Thousands of landslide data being taken as the nation wide statistics of sampling and the two state variables of landslide being processed with two methods described in the references, the main types of lithologica...Thousands of landslide data being taken as the nation wide statistics of sampling and the two state variables of landslide being processed with two methods described in the references, the main types of lithological groups of landslides in China have been sieved and selected.On the other hand, through the displacement table of Pascal Yanghui triangle used in the information encoding theory, the mark weight of sampling can be calculated and the main lithological groups which have close relationship with landslide occurrence can be gained.In comparison with the both results, the characteristics of main sliding lithological groups are determinated, and the main distribution regions of landslides can be prognosticated.展开更多
By using solvothermal method, two new main group metal coordination polymers based on 2,5-furandicarboxylic acid (H2FDA) ligand, [Sr2(FDA)E(H2O)5]n (1) and [Ba4(FDA)4(H2O)10]n (2), were produced and char...By using solvothermal method, two new main group metal coordination polymers based on 2,5-furandicarboxylic acid (H2FDA) ligand, [Sr2(FDA)E(H2O)5]n (1) and [Ba4(FDA)4(H2O)10]n (2), were produced and characterized by single-crystal X-ray diffraction analyses, elemental analyses, IR, and powder X-ray diffraction. Compound 1 crystallizes in monoclinic, space group C2/c with a = 13.454(3), b = 13.426(3), c = 20.166(4) A, β = 107.06(3)°, V = 3482.4(13)A^3, Dc = 2.188 g/cm^3, CIEH14Sr2O15, Mr = 573.47, F(000) = 2256,μ(MoKα)= 6.21 mm^-1, Z = 8, R = 0.0522 and wR = 0.1229 for 2493 observed reflections (I〉 2σ(I)), and R = 0.0689 and wR = 0.1324 for all data. Compound 2 crystallizes in triclinic, space group el with α = 6.8382(14), b = 10.932(2), c = 25.571(5) A,α = 94.64(3), β= 95.41(3), γ = 107.83(3)°, V= 1799.4(6) A3, Dc = 2.484 g/cm^3, C24H28Ba4O30, Mr = 1345.82, F(000) = 1272,μ(MoKa) = 4.43 mm^-1, Z = 2, R = 0.0485 and wR = 0.0906 for 5020 observed reflections (I〉 2σ(I)), and R = 0.0706 and wR = 0.0991 for all data. In 1, the trinuclear clusters Sr3 are connected with adjacent four clusters by a carboxylate group to produce a two-dimensional (2D) sheet, which is extended by a FDA-based pillar into a 3D framework. In 2, neighbouring trinuclear clusters Ba3 are linked through two -O-C-O- of FDA^2- ligands to form one-dimensional (1D) chains, which are connected by a FDA-based pillar to construct a 2D framework. The thermal stabilities of 1 and 2 are also investigated.展开更多
Electrocatalytic N_(2) reduction under ambient-condition is considered to be the most appealing strategy to the conventional Haber-Bosch process for synthetic ammonia to alleviate greenhouse emissions and reduce envir...Electrocatalytic N_(2) reduction under ambient-condition is considered to be the most appealing strategy to the conventional Haber-Bosch process for synthetic ammonia to alleviate greenhouse emissions and reduce environmental pollution, mainly powered by renewable energy. Recent years, rapid advances have been gained in this attractive research field, and numerous electrocatalysts have been exploited. However, its conversion efficiency is still far behind the requirement of industrial applications owing to the breakage of the N≡N triple bond, which is an energetically challenging kinetically complex multistep reaction and the strong competing reaction of hydrogen evolution reaction. Recently, main group metal-based catalysts have been demonstrated promising application prospect for ammonia production, significantly boosting their further application in this field. However, a comprehensive review of main group metal-based catalysts towards electrochemical ammonia production applications is still lacking. In this review, the fundamentals of N_(2) reduction, such as the reaction pathways, the reaction potential and the challenges of N_(2) reduction have been comprehensively discussed. And then, the role, mechanism, and effect of each main group element-based catalysts used for N_(2) reduction (Li, K, Al, Ga, Sn, Sb, Bi, and their compounds) are systematically summarized. Finally, several state-of-the-art strategies to promote their NRR catalytic performance, as well as the existing problems and prospects are put forward. This review is expected to guide the design and establishment of more efficient electrocatalytic N_(2) reduction systems based on main group metal elements in the future.展开更多
