A new type of dianionic Ir(Ⅲ) CCC pincer complexes(SNHC-Ir, 1a–1c) is successfully designed and synthesized by developing a one-step methodology, which involves an initial coordination of Ir(I) with the NHC and subs...A new type of dianionic Ir(Ⅲ) CCC pincer complexes(SNHC-Ir, 1a–1c) is successfully designed and synthesized by developing a one-step methodology, which involves an initial coordination of Ir(I) with the NHC and subsequent metallation of double sp2C–H bonds. This method is considerably useful over those reported by using strong coordination ligand or carbonic anion exchange,and would provide an alternative efficient template of organometallics synthesis. Experimental and density functional theory(DFT) calculation results indicate that the spirocyclic framework is a favourable factor for the facile formation and stabilization of these complexes. Primary investigation shows that chloride 1b can well catalyze homo and hetero addition of styrene derivatives and remote olefin isomerization, which represents the first catalytic application of the dianionic CCC pincer complexes.展开更多
Manipulating magnetic couplings in molecular magnets is of great importance in improving the mag-netic properties of such materials.It has been proved that by adjusting the strength of magnetic cou-plings and the arra...Manipulating magnetic couplings in molecular magnets is of great importance in improving the mag-netic properties of such materials.It has been proved that by adjusting the strength of magnetic cou-plings and the arrangement of the intermolecular magnetic dipoles,magnetic blocking can be significantly enhanced.Herein manipulating the intramolecular dipole interactions by ligand modifica-tion was attempted with the use of three closely related dinuclear Er(Ⅲ)complexes of a common chemical formula of[(COT^(R))Er(μ-CI)(THF)]_(2)(COT^(R)is monosubstituted cyclooctatetraenide dianions with R=diphenylmethylsilyl(Ph_(2)MeS)for 1,triethylsilyl(TES)for 2,and triisopropylsilyl(TIPS)for 3).Each of these complexes features a centrosymmetric dinuclear core unit with their component Er(Ⅲ)ions doubly bridged by two chloro ligands and further coordinated with a capping substituted corR ligand and a coordinated THF molecule.Magnetic studies reveal that the complexes display similar ferromagnetic couplings with comparable single-molecule magnetic behaviors.The ferromagnetic couplings dominated by the intramolecular dipole interactions are found to be 0.7614,0.7380,and 0.5635 cm^(-1)for 1,2,and 3,respectively.The angles(θ)between the magnetic easy axes and the intramolecular Er-Er lines are 24.88(2)°,25.23(1),and 31.85(5),leading to transversal dipole fields of 0.0114,0.0113,and 0.0125 T for 1,2,and 3,respectively.Although the different ligand substitution generates a sizable difference of about 7 in theθangle,the resulting difference in the dipole interactions is not sufficiently strong to cause any significant differences in their magnetic properties.Further change in theθangles to the"side-by-side"(θ=90°)or"head-to-tail"(θ=0°)arrangement of the magnetic easy axes,achievable by rational mo-lecular design,is expected to lead to molecular magnetic materials with much enhanced properties.展开更多
A series of half-sandwich group IV metal complexes with tridentate monoanionic phenoxy-imine arylsulfide [O-NS] ligand [2-Bu^t4-Me-6-（（2-（SC6H5）C6H4N = CHC6H2O）]- （La） and dianionic phenoxy-amine arylsulfide [O...A series of half-sandwich group IV metal complexes with tridentate monoanionic phenoxy-imine arylsulfide [O-NS] ligand [2-Bu^t4-Me-6-（（2-（SC6H5）C6H4N = CHC6H2O）]- （La） and dianionic phenoxy-amine arylsulfide [O-N-S] ligand [2-Bu^t4-Me-6-（（2-（SC6H5）C6H4N-CH2C6H2O）]2- （Lb） have been synthesized and characterized. Lb was obtained easily in high yield by reduction