen Ting Jiang Jianhua Hou Tingting Zhang Geshan Zhang Yongcai Zhang Xiaozhi Wang School of Environmental Science and Engineering Yangzhou UniversityYangzhou 225000China Guangling College Yangzhou UniversityYangzhou 225009China Jiangsu Collaborative Innovation Center for Solid Organic Waste Resource Utilization Nanjing 210095China College of Chemical Engineering Zhejiang University of TechnologyHangzhou 310014China National Local Joint Engineering Laboratory to Functional Adsorption Material Technology for the Environmental Protection Soochow UniversitySuzhou 215123China

In this work,a high-efficiency photocatalytic BiOCl material with a visible light absorption range was successfully prepared by one-pot molecular self-assembly and particle recrystallization method at room temperature.In the process of crystal growth,tartaric acid,as a structure control agent,gradually transforms the stacked two-dimensional nano-sheet-like BiOCl into a hierarchical structure composed of petallike nano-sheets through hydrogen bonding.Besides,the acid etching of organic carboxylic acid on the crystal surface increases the number of micropores and mesopores,thereby the reaction interface.The thiourea(TU)molecules adsorbed on the BiOCl surface with a strong electronic effect introduce oxygen vacancies(OVs)under the condition of low oxygen content.The synergistic effect of hierarchical structure and OVs reduces the recombination of photogenerated carriers,but absorbs more O_(2)and OH−to generate a large number of superoxide radicals(·O_(2)−)and hydroxyl radicals(·OH)effectively.The photocatalytic performance of the synthesized BiOCl material has been significantly improved,and it can effectively degrade 94.15%of rhodamine B(RhB)within 20 min.Furthermore,90.95%of tetracycline(TC),93.76%of ciprofloxacin(CIP),and 85.53%of methyl orange(MO)can be removed in 80 min.Therefore,our work provides an effective method for preparing BiOCl with visible light catalytic activity,which,of course,can be used to treat and repair actual environmental problems under mild conditions.

关键词： BiOCl Carboxylic acid Oxygen vacancy radicals Photocatalytic

A Photo-Responsive Charge-Assisted Hydrogen-Bonded Organic Network with Ultra-Stable Viologen radicals

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Chinese Journal of Chemistry 2022年第3期40卷 351-356页

作者： Shi-Li Li Yuan Shen Wen Yang Yu-Jie Wang Zhikai Qi Jian Zhang Xian-Ming Zhang Key Laboratory of Magnetic Molecules&Magnetic Information Materials Ministry of EducationSchool of Chemistry&Material ScienceShanxi Normal UniversityToiyuonShanxi 030006China School of Chemistry and Chemical Engineering Taiyuan University of TechnologyTaiyuanShanxi 030024China

Hydrogen-bonded organic networks(HONs)have attracted intense research interest due to their mild synthesis conditions,good solvent processability and strong reproducibility.Most HONs are constructed by electrically neutral organic ligands through intermo-lecular interactions such as weak hydrogen bonding,n-n stacking.But there are a few charge-assisted hydrogen-bonding networks(CAHONs)constructed by oppositely charged organic components.Under hydrothermal conditions,we successfully synthesized a 3D CAHON(H2CV)(H2BTEC)(1)constructed by H2CV(CV=N,N′-4,4′-bipyridine dipropionate)and H4BTEC(H_(4)BTEC=1,2,4,5-benzene-tetracarboxylic acid)through multiple charge-assisted hydrogen bonding.Upon soft X-ray,ultraviolet light or sunlight irradiation under ambient conditions,1 quickly changes from colorless to blue(IP),and kinetic calculations show that its photochromism meets first-order dynamics.Interestingly,the colored crystals IP with long-lived colored radicals will not fade after being placed for more than two months at room temperature in air,owing to the fact that the photogenerated viologen radicals can be stabilized by the abundant hydrogen bonds,the coplanar pyridinium rings and the slow electron-hole recombination.Moreover,1 is a typical direct band gap semiconductor,evidenced by the calculated band gap of 3.24 eV,in agreement with the experimental value of 3.40 eV.In view of its strong colored stability,1 is designed for distinctive inkless printing.

