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
Due to their unique physicochemical properties,the anion radical and dianion of perylene diimide derivatives(PDIs)recently attracted significant attention for organic semiconductors.However,the impact of packing struc...Due to their unique physicochemical properties,the anion radical and dianion of perylene diimide derivatives(PDIs)recently attracted significant attention for organic semiconductors.However,the impact of packing structure and the radical content for carrier transport in the solid state still need to be determined.Bringing the electron-withdrawing groups is an effective strategy for enablingπ−πstacking distance.Here,bay-tetrachloro-substituted PDI(B-4Cl-PDI)anion radical and dianion films were fabricated quantitatively doped with N_(2)H_(4)·H_(2)O.The radical contents were quantitatively calculated by absorption spectra in different doping ratios.The X-ray powder diffraction patterns showed that the anion radical presented a crystalline structure,and dianion aggregates exhibited an amorphous structure.With precise manipulation of the radical content,the anion radical aggregates and dianion aggregates showed the maximum electrical conductivity value of 0.024 and 0.0018 S/cm,respectively.The experiment results show that doping level and aggregate structure play a crucial role in electronic transport properties.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
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
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
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National Key R&D Program of China(No.2020YFA0714604)National Natural Science Foundation of China(Nos.U20A6002,91833304,5152100222005107,52203221)+4 种基金Basic and Applied Basic Research Major Program of Guangdong Province,China(No.2019B030302007)Research and Development Funds for Science and Technology Program of Guangzhou,China(No.202007020004)Natural Science Foundation of Guangdong Province,China(Nos.2019B121205002,2022A1515010063)Fund of the Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates,China(No.2019B030301003)Funding by Science and Technology Projects in Guangzhou,China(Nos.202102020401,202102020561).
文摘Due to their unique physicochemical properties,the anion radical and dianion of perylene diimide derivatives(PDIs)recently attracted significant attention for organic semiconductors.However,the impact of packing structure and the radical content for carrier transport in the solid state still need to be determined.Bringing the electron-withdrawing groups is an effective strategy for enablingπ−πstacking distance.Here,bay-tetrachloro-substituted PDI(B-4Cl-PDI)anion radical and dianion films were fabricated quantitatively doped with N_(2)H_(4)·H_(2)O.The radical contents were quantitatively calculated by absorption spectra in different doping ratios.The X-ray powder diffraction patterns showed that the anion radical presented a crystalline structure,and dianion aggregates exhibited an amorphous structure.With precise manipulation of the radical content,the anion radical aggregates and dianion aggregates showed the maximum electrical conductivity value of 0.024 and 0.0018 S/cm,respectively.The experiment results show that doping level and aggregate structure play a crucial role in electronic transport properties.
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.
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.