of ligand La with excess LiAlH4 in cool diethyl ether. Half-sandwich Group Ⅳ metal complexes CpTi[O-NS]Cl2 （1a）, CpZr[O-NS]Cl2 （1b）, CpTi[O-N-S]Cl （2a）, CpZr[O-N-S]Cl （2b） and CpZr[O-N-S]Cl （2c） were synthesized by the reactions of La and Lb with CpTiCl3, CpZrCl3 and Cp ZrCl3, and characterized by IR, ^1H-NMR, ^13C-NMR and elemental analysis. In addition, an X-ray structure analysis was performed on ligand Lb. The title Group IV half-sandwich bearing tridentate [O,N,S] ligands show good catalytic activities for ethylene polymerization in the presence of methylaluminoxane （MAO） as co-catalyst up to 1.58 × 10^7 g-PE.mol-Zr-1.h-1. The good catalytic activities can be maintained even at high temperatures such as 100 ℃ exhibiting the excellent thermal stability for these half-sandwich metal pre-catalysts.展开更多
Piperonyl methyl ketone was obtained by oxidizing isosafrole with hydrogen peroxide and formic acid. Dianion of ethyl acetoacetate reacted with piperonyl methyl ketone and 5, 6-dihydro-6-methyl-6-piperonyl-2H-pyran-2...Piperonyl methyl ketone was obtained by oxidizing isosafrole with hydrogen peroxide and formic acid. Dianion of ethyl acetoacetate reacted with piperonyl methyl ketone and 5, 6-dihydro-6-methyl-6-piperonyl-2H-pyran-2, 4-dione was prepared, which reacted with substituted anilines in the presence of ethyl orthoformate to obtain 3-anilinomethylene-5, 6- dihydro- 6-methyl-6-piperonyl-2H-pyran-2, 4-diones. Their structures were confirmed by 1HNMR and elemental analysis.展开更多
β-Keto-δ-valerolactones, which were obtained by reaction of acetoacetate with aldehydes or ketones, reacted with carbon disulfide, alkyl halides and a new condensation reaction was developed. The structures of the p...β-Keto-δ-valerolactones, which were obtained by reaction of acetoacetate with aldehydes or ketones, reacted with carbon disulfide, alkyl halides and a new condensation reaction was developed. The structures of the products 3 were confirmed by HNMR spectra and elemental 1 analysis.展开更多
The equilibrium geometries, energies, harmonic vibrational frequencies, and nucleus independent chemical shifts （NICS） of the new type sandwich structures [As4MAs4]^n- （M = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt; n ...The equilibrium geometries, energies, harmonic vibrational frequencies, and nucleus independent chemical shifts （NICS） of the new type sandwich structures [As4MAs4]^n- （M = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt; n = 0, 1 or 2） are investigated at the B3LYP level. All the [As4MAs4]^n- species adopt staggered （D4d） conformations as their stable structures and eclipsed （D4h） conformations as their transition states, and once the sandwich complexes are formed, the As4^2- square properties remain unchanged. The NICS calculation confirms that the complexes of Fe, Co, and Ni are aromatic with negative NICS values, and those of Ru, Rh, and lx exhibit slight aromaticity, while those of Pd, Os, and Pt show slight antiaromaticity.展开更多
MgATP is a stable complex formed by the chelation of Mg^(2+)with deprotonated adenosine-5'-triphosphate(ATP).In the cellular environment,MgATP plays a critical role in ATP hydrolysis,releasing substantial energy t...MgATP is a stable complex formed by the chelation of Mg^(2+)with deprotonated adenosine-5'-triphosphate(ATP).In the cellular environment,MgATP plays a critical role in ATP hydrolysis,releasing substantial energy to support essential biological functions.To understand the structure and stabilization mechanism of MgATP,we conducted a joint negative ion photoelectron spectroscopic and computational study of the[ATP^(4-)·Mg^(2+)]^(2-)complex dianion,using[ATP^(4-)·2H^(+)]^(2-)as a reference.The experimentally determined adiabatic and vertical detachment energies(ADE and VDE)of[ATP^(4-)·Mg^(2+)]^(2-)at 