New appronches were applied to improve the molecular connectivity indices m^X^τ. The vertex valence is redefined and it was reasonable for hydrogen atom. The distances between vertices were used to propose novel conn...New appronches were applied to improve the molecular connectivity indices m^X^τ. The vertex valence is redefined and it was reasonable for hydrogen atom. The distances between vertices were used to propose novel connectivity topological indexes. The vertices and the distances in a molecular graph were taken into account in this definition. The linear regression was used to develop the structural property models. The results indicate that the novel connectivity topological indexes are useful model parameters for Quantitative Strncture-Property Relationship ( QSPR ) analysis.展开更多
Designing catalysts with highly active,selectivity,and stability for electrocatalytic CO_(2)to formate is currently a severe challenge.Herein,we developed an electronic structure engineering on carbon nano frameworks ...Designing catalysts with highly active,selectivity,and stability for electrocatalytic CO_(2)to formate is currently a severe challenge.Herein,we developed an electronic structure engineering on carbon nano frameworks embedded with nitrogen and sulfur asymmetrically dual-coordinated indium active sites toward the efficient electrocatalytic CO_(2)reduction reaction.As expected,atomically dispersed In-based catalysts with In-S_(1)N_(3)atomic interface with asymmetrically coordinated exhibited high efficiency for CO_(2)reduction reaction(CO_(2)RR)to formate.It achieved a maximum Faradaic efficiency(FE)of 94.3%towards formate generation at−0.8 V vs.reversible hydrogen electrode(RHE),outperforming that of catalysts with In-S2N2 and In-N4 atomic interface.And at a potential of−1.10 V vs.RHE,In-S_(1)N_(3)achieves an impressive Faradaic efficiency of 93.7%in flow cell.The catalytic performance of In-S_(1)N_(3)sites was confirmed to be enhanced through in-situ X-ray absorption near-edge structure(XANES)measurements under electrochemical conditions.Our discovery provides the guidance for performance regulation of main group metal catalysts toward CO_(2)RR at atomic scale.展开更多
Two isomers of a sandwich-type anion [Ge_(9)-In-Ge_(9)]^(5–) were synthesized by controlling the chelating agents (2,2,2-crypt/18-C-6). Further reactions with early/late transition metal complexes, Mo(CO)_(6) and Ni(...Two isomers of a sandwich-type anion [Ge_(9)-In-Ge_(9)]^(5–) were synthesized by controlling the chelating agents (2,2,2-crypt/18-C-6). Further reactions with early/late transition metal complexes, Mo(CO)_(6) and Ni(COD)_(2), respectively, yielded two new types of inorganic sandwich derivatives: a half-sandwich cluster [Ge_(9)-In-Mo(CO)_(5)]^(3–) with a low-valence In(I) center and an unsymmetrical sandwich-type cluster {[(Ni@Ge_(9))In(Ni_(0.648)@Ge_(9))]}^(5–) due to the insertion of Ni atoms, respectively. The isolation of these new derivatives demonstrates the reactivity of sandwich-type [Ge_(9)-In-Ge_(9)]^(5–) acting as the precursor, which provides some enlightenment for constructing new inorganic sandwich compounds.展开更多
Electrical contact materials are generally Ag-or Cu-based composites and play a critical role in ensuring the reliability and efficiency of electrical equipments and electronic instruments.The MAX(M is an early transi...Electrical contact materials are generally Ag-or Cu-based composites and play a critical role in ensuring the reliability and efficiency of electrical equipments and electronic instruments.The MAX(M is an early transition metal,A is an element from III or IV main groups,and X is carbon or/and nitrogen)phase ceramics display a unique combination of properties and may serve as an ideal reinforcement phase for electrical contact materials.The biological materials evolved in nature generally exhibit three-dimensional(3D)interpenetrating-phase architectures,which may offer useful inspiration for the architectural design of electrical contact materials.Here,a series of bi-continuous Ag-Ti_(3)SiC_(2) MAX phase composites with high ceramic contents exceeding 50 vol.