Reaction of 4,4’-(1,4-phenylene)bis(5-acetyl-6-methyl-2-thioxo-1,2-dihydropyridine-3-carbonitrile) (1) with methyl iodide afforded the 4,4’-(1,4-phenylene)bis(5-acetyl-6-methyl-2-(methylthio)nicotinonitrile) (2). Th...Reaction of 4,4’-(1,4-phenylene)bis(5-acetyl-6-methyl-2-thioxo-1,2-dihydropyridine-3-carbonitrile) (1) with methyl iodide afforded the 4,4’-(1,4-phenylene)bis(5-acetyl-6-methyl-2-(methylthio)nicotinonitrile) (2). The reaction of 2 with hydrazine hydrate followed by diazotization reaction af-forded the 1,1’-(1,4-phenylenebis(3-amino-6-methyl-1H-pyrazolo[3,4-b]pyridine-4,5-diyl))bis(e-than-1-one) (3) and 1,1’-(1,4-phenylenebis(3-(chlorodiazenyl)-6-methyl-1H-pyrazolo[3,4-b]-pyridine-4,5-diyl))bis(ethan-1-one) (4) respectively. On the other hand, reaction of 4 with malononitrile, 2-cyanoethanethioamide, ethyl acetoacetate, acetyl acetone, ethyl benzoylacetate, diethylmalonate, ethyl cyanoacetate and phenacylbromide aiming to build up pyrazolotriazine or pyrazole ring on the ring system of 4. Structures of all newly synthesized heterocyclic compounds in the present study were confirmed by considering the data of IR, 1H NMR, mass spectra as well as that of elemental analyses.展开更多
A series of“half-sandwich”bis(imino)pyridyl iron complexes with a substituted 8-(p-Xphenyl)naphthylamine(X=OMe,Me,CF3)was designed and synthesized by combining weakπ-πinteraction with steric and electronic tunings...A series of“half-sandwich”bis(imino)pyridyl iron complexes with a substituted 8-(p-Xphenyl)naphthylamine(X=OMe,Me,CF3)was designed and synthesized by combining weakπ-πinteraction with steric and electronic tunings.The weak noncovalentπ-πinteraction as well as the steric and electronic effects of bis(imino)pyridyl iron complexes were identified by experimental analyses and calculations.The roles of weakπ-πinteraction,steric bulk,and electronic tuning on the ethylene polymerization performance of bis(imino)pyridyl iron catalysts were studied in detail.The combination ofπ-πinteraction with steric and electronic tunings can access to thermally stable bis(imino)pyridyl iron at 130°C.展开更多
Luminescent rare earth complexes based on interconfigurational 5d-4f transition have characteristics of adjustable emission spectra and short excited state lifetimes,showing potential applications in display,lighting ...Luminescent rare earth complexes based on interconfigurational 5d-4f transition have characteristics of adjustable emission spectra and short excited state lifetimes,showing potential applications in display,lighting and other fields.In this work,nine Ce^(3+),Eu^(2+)and Yb^(2+)complexes with spiro-bis(pyrazolyl)borate ligands,where pyrazolyl stands for pyrazolyl,3-methylpyrazolyl,or 3,5-dimethylpyrazolyl,were designed and synthesized.Ce^(3+)complexes show emission colors of blue,with photoluminescence quantum yields(PLQYs)of 94%-100%;Eu^(2+)complexes show emission colors of yellow-green,with PLQYs of 60%-78%;Yb^(2+)complexes show emission colors of orange or red,with PLQYs of 3%-4%.In addition,the crystal structures and theoretical calculation results show C-H…M interactions between bridge-head H atoms of the spirane and central metal ions in these complexes.It is found that the introduction of spirane with large steric hindrance and the existence of C-H…M interactions can improve the stability of the complexes in air atmosphere.展开更多
文摘Reaction of 4,4’-(1,4-phenylene)bis(5-acetyl-6-methyl-2-thioxo-1,2-dihydropyridine-3-carbonitrile) (1) with methyl iodide afforded the 4,4’-(1,4-phenylene)bis(5-acetyl-6-methyl-2-(methylthio)nicotinonitrile) (2). The reaction of 2 with hydrazine hydrate followed by diazotization reaction af-forded the 1,1’-(1,4-phenylenebis(3-amino-6-methyl-1H-pyrazolo[3,4-b]pyridine-4,5-diyl))bis(e-than-1-one) (3) and 1,1’-(1,4-phenylenebis(3-(chlorodiazenyl)-6-methyl-1H-pyrazolo[3,4-b]-pyridine-4,5-diyl))bis(ethan-1-one) (4) respectively. On the other hand, reaction of 4 with malononitrile, 2-cyanoethanethioamide, ethyl acetoacetate, acetyl acetone, ethyl benzoylacetate, diethylmalonate, ethyl cyanoacetate and phenacylbromide aiming to build up pyrazolotriazine or pyrazole ring on the ring system of 4. Structures of all newly synthesized heterocyclic compounds in the present study were confirmed by considering the data of IR, 1H NMR, mass spectra as well as that of elemental analyses.
基金supported by the State Key Research Development Program of China(No.2021YFB3800701)National Natural Science Foundation of China(NSFC,No.52173016)+2 种基金Guangdong Basic and Applied Basic Research Foundation(Nos.2024A1515012784,2024A1515011102,and 2023A1515110549)Fundamental Research Funds for the Central Universities,Sun Yat-sen University(No.24qnpy047)PetroChina Scientific and Technological Projects(No.2022DJ6308).
文摘A series of“half-sandwich”bis(imino)pyridyl iron complexes with a substituted 8-(p-Xphenyl)naphthylamine(X=OMe,Me,CF3)was designed and synthesized by combining weakπ-πinteraction with steric and electronic tunings.The weak noncovalentπ-πinteraction as well as the steric and electronic effects of bis(imino)pyridyl iron complexes were identified by experimental analyses and calculations.The roles of weakπ-πinteraction,steric bulk,and electronic tuning on the ethylene polymerization performance of bis(imino)pyridyl iron catalysts were studied in detail.The combination ofπ-πinteraction with steric and electronic tunings can access to thermally stable bis(imino)pyridyl iron at 130°C.
基金Project supported by the National Key R&D Program of China(2021YFB3500400,2021YFB3501800,2022YFB3503700,2023YFB3506901)the National Natural Science Foundation of China(22071003,92156016,62104013)。
文摘Luminescent rare earth complexes based on interconfigurational 5d-4f transition have characteristics of adjustable emission spectra and short excited state lifetimes,showing potential applications in display,lighting and other fields.In this work,nine Ce^(3+),Eu^(2+)and Yb^(2+)complexes with spiro-bis(pyrazolyl)borate ligands,where pyrazolyl stands for pyrazolyl,3-methylpyrazolyl,or 3,5-dimethylpyrazolyl,were designed and synthesized.Ce^(3+)complexes show emission colors of blue,with photoluminescence quantum yields(PLQYs)of 94%-100%;Eu^(2+)complexes show emission colors of yellow-green,with PLQYs of 60%-78%;Yb^(2+)complexes show emission colors of orange or red,with PLQYs of 3%-4%.In addition,the crystal structures and theoretical calculation results show C-H…M interactions between bridge-head H atoms of the spirane and central metal ions in these complexes.It is found that the introduction of spirane with large steric hindrance and the existence of C-H…M interactions can improve the stability of the complexes in air atmosphere.