20 K are 3.51±0.05 eV and 3.82±0.05 eV,respectively.The major spectral features of[ATP^(4-)·Mg^(2+)]^(2-)are attributed to two theoretically identified isomers with unfolded geometries,which are stabilized primarily by electrostatic interactions between Mg^(2+)and the triphosphate and ribose groups,with four deprotonated oxygens forming a pseudo-tetrahedral coordination.In contrast,[ATP^(4-)·2H^(+)]^(2-)exhibits a fundamentally different stabilization mechanism.Although most of the fifteen identified[ATP^(4-)·2H^(+)]^(2-)isomers also adopt unfolded geometries,they are primarily stabilized by intramolecular hydrogen bonds within the triphosphate group and between triphosphate and ribose groups.The interaction between ATP^(4-)and two protons is found to be much weaker than that with Mg^(2+),and[ATP^(4-)·2H^(+)]^(2-)exhibits substantial structural flexibility compared to[ATP^(4-)·Mg^(2+)]^(2-)due to the conformational constraint of the triphosphate chain by Mg^(2+).Thirteen[ATP^(4-)·2H^(+)]^(2-)isomers with unfolded geometries likely account for the major high-EBE(electron-binding-energy)spectral features.Notably,for the first time,a low EBE and temperature-dependent spectral feature is observed and attributed to two folded isomers of[ATP^(4-)·2H^(+)]^(2-),which exist at 20 K but disappear at room temperature.This study provides valuable molecular-level insights into cellular MgATP that resides within the hydrophobic pockets of proteins.展开更多
Many sandwich-type lanthanide complexes show extremely high energy barriers(Ueff)for the reversal of magnetization and high blocking temperatures,being the star molecules in the research area of single-molecule magnet...Many sandwich-type lanthanide complexes show extremely high energy barriers(Ueff)for the reversal of magnetization and high blocking temperatures,being the star molecules in the research area of single-molecule magnets.Herein,the preparation,structural determination,and magnetic property studies of two ansa-bridged Er-COT(COT=cyclooctatetraenyl dianion)complexes[KDME_(2)][Er((η^(8)-COT-Si^(Me2))_(2)O)](1)and[KDME_(2)][Er((η^(8)-COT-Si^(iPr2))_(2)O)]K[Er((η^(8)-COT-Si^(iPr2))_(2)O)](2)were reported.The Er(Ⅲ)ions in both complexes are sandwiched by two COT rings which are ansa-bridged by a[Si-O-Si]group.Magnetic studies reveal both complexes display slow magnetic relaxations with comparable energy barriers(228(5)K for 1,and 196(4)K for 2)and blocking temperatures(10.5 K for both complexes).The difference in the relaxation times(τ)for the two complexes was studied in details:different molecular vibrations induced by the substituents are the main reason forτfor 1 being about 10 times longer than for 2 at the same temperature above 10 K,while the quantum tunnelling of magnetization relaxation time(τQTM)for 2 is about 10 times longer than for 1 below 8 K,probably owing to the different dipolar interactions.Further rearrangement of molecular network with such ansa-bridged SMMs is promising to design molecular magnetic materials with enhanced properties or new properties.展开更多
Neutral perylene bisimides(PBI) are well-known n-type organic semiconductors, with number of challenging electronic properties in their neutral and reduced states. We report the characteristic electronic properties of...Neutral perylene bisimides(PBI) are well-known n-type organic semiconductors, with number of challenging electronic properties in their neutral and reduced states. We report the characteristic electronic properties of PBI anionic films. We unexpectedly discovered that pristine PBI dianion film showed p-type character, while oxidized dianion film(dominant neutral state with few radical anions) showed normal n-type semiconductor character based on Seebeck effect measurements. Both kinds of films exhibit high electrical conductivity with a potential for thermoelectric applications. The mechanism of polarity reversal is proposed.展开更多