%and having micron-and ultrafine-scaled 3D interpenetrating-phase architectures,wherein both constituents were continuous and mutually interspersed,were exploited by pressureless infiltration of Ag melt into partially sintered Ti_(3)SiC_(2) scaffolds.The mechanical and electrical properties as well as the friction and wear performance of the composites were investigated and revealed to be closely dependent on the ceramic contents and characteristic structural dimensions.The composites exhibited a good combination of properties with high hardness over 2.3 GPa,high flexural strength exceeding 530 MPa,decent fracture toughness over 10 MPa·m^(1/2),and good wear resistance with low wear rate at an order of 10^(-5)mm^(3)/(N·m),which were much superior compared to the counterparts made by powder metallurgy methods.In particular,the hardness,electrical conductivity,strength,and fracture toughness of the composites demonstrated a simultaneous improvement as the structure was refined from micron-to ultrafine-scales at equivalent ceramic contents.The good combination of properties along with the facile processing route makes the Ag-Ti_(3)SiC_(2)3D interpenetrating-phase composites appealing for electrical contact applications.展开更多
Photoabsorption charge separation/transfer and surface reaction are the three main factors influencing the efficiency of photocatalysis.Band structure engineering has been extensively applied to improve the light abso...Photoabsorption charge separation/transfer and surface reaction are the three main factors influencing the efficiency of photocatalysis.Band structure engineering has been extensively applied to improve the light absorption of photocatalysts,however,most of the developed photocatalysts still suffer from low photocatalytic performance due to the limited active site(s)and fast recombination of photogenerated charge carriers.In this work,atomically dispersed main group magnesium(Mg)is introduced onto CdS monodispersed nanospheres,which greatly enhances the photocatalytic hydrogen evolution reaction.The photocatalytic hydrogen evolution reaction rate reaches 30.6 mmol·gcatalyst^(-1)·h^(-1),which is about 11.8 and 2.5 times that of pure CdS and Pt(2 wt.%)-CdS.The atomically dispersed Mg on CdS acts as an electron sink to trap photogenerated electrons,and at the same time,greatly reduces the Gibbs free energy of hydrogen evolution reaction(HER)and accelerates HER.展开更多
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 escap...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.展开更多
Carboranes are a class of polyhedral boron-carbon molecular clusters,they can serve as versatile ligands in stabilizing low-valent main group element compounds,due to their exceptionally thermal and chemical stabiliti...Carboranes are a class of polyhedral boron-carbon molecular clusters,they can serve as versatile ligands in stabilizing low-valent main group element compounds,due to their exceptionally thermal and chemical stabilities,easy modifications at the cage carbon vertices,as well as large spherical steric effects.These carborane-based ligands provide interesting opportunities for the synthesis of low-valent main group element compounds with novel structure and reactivity,which indeed enrich the chemistry of low-valent element main group compounds.This review summarizes the recent advances in the chemistry of lowvalent group 13 and group 14 element compounds supported by carborane-based ligands.Achievements and perspectives in this new and flourishing field are discussed in this review.展开更多