关键词： Hydrogen-bonded organic networks radicals Photochromism Inkless printing Electron transfer

Crystalline Germanium-Dipyrromethene radicals:from a Delocalized Neutral to a Localized Cation

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Chinese Journal of Chemistry 2022年第20期40卷 2387-2392页

作者： Yuyang Dai Manling Bao Wenjuan Wang Zhuofeng Xie Chunmeng Liu Yuanting Su College of Chemistry Chemical Engineering and Materials ScienceSchool of Radiation Medicine and ProtectionSoochow UniversitySuzhouJiangsu215123 China State Key Laboratory of Coordination Chemistry Nanjing UniversityNanjingJiangsu210023 China

Both dipyrromethene complexes and radicals of heavier main group elements have been of high interest.However,cationic germanium radicals and dipyrromethene-based radicals of heavier main group elements are still escaped to be isolated.Herein,we report the isolation and full characterization of a neutral Ge(I)-masked dipyrromethene-based radical 3 and the first cationic Ge(III)-centered radical 5^(·+)as stable crystalline solids.3 behaves as a germanium(I)radical in its reaction with diphenyl disulfide to form the Ge-S bond,although X-ray crystallographic,EPR spectroscopic,computational studies revealed that the unpaired electron of 3 is mainly delocalized over the C_(9)N_(2)Ge backbone and the allylic radical character is also significant in 3.In contrast to 3,the spin density of 5^(·+)is mainly localized at the Ge center with minor contribution from the dipyrromethene ligand.Moreover,reduction of 5^(·+)with potassium graphite quantitatively regenerates 5,illustrating a reversible one-electron redox pair.

关键词： radicals Main group element Germanium Dipyrromethene X-ray diffraction

Nucleophilic radicals as Hydrogen Atom Abstractors in C(sp3)-H Functionalization Reactions

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Chinese Journal of Chemistry 2023年第5期41卷 544-547页

作者： Tao Li Jian Li Haohua Huo State Key Laboratory of Physical Chemistry of Solid Surfaces Key Laboratory of Chemical Biology of Fujian ProvinceCollege of Chemistry and Chemical EngineeringXiamen UniversityXiamen 361005China

Hydrogen atom transfer(HAT)is an elementary mechanistic step in organic synthesis.The photoredox-catalyzed HAT has transformed organic synthesis by enabling the activation and subsequent cross-coupling of traditionall... 详细信息

关键词： radicals Hydrogen atom transfer(HAT) C(sp^(3))-H functionalization Polarity matching Photocatalysis

Organic Functional Free radicals

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Chemical Research in Chinese Universities 2023年第2期39卷 159-160页

作者： LI Feng State Key Laboratory of Supramolecular Structure and Materials College of ChemistryJilin UniversityChangchun130012P.R.China

Organic free radicals are characterized by their"open-shell"electronic structures,meaning that they contain one or more unpaired electrons in singly occupied molecular orbitals(SOMOs),which is in contrast to the closed-shell structure of traditional organic molecules containing paired electrons in all their occupied orbitals.The unpaired electrons endow organic free radicals with distinct fluorescent,magnetic,and electronic properties,which have garnered significant attention.Although most free radicals are highly unstable,their stability can be greatly enhanced through reasonable structural modifications.In fact,various series of stable free radicals have been developed that can be isolated and stored under ambient atmosphere for extended periods of time.The resolution of the stability issue has opened up the possibilities for functionalizing organic free radicals.

关键词： occupied stability radicals

Computational mechanistic investigation of radiation damage of adenine induced by hydroxyl radicals

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Chinese Physics B 2018年第2期27卷 64-70页

作者：谈荣日刘慧宣寻大毛宗文军 College of Communication and Electronics Jiangxi Science & Technology Normal University Institute of High Energy Physics Chinese Academy of Sciences

The radiation damage of adenine base was studied by B3LYP and MP2 methods in the presence of hydroxyl radicals to probe the reactivities of five possible sites of an isolated adenine molecule. Both methods predict that the C8 site is the more vulnerable than the other sites. For its bonding covalently with the hydroxyl radicals, B3LYP predicts a barrierless pathway, while MP2 finds a transition state with an energy of 106.1 kJ/mol. For the hydroxylation at the C2 site, the barrier was calculated to be 165.3 kJ/mol using MP2 method. For the dehydrogenation reactions at five sites of adenine, B3LYP method predicts that the free energy barrier decreases in the order of H8 〉 H2 〉 HN62 〉 HN61 〉 HN9.

关键词： DNA damage radicals adenine dehydrogenation