A 1,2,3,4-tetrahydro[60]fullerene with a five-membered heterocycle fused to a[5,6]junction was obtained with high regioselectivity by electrochemical functionalization of a[60]fulleroindoline.The structure was determi...A 1,2,3,4-tetrahydro[60]fullerene with a five-membered heterocycle fused to a[5,6]junction was obtained with high regioselectivity by electrochemical functionalization of a[60]fulleroindoline.The structure was determined by spectroscopic data.A plausible reaction mechanism supported by computational calculations is proposed.展开更多
Ligands play a key role in controlling activity of organometallic complexes so that development of new ligands to overcome the challenge is the main topic of modern chemistry.The first example of 1,1-hydride migratory...Ligands play a key role in controlling activity of organometallic complexes so that development of new ligands to overcome the challenge is the main topic of modern chemistry.The first example of 1,1-hydride migratory insertion and intramolecular redox reaction has been realized in this work by applying a new ligand in rare-earth metal chemistry.The novel rare-earth metal complexes L^(Mes)RECH2TMS(THF)(RE=Y(1a),Dy(1b),Er(1c),Yb(1d),L^(Mes)=1-(3-(2,6-iPr_(2)C_(6)H_(3)N=CH)C8H4N)-CH_(2)CH_(2)-3-(2-CH2–4,6-Me_(2)C_(6)H_(2))-(N(CH)_(2)NC),THF=tetrahydrofuran)bearing a ligand with imino,indolyl,NHC(N-heterocyclic carbene)multiple functionalities were synthesized and characterized.Treatment of complexes 1 with silanes(PhSiH3or PhSiH2Me or PhSiD3)selectively produced the unprecedented 1,1-hydride(or deuterated H)migratory insertion of the indolyl moiety of the novel unsymmetrical dinuclear rare-earth metal complexes 2.The complex 2a reacts with Ph_(2)C=O to give the selective C=O double bond insertion to the RE–Co-methylene-Mesbond product 3a which further reacts with another Ph_(2)C=O(or DMAP,4-N,N-dimethylaminopyridine)affording the novelμ-η^(2):η^(3)-dianionic 3-iminoindolyl dinuclear rare-earth metal complex 4a.The latter is formed through an unusual intramolecular redox reaction(through electron migration from the 2-carbanion of the indolyl ring to the imino motif)resulting in the re-aromatization of the indolyl ring.展开更多
基金This work was supported by the National Natural Science Foundation of China(21502080,21772076,21871117,21772071,21702136,91956203)the“111”Program of Ministry of Education of China,the Major Project(2018ZX09711001-005-002)of Ministry of Science and Technology of China+2 种基金the Science and Technology Commission of Shanghai Municipality(19IC1430100)This work was supported by the High-Performance Computing Center of Shanghai Jiao Tong UniversityAlso,we thank Prof.Qing-Wei Zhang from the University of Science and Technology of China for his helpful discussion.
文摘A new type of dianionic Ir(Ⅲ) CCC pincer complexes(SNHC-Ir, 1a–1c) is successfully designed and synthesized by developing a one-step methodology, which involves an initial coordination of Ir(I) with the NHC and subsequent metallation of double sp2C–H bonds. This method is considerably useful over those reported by using strong coordination ligand or carbonic anion exchange,and would provide an alternative efficient template of organometallics synthesis. Experimental and density functional theory(DFT) calculation results indicate that the spirocyclic framework is a favourable factor for the facile formation and stabilization of these complexes. Primary investigation shows that chloride 1b can well catalyze homo and hetero addition of styrene derivatives and remote olefin isomerization, which represents the first catalytic application of the dianionic CCC pincer complexes.