Theσ-bond activation by main group element has received enormous attention from theoretical and experimental chemists.Here,the reaction of C-X(X=Cl,Br,I)bonds in benzyl and allyl halides with a pincer-type phosphorus...Theσ-bond activation by main group element has received enormous attention from theoretical and experimental chemists.Here,the reaction of C-X(X=Cl,Br,I)bonds in benzyl and allyl halides with a pincer-type phosphorus(Ⅲ)species was reported.A series of structurally robust phosphorus(Ⅴ)compounds were formed via the formal oxidative addition reactions of C-X bonds to the phosphorus(Ⅲ)center.Density functional theory calculations show that the nucleophilic addition process is more favorable than the direct oxidative addition mechanism.Isomerization of bent structures of phosphorus(Ⅲ)compound to poorly nucleophilic compounds to undergo further C-X bond activation can be rationalized by frontier molecule orbital analysis.This study not only provides a deep understanding of the reactivity of phosphorus(Ⅲ)species but also demonstrates a potential of main group elements for the small-molecule activation.展开更多
We have discovered a route to access the longest low-valent molecular silaphospha-chain,a sevenmembered chain structure that incorporates three silicon and four phosphorus atoms by stepwise activation of white phospho...We have discovered a route to access the longest low-valent molecular silaphospha-chain,a sevenmembered chain structure that incorporates three silicon and four phosphorus atoms by stepwise activation of white phosphorus(P_(4))using two different silylene precursors.The chain species was formed via a highly reactive polyphosphide intermediate.The isolation of a stable analogue of this reaction intermediate was achieved by stepwise reaction with mono and bis(silylenes).Due to the rigidity of the ferrocenediyl framework of the bis(silylene),the isomerization process of the chain structure was hampered.Theoretical studies such as natural bond orbital and atoms in molecules analyses of the seven-membered chain species indicated some degree of delocalization of the double bond system.展开更多
文摘Thousands of landslide data being taken as the nation wide statistics of sampling and the two state variables of landslide being processed with two methods described in the references, the main types of lithological groups of landslides in China have been sieved and selected.On the other hand, through the displacement table of Pascal Yanghui triangle used in the information encoding theory, the mark weight of sampling can be calculated and the main lithological groups which have close relationship with landslide occurrence can be gained.In comparison with the both results, the characteristics of main sliding lithological groups are determinated, and the main distribution regions of landslides can be prognosticated.
基金supported by URT program of Beijing Institute of Petrochemical Technology(2015J00058 and 2015J00056)
文摘By using solvothermal method, two new main group metal coordination polymers based on 2,5-furandicarboxylic acid (H2FDA) ligand, [Sr2(FDA)E(H2O)5]n (1) and [Ba4(FDA)4(H2O)10]n (2), were produced and characterized by single-crystal X-ray diffraction analyses, elemental analyses, IR, and powder X-ray diffraction. Compound 1 crystallizes in monoclinic, space group C2/c with a = 13.454(3), b = 13.426(3), c = 20.166(4) A, β = 107.06(3)°, V = 3482.4(13)A^3, Dc = 2.188 g/cm^3, CIEH14Sr2O15, Mr = 573.47, F(000) = 2256,μ(MoKα)= 6.21 mm^-1, Z = 8, R = 0.0522 and wR = 0.1229 for 2493 observed reflections (I〉 2σ(I)), and R = 0.0689 and wR = 0.1324 for all data. Compound 2 crystallizes in triclinic, space group el with α = 6.8382(14), b = 10.932(2), c = 25.571(5) A,α = 94.64(3), β= 95.41(3), γ = 107.83(3)°, V= 1799.4(6) A3, Dc = 2.484 g/cm^3, C24H28Ba4O30, Mr = 1345.82, F(000) = 1272,μ(MoKa) = 4.43 mm^-1, Z = 2, R = 0.0485 and wR = 0.0906 for 5020 observed reflections (I〉 2σ(I)), and R = 0.0706 and wR = 0.0991 for all data. In 1, the trinuclear clusters Sr3 are connected with adjacent four clusters by a carboxylate group to produce a two-dimensional (2D) sheet, which is extended by a FDA-based pillar into a 3D framework. In 2, neighbouring trinuclear clusters Ba3 are linked through two -O-C-O- of FDA^2- ligands to form one-dimensional (1D) chains, which are connected by a FDA-based pillar to construct a 2D framework. The thermal stabilities of 1 and 2 are also investigated.