基金the National Natural Science Foundation of China(92261203,22101116,21971106)the Science Research Foun dation of jilin Province(YDZJ202301ZYTS478)。
文摘Manipulating magnetic couplings in molecular magnets is of great importance in improving the mag-netic properties of such materials.It has been proved that by adjusting the strength of magnetic cou-plings and the arrangement of the intermolecular magnetic dipoles,magnetic blocking can be significantly enhanced.Herein manipulating the intramolecular dipole interactions by ligand modifica-tion was attempted with the use of three closely related dinuclear Er(Ⅲ)complexes of a common chemical formula of[(COT^(R))Er(μ-CI)(THF)]_(2)(COT^(R)is monosubstituted cyclooctatetraenide dianions with R=diphenylmethylsilyl(Ph_(2)MeS)for 1,triethylsilyl(TES)for 2,and triisopropylsilyl(TIPS)for 3).Each of these complexes features a centrosymmetric dinuclear core unit with their component Er(Ⅲ)ions doubly bridged by two chloro ligands and further coordinated with a capping substituted corR ligand and a coordinated THF molecule.Magnetic studies reveal that the complexes display similar ferromagnetic couplings with comparable single-molecule magnetic behaviors.The ferromagnetic couplings dominated by the intramolecular dipole interactions are found to be 0.7614,0.7380,and 0.5635 cm^(-1)for 1,2,and 3,respectively.The angles(θ)between the magnetic easy axes and the intramolecular Er-Er lines are 24.88(2)°,25.23(1),and 31.85(5),leading to transversal dipole fields of 0.0114,0.0113,and 0.0125 T for 1,2,and 3,respectively.Although the different ligand substitution generates a sizable difference of about 7 in theθangle,the resulting difference in the dipole interactions is not sufficiently strong to cause any significant differences in their magnetic properties.Further change in theθangles to the"side-by-side"(θ=90°)or"head-to-tail"(θ=0°)arrangement of the magnetic easy axes,achievable by rational mo-lecular design,is expected to lead to molecular magnetic materials with much enhanced properties.
基金financially supported by the Shanghai Science and Technology Committee(08DZ2270500,08DJ1400103)Shanghai Leading Academic Discipline Project(B108)the National Basic Research Program of China(2009CB825300,2010DFA41160)
文摘A series of half-sandwich group IV metal complexes with tridentate monoanionic phenoxy-imine arylsulfide [O-NS] ligand [2-Bu^t4-Me-6-（（2-（SC6H5）C6H4N = CHC6H2O）]- （La） and dianionic phenoxy-amine arylsulfide [O-N-S] ligand [2-Bu^t4-Me-6-（（2-（SC6H5）C6H4N-CH2C6H2O）]2- （Lb） have been synthesized and characterized. Lb was obtained easily in high yield by reduction of ligand La with excess LiAlH4 in cool diethyl ether. Half-sandwich Group Ⅳ metal complexes CpTi[O-NS]Cl2 （1a）, CpZr[O-NS]Cl2 （1b）, CpTi[O-N-S]Cl （2a）, CpZr[O-N-S]Cl （2b） and CpZr[O-N-S]Cl （2c） were synthesized by the reactions of La and Lb with CpTiCl3, CpZrCl3 and Cp ZrCl3, and characterized by IR, ^1H-NMR, ^13C-NMR and elemental analysis. In addition, an X-ray structure analysis was performed on ligand Lb. The title Group IV half-sandwich bearing tridentate [O,N,S] ligands show good catalytic activities for ethylene polymerization in the presence of methylaluminoxane （MAO） as co-catalyst up to 1.58 × 10^7 g-PE.mol-Zr-1.h-1. The good catalytic activities can be maintained even at high temperatures such as 100 ℃ exhibiting the excellent thermal stability for these half-sandwich metal pre-catalysts.
文摘Piperonyl methyl ketone was obtained by oxidizing isosafrole with hydrogen peroxide and formic acid. Dianion of ethyl acetoacetate reacted with piperonyl methyl ketone and 5, 6-dihydro-6-methyl-6-piperonyl-2H-pyran-2, 4-dione was prepared, which reacted with substituted anilines in the presence of ethyl orthoformate to obtain 3-anilinomethylene-5, 6- dihydro- 6-methyl-6-piperonyl-2H-pyran-2, 4-diones. Their structures were confirmed by 1HNMR and elemental analysis.
文摘β-Keto-δ-valerolactones, which were obtained by reaction of acetoacetate with aldehydes or ketones, reacted with carbon disulfide, alkyl halides and a new condensation reaction was developed. The structures of the products 3 were confirmed by HNMR spectra and elemental 1 analysis.
文摘The equilibrium geometries, energies, harmonic vibrational frequencies, and nucleus independent chemical shifts （NICS） of the new type sandwich structures [As4MAs4]^n- （M = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt; n = 0, 1 or 2） are investigated at the B3LYP level. All the [As4MAs4]^n- species adopt staggered （D4d） conformations as their stable structures and eclipsed （D4h） conformations as their transition states, and once the sandwich complexes are formed, the As4^2- square properties remain unchanged. The NICS calculation confirms that the complexes of Fe, Co, and Ni are aromatic with negative NICS values, and those of Ru, Rh, and lx exhibit slight aromaticity, while those of Pd, Os, and Pt show slight antiaromaticity.
基金was supported by the U.S.Department of Energy(DOE),Office of Science,Office of Basic Energy Sciences,Division of Chemical Sciences,Geosciences,and Biosciences,Condensed Phase and Interfacial Molecular Science program,FWP 16248.
文摘MgATP is a stable complex formed by the chelation of Mg^(2+)with deprotonated adenosine-5'-triphosphate(ATP).In the cellular environment,MgATP plays a critical role in ATP hydrolysis,releasing substantial energy to support essential biological functions.To understand the structure and stabilization mechanism of MgATP,we conducted a joint negative ion photoelectron spectroscopic and computational study of the[ATP^(4-)·Mg^(2+)]^(2-)complex dianion,using[ATP^(4-)·2H^(+)]^(2-)as a reference.The experimentally determined adiabatic and vertical detachment energies(ADE and VDE)of[ATP^(4-)·Mg^(2+)]^(2-)at 20 K are 3.51±0.05 eV and 3.82±0.05 eV,respectively.The major spectral features of[ATP^(4-)·Mg^(2+)]^(2-)are attributed to two theoretically identified isomers with unfolded geometries,which are stabilized primarily by electrostatic interactions between Mg^(2+)and the triphosphate and ribose groups,with four deprotonated oxygens forming a pseudo-tetrahedral coordination.In contrast,[ATP^(4-)·2H^(+)]^(2-)exhibits a fundamentally different stabilization mechanism.Although most of the fifteen identified[ATP^(4-)·2H^(+)]^(2-)isomers also adopt unfolded geometries,they are primarily stabilized by intramolecular hydrogen bonds within the triphosphate group and between triphosphate and ribose groups.The interaction between ATP^(4-)and two protons is found to be much weaker than that with Mg^(2+),and[ATP^(4-)·2H^(+)]^(2-)exhibits substantial structural flexibility compared to[ATP^(4-)·Mg^(2+)]^(2-)due to the conformational constraint of the triphosphate chain by Mg^(2+).Thirteen[ATP^(4-)·2H^(+)]^(2-)isomers with unfolded geometries likely account for the major high-EBE(electron-binding-energy)spectral features.Notably,for the first time,a low EBE and temperature-dependent spectral feature is observed and attributed to two folded isomers of[ATP^(4-)·2H^(+)]^(2-),which exist at 20 K but disappear at room temperature.This study provides valuable molecular-level insights into cellular MgATP that resides within the hydrophobic pockets of proteins.
基金supported by the National Natural Science Foundation of China(92261203,22101116,and 21971106)Key Laboratory of Rare Earth Chemistry of Guangdong Higher Education Institutes(2022KSYS006)+1 种基金the Stable Support Plan Program of Shenzhen Natural Science Fund(20200925161141006)Shenzhen Fundamental Research Program(JCYJ20220530115001002 and JCYJ20220818100417037).