基金This work was supported by the National Natural Science Foundation of China(No.52071171)the Liaoning Revitalization Talents Program-Pan Deng Scholars(XLYC1802005)+4 种基金the Liaoning Bai-QianWan Talents Program(LNBQW2018B0048)the National Science Fund of Liaoning Province for Excellent Young Scholars(2019-YQ-04)the Key Project of Scientific Research of the Education Department of Liaoning Province(LZD201902)the Department of Education of Liaoning Province(LQN201903 and LQN202008)the Foundation for Young Scholars of Liaoning University(LDQN2019007).
文摘Electrocatalytic N_(2) reduction under ambient-condition is considered to be the most appealing strategy to the conventional Haber-Bosch process for synthetic ammonia to alleviate greenhouse emissions and reduce environmental pollution, mainly powered by renewable energy. Recent years, rapid advances have been gained in this attractive research field, and numerous electrocatalysts have been exploited. However, its conversion efficiency is still far behind the requirement of industrial applications owing to the breakage of the N≡N triple bond, which is an energetically challenging kinetically complex multistep reaction and the strong competing reaction of hydrogen evolution reaction. Recently, main group metal-based catalysts have been demonstrated promising application prospect for ammonia production, significantly boosting their further application in this field. However, a comprehensive review of main group metal-based catalysts towards electrochemical ammonia production applications is still lacking. In this review, the fundamentals of N_(2) reduction, such as the reaction pathways, the reaction potential and the challenges of N_(2) reduction have been comprehensively discussed. And then, the role, mechanism, and effect of each main group element-based catalysts used for N_(2) reduction (Li, K, Al, Ga, Sn, Sb, Bi, and their compounds) are systematically summarized. Finally, several state-of-the-art strategies to promote their NRR catalytic performance, as well as the existing problems and prospects are put forward. This review is expected to guide the design and establishment of more efficient electrocatalytic N_(2) reduction systems based on main group metal elements in the future.
基金Funded bythe Natural Science andthe Education Office Founda-tion of Hubei Province(No.2005ABA016 and 2004Q002)
文摘New appronches were applied to improve the molecular connectivity indices m^X^τ. The vertex valence is redefined and it was reasonable for hydrogen atom. The distances between vertices were used to propose novel connectivity topological indexes. The vertices and the distances in a molecular graph were taken into account in this definition. The linear regression was used to develop the structural property models. The results indicate that the novel connectivity topological indexes are useful model parameters for Quantitative Strncture-Property Relationship ( QSPR ) analysis.
基金the Anhui Provincial Department of Education(No.KJ2021A1125)the National Natural Science Foundation of China(No.12374390)+1 种基金Ningbo 3315 Innovative Teams Program(No.2019A-14-C)the member of Youth Innovation Promotion Association Foundation of CAS,China(No.2023310).
文摘Designing catalysts with highly active,selectivity,and stability for electrocatalytic CO_(2)to formate is currently a severe challenge.Herein,we developed an electronic structure engineering on carbon nano frameworks embedded with nitrogen and sulfur asymmetrically dual-coordinated indium active sites toward the efficient electrocatalytic CO_(2)reduction reaction.As expected,atomically dispersed In-based catalysts with In-S_(1)N_(3)atomic interface with asymmetrically coordinated exhibited high efficiency for CO_(2)reduction reaction(CO_(2)RR)to formate.It achieved a maximum Faradaic efficiency(FE)of 94.3%towards formate generation at−0.8 V vs.reversible hydrogen electrode(RHE),outperforming that of catalysts with In-S2N2 and In-N4 atomic interface.And at a potential of−1.10 V vs.RHE,In-S_(1)N_(3)achieves an impressive Faradaic efficiency of 93.7%in flow cell.The catalytic performance of In-S_(1)N_(3)sites was confirmed to be enhanced through in-situ X-ray absorption near-edge structure(XANES)measurements under electrochemical conditions.Our discovery provides the guidance for performance regulation of main group metal catalysts toward CO_(2)RR at atomic scale.
基金supported by the National Natural Science Foundation of China(Nos.92161102 and 21971118)the Nat-ural Science Foundation of Tianjin City(Nos.21JCZXJC00140 and 20JCYBJC01560)as well as the 111 project(B18030)from Ministry of Education China to Z.M.S.and the Tianjin Research Innovation Project for Postgraduate Students(2020YJSB150)the Ph.D.Can-didate Research Innovation Fund of NKU School of Materials Sci-ence and Engineering to H.-L.X.
文摘Two isomers of a sandwich-type anion [Ge_(9)-In-Ge_(9)]^(5–) were synthesized by controlling the chelating agents (2,2,2-crypt/18-C-6). Further reactions with early/late transition metal complexes, Mo(CO)_(6) and Ni(COD)_(2), respectively, yielded two new types of inorganic sandwich derivatives: a half-sandwich cluster [Ge_(9)-In-Mo(CO)_(5)]^(3–) with a low-valence In(I) center and an unsymmetrical sandwich-type cluster {[(Ni@Ge_(9))In(Ni_(0.648)@Ge_(9))]}^(5–) due to the insertion of Ni atoms, respectively. The isolation of these new derivatives demonstrates the reactivity of sandwich-type [Ge_(9)-In-Ge_(9)]^(5–) acting as the precursor, which provides some enlightenment for constructing new inorganic sandwich compounds.
基金supports from the National Key R&D Program of China(No.2020YFA0710404)the National Natural Science Foundation of China(No.52173269),the KC Wong Education Foundation(No.GJTD-2020-09)the Liaoning Revitalization Talents Program,and the Youth Innovation Promotion Association CAS(No.2019191).
文摘Electrical contact materials are generally Ag-or Cu-based composites and play a critical role in ensuring the reliability and efficiency of electrical equipments and electronic instruments.The MAX(M is an early transition metal,A is an element from III or IV main groups,and X is carbon or/and nitrogen)phase ceramics display a unique combination of properties and may serve as an ideal reinforcement phase for electrical contact materials.The biological materials evolved in nature generally exhibit three-dimensional(3D)interpenetrating-phase architectures,which may offer useful inspiration for the architectural design of electrical contact materials.Here,a series of bi-continuous Ag-Ti_(3)SiC_(2) MAX phase composites with high ceramic contents exceeding 50 vol.%and having micron-and ultrafine-scaled 3D interpenetrating-phase architectures,wherein both constituents were continuous and mutually interspersed,were exploited by pressureless infiltration of Ag melt into partially sintered Ti_(3)SiC_(2) scaffolds.The mechanical and electrical properties as well as the friction and wear performance of the composites were investigated and revealed to be closely dependent on the ceramic contents and characteristic structural dimensions.The composites exhibited a good combination of properties with high hardness over 2.3 GPa,high flexural strength exceeding 530 MPa,decent fracture toughness over 10 MPa·m^(1/2),and good wear resistance with low wear rate at an order of 10^(-5)mm^(3)/(N·m),which were much superior compared to the counterparts made by powder metallurgy methods.In particular,the hardness,electrical conductivity,strength,and fracture toughness of the composites demonstrated a simultaneous improvement as the structure was refined from micron-to ultrafine-scales at equivalent ceramic contents.The good combination of properties along with the facile processing route makes the Ag-Ti_(3)SiC_(2)3D interpenetrating-phase composites appealing for electrical contact applications.
基金We are grateful for the financial support from the Natural Science Foundation of China(51979081)Fundamental Research Funds for the Central Universities(No.B200202103)+2 种基金Ministry of Education of Singapore(Tier 1:RG4/20 and Tier 2:MOET2EP10120-0002)Agency for Science,Technology and Research(AME IRG:A20E5c0080)PAPD。
文摘Photoabsorption charge separation/transfer and surface reaction are the three main factors influencing the efficiency of photocatalysis.Band structure engineering has been extensively applied to improve the light absorption of photocatalysts,however,most of the developed photocatalysts still suffer from low photocatalytic performance due to the limited active site(s)and fast recombination of photogenerated charge carriers.In this work,atomically dispersed main group magnesium(Mg)is introduced onto CdS monodispersed nanospheres,which greatly enhances the photocatalytic hydrogen evolution reaction.The photocatalytic hydrogen evolution reaction rate reaches 30.6 mmol·gcatalyst^(-1)·h^(-1),which is about 11.8 and 2.5 times that of pure CdS and Pt(2 wt.%)-CdS.The atomically dispersed Mg on CdS acts as an electron sink to trap photogenerated electrons,and at the same time,greatly reduces the Gibbs free energy of hydrogen evolution reaction(HER)and accelerates HER.