文摘Many sandwich-type lanthanide complexes show extremely high energy barriers(Ueff)for the reversal of magnetization and high blocking temperatures,being the star molecules in the research area of single-molecule magnets.Herein,the preparation,structural determination,and magnetic property studies of two ansa-bridged Er-COT(COT=cyclooctatetraenyl dianion)complexes[KDME_(2)][Er((η^(8)-COT-Si^(Me2))_(2)O)](1)and[KDME_(2)][Er((η^(8)-COT-Si^(iPr2))_(2)O)]K[Er((η^(8)-COT-Si^(iPr2))_(2)O)](2)were reported.The Er(Ⅲ)ions in both complexes are sandwiched by two COT rings which are ansa-bridged by a[Si-O-Si]group.Magnetic studies reveal both complexes display slow magnetic relaxations with comparable energy barriers(228(5)K for 1,and 196(4)K for 2)and blocking temperatures(10.5 K for both complexes).The difference in the relaxation times(τ)for the two complexes was studied in details:different molecular vibrations induced by the substituents are the main reason forτfor 1 being about 10 times longer than for 2 at the same temperature above 10 K,while the quantum tunnelling of magnetization relaxation time(τQTM)for 2 is about 10 times longer than for 1 below 8 K,probably owing to the different dipolar interactions.Further rearrangement of molecular network with such ansa-bridged SMMs is promising to design molecular magnetic materials with enhanced properties or new properties.
基金supported by the National Natural Science Foundation of China (51573055, 51373054, 21334002, 51403063)National Basic Research Program of China (2014CB643504)+2 种基金Fundamental Research Funds for the Central UniversitiesChina Postdoctoral Science Fund (2014M562174)Introduced Innovative Research & Development Team of Guangdong (201101C0105067115)
文摘Neutral perylene bisimides(PBI) are well-known n-type organic semiconductors, with number of challenging electronic properties in their neutral and reduced states. We report the characteristic electronic properties of PBI anionic films. We unexpectedly discovered that pristine PBI dianion film showed p-type character, while oxidized dianion film(dominant neutral state with few radical anions) showed normal n-type semiconductor character based on Seebeck effect measurements. Both kinds of films exhibit high electrical conductivity with a potential for thermoelectric applications. The mechanism of polarity reversal is proposed.
基金the National Natural Science Foundation of China(No.21132007)Specialized Research Fund for the Doctoral Program of Higher Education(No.20123402130011).
文摘A 1,2,3,4-tetrahydro[60]fullerene with a five-membered heterocycle fused to a[5,6]junction was obtained with high regioselectivity by electrochemical functionalization of a[60]fulleroindoline.The structure was determined by spectroscopic data.A plausible reaction mechanism supported by computational calculations is proposed.
基金supported by the National Natural Science Foundation of China(22031001,21871004,21861162009,22171004)the grants from the Education Department of Anhui Province(GXXT-2021-052)。
文摘Ligands play a key role in controlling activity of organometallic complexes so that development of new ligands to overcome the challenge is the main topic of modern chemistry.The first example of 1,1-hydride migratory insertion and intramolecular redox reaction has been realized in this work by applying a new ligand in rare-earth metal chemistry.The novel rare-earth metal complexes L^(Mes)RECH2TMS(THF)(RE=Y(1a),Dy(1b),Er(1c),Yb(1d),L^(Mes)=1-(3-(2,6-iPr_(2)C_(6)H_(3)N=CH)C8H4N)-CH_(2)CH_(2)-3-(2-CH2–4,6-Me_(2)C_(6)H_(2))-(N(CH)_(2)NC),THF=tetrahydrofuran)bearing a ligand with imino,indolyl,NHC(N-heterocyclic carbene)multiple functionalities were synthesized and characterized.Treatment of complexes 1 with silanes(PhSiH3or PhSiH2Me or PhSiD3)selectively produced the unprecedented 1,1-hydride(or deuterated H)migratory insertion of the indolyl moiety of the novel unsymmetrical dinuclear rare-earth metal complexes 2.The complex 2a reacts with Ph_(2)C=O to give the selective C=O double bond insertion to the RE–Co-methylene-Mesbond product 3a which further reacts with another Ph_(2)C=O(or DMAP,4-N,N-dimethylaminopyridine)affording the novelμ-η^(2):η^(3)-dianionic 3-iminoindolyl dinuclear rare-earth metal complex 4a.The latter is formed through an unusual intramolecular redox reaction(through electron migration from the 2-carbanion of the indolyl ring to the imino motif)resulting in the re-aromatization of the indolyl ring.