基金support from the National Natural Science Foundation of China(Grant 22001184,Y.S.,11904425,C.L.)the Natural Science Foundation of Jiangsu Province(Grant BK20200849,Y.S.)+1 种基金the Natural Science Foundation of Jiangsu Higher Education Institutions of China(Grant 20KJB150002,Y.S.)the Entrepreneurship and Innovation Talent Program of Jiangsu Province(Y.S.,JSSCBS20210664,C.L.).
文摘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.
基金the National Natural Science Foundation of China(No.21901039)the Natural Science Foundation of Jiangsu Province(No.BK20190327)。
文摘Carboranes are a class of polyhedral boron-carbon molecular clusters,they can serve as versatile ligands in stabilizing low-valent main group element compounds,due to their exceptionally thermal and chemical stabilities,easy modifications at the cage carbon vertices,as well as large spherical steric effects.These carborane-based ligands provide interesting opportunities for the synthesis of low-valent main group element compounds with novel structure and reactivity,which indeed enrich the chemistry of low-valent element main group compounds.This review summarizes the recent advances in the chemistry of lowvalent group 13 and group 14 element compounds supported by carborane-based ligands.Achievements and perspectives in this new and flourishing field are discussed in this review.
基金supported by the National Natural Science Foundation of China(Nos.21772088 and 21573179)the Natural Science Foundation of Jiangsu Province(No.BK20170635)the Young Elite Scientist Sponsorship Program of China Association of Science and Technology,the program of Jiangsu SpeciallyAppointed Professor and Shuangchuang Talent Plan of Jiangsu Province。
文摘Theσ-bond activation by main group element has received enormous attention from theoretical and experimental chemists.Here,the reaction of C-X(X=Cl,Br,I)bonds in benzyl and allyl halides with a pincer-type phosphorus(Ⅲ)species was reported.A series of structurally robust phosphorus(Ⅴ)compounds were formed via the formal oxidative addition reactions of C-X bonds to the phosphorus(Ⅲ)center.Density functional theory calculations show that the nucleophilic addition process is more favorable than the direct oxidative addition mechanism.Isomerization of bent structures of phosphorus(Ⅲ)compound to poorly nucleophilic compounds to undergo further C-X bond activation can be rationalized by frontier molecule orbital analysis.This study not only provides a deep understanding of the reactivity of phosphorus(Ⅲ)species but also demonstrates a potential of main group elements for the small-molecule activation.
基金supported by the Deutsche Forschungsgemeinschaft(DFG)[project no.470309834(Ro2008/21-1 and HI 2063/1-1)]the support by the state of Baden-Württemberg through bwHPC and DFG[grant no.INST 40/467-1 FUGG(JUSTUS cluster)].
文摘We have discovered a route to access the longest low-valent molecular silaphospha-chain,a sevenmembered chain structure that incorporates three silicon and four phosphorus atoms by stepwise activation of white phosphorus(P_(4))using two different silylene precursors.The chain species was formed via a highly reactive polyphosphide intermediate.The isolation of a stable analogue of this reaction intermediate was achieved by stepwise reaction with mono and bis(silylenes).Due to the rigidity of the ferrocenediyl framework of the bis(silylene),the isomerization process of the chain structure was hampered.Theoretical studies such as natural bond orbital and atoms in molecules analyses of the seven-membered chain species indicated some degree of delocalization of the double bond system.