A Ni(Ⅱ)coordination complex 1 with a novel boron-oxamido radical ligand was synthesized and isolated.Reactions of 1 with N,N-dimethyl-4-pyridinamine(DMAP)and 4,4'-bpy resulted in 2 and 3,respectively,accompanied ...A Ni(Ⅱ)coordination complex 1 with a novel boron-oxamido radical ligand was synthesized and isolated.Reactions of 1 with N,N-dimethyl-4-pyridinamine(DMAP)and 4,4'-bpy resulted in 2 and 3,respectively,accompanied by the spin state transition from S=1/2 to S=3/2.Both 2 and 3 were isolated as stable crystals and characterized to feature an S=3/2 spin state,with the S=1 Ni(Ⅱ)atoms ferromagnetically coupled with the ligand-centred radicals,by SQUID measurement and EPR spectroscopy.Complex 3 represents the first example of one-dimensional magnetic chain constructed by S=3/2 Ni(Ⅱ)-radical units.展开更多
It is highly urgent to develop synthetic strategies to make new category of stable luminescent radicals with desired emission wavelength.In this study,we have isolated two dioxoborocyclic radicals(3 and 4)by a direct ...It is highly urgent to develop synthetic strategies to make new category of stable luminescent radicals with desired emission wavelength.In this study,we have isolated two dioxoborocyclic radicals(3 and 4)by a direct synthetic route.They were characterized by UV,EPR spectroscopy and SQUID measurements.Their structures were obtained by single-crystal X-ray diffraction.Both radicals produce blue-photoluminescence(458 nm for 3 and 478 nm for 4)by radiative decay from higher excited states(D_(2)/D_(3))to the ground state(D_(0))based on theoretical calculation,breaking Kasha rule.The work records a new kind of radical emitters and the first stable radicals with blue emission bands.展开更多
Phenalenyl derivatives have been of tremendous interest due to their reversible dimerization in response to the external stimuli such as temperature.However,most of PLY derivatives only show the reversibility dependen...Phenalenyl derivatives have been of tremendous interest due to their reversible dimerization in response to the external stimuli such as temperature.However,most of PLY derivatives only show the reversibility dependent on temperature.Herein,we report a unique PLY-based radical anionic salt with reversibleσ-dimerization controlled by solvent rather than temperature.The structure and reversibility of this PLY anion system have been spectroscopically,crystallographically,and theoretically investigated.The molecule exists mainly as theσ-dimer form of K2[σ-12]in toluene,while it can be broken into the monomeric radical anion 1•–by re-dissolving in THF.Moreover,when THF is replaced with toluene,radical 1•–could beσ-dimerized back again.Theoretical calculations reveal that the potassium ions are necessary for the formation of theσ-dimer and the solvent polarity controls theσ-dimerization by regulating the presence of K+.展开更多
Summary of main observation and conclusion The coordination of silver cation to dlphosphene Mes"P=PMes"(1,Mes*=tBu3C6H2)was investigated in detail.The reaction of 1 with Ag(Al(ORF)4)(ORF=OC[CF3]3)in the rati...Summary of main observation and conclusion The coordination of silver cation to dlphosphene Mes"P=PMes"(1,Mes*=tBu3C6H2)was investigated in detail.The reaction of 1 with Ag(Al(ORF)4)(ORF=OC[CF3]3)in the ratios of 2:1,3:2 and 1:2 led to the formation of the first cationic silver linked diphos-phene complexes 2-4.Complexes 2 and 3 contain two and three diphosphene molecules linked by the linear Ag(Ⅰ)cation,respectively,and they feature unusual zig-ag topologies.Complex 4 is a dinuclear silver complex,and each Ag(Ⅰ)center features a tetrahedral geometry,coordinated by one phospho-rus atom of diphosphene 1 and three chloro atoms of two CH2Cl molecules.展开更多
基金the National Key R&D Program of China(Grant 2018YFA0306004)the National Natural Science Foundation of China(Grant 21525102)for financial support.
文摘A Ni(Ⅱ)coordination complex 1 with a novel boron-oxamido radical ligand was synthesized and isolated.Reactions of 1 with N,N-dimethyl-4-pyridinamine(DMAP)and 4,4'-bpy resulted in 2 and 3,respectively,accompanied by the spin state transition from S=1/2 to S=3/2.Both 2 and 3 were isolated as stable crystals and characterized to feature an S=3/2 spin state,with the S=1 Ni(Ⅱ)atoms ferromagnetically coupled with the ligand-centred radicals,by SQUID measurement and EPR spectroscopy.Complex 3 represents the first example of one-dimensional magnetic chain constructed by S=3/2 Ni(Ⅱ)-radical units.
基金the National Key R&D Program of China(Grants Nos.2016YFA0300404 and 2018YFA0306004,X.W.)the National Natural Science Foundation of China(Grants No.21525102 and 21690062 X.W.,Grants No.22033007 J.J.)for financial support.The calculations were performed at the High-Performance Computing Center of Nanjing University and the Supercomputing Center of University of Science and Technology of China.
文摘It is highly urgent to develop synthetic strategies to make new category of stable luminescent radicals with desired emission wavelength.In this study,we have isolated two dioxoborocyclic radicals(3 and 4)by a direct synthetic route.They were characterized by UV,EPR spectroscopy and SQUID measurements.Their structures were obtained by single-crystal X-ray diffraction.Both radicals produce blue-photoluminescence(458 nm for 3 and 478 nm for 4)by radiative decay from higher excited states(D_(2)/D_(3))to the ground state(D_(0))based on theoretical calculation,breaking Kasha rule.The work records a new kind of radical emitters and the first stable radicals with blue emission bands.
基金financial support from the National Natural Science Foundation of China(Grants 21690062,X.W.,22001184,Y.S.)the National Key R&D program of China(Grant 2018YFA0306004,X.W.)+1 种基金the National Science Foundation of Jiangsu Province(Grant BK20200849)the National Science Foundation of Jiangsu Higher Education Institutions of China(Grant 20KJB150002,Y.S.)。
文摘Phenalenyl derivatives have been of tremendous interest due to their reversible dimerization in response to the external stimuli such as temperature.However,most of PLY derivatives only show the reversibility dependent on temperature.Herein,we report a unique PLY-based radical anionic salt with reversibleσ-dimerization controlled by solvent rather than temperature.The structure and reversibility of this PLY anion system have been spectroscopically,crystallographically,and theoretically investigated.The molecule exists mainly as theσ-dimer form of K2[σ-12]in toluene,while it can be broken into the monomeric radical anion 1•–by re-dissolving in THF.Moreover,when THF is replaced with toluene,radical 1•–could beσ-dimerized back again.Theoretical calculations reveal that the potassium ions are necessary for the formation of theσ-dimer and the solvent polarity controls theσ-dimerization by regulating the presence of K+.
基金We thank the National Key R&D Progrgm of China(Grants 2016YFA0300404 and 2018YFA0306004,X.W.),the National Nat-ural Science Foundation of China(Grants 21525102 and 21690062,X.W,21601082,G.I.),and the Fundamental Research Funds for the Central Universities(14380191,X.W.and 14380194,G.T.)for financial support.L.Z.would like to thank the financial support from Guangxi University of Science and Technology(Nos.03190227 and 03190228).The calculations were performed at the High-Performance Computing Center of Nanjing University.
文摘Summary of main observation and conclusion The coordination of silver cation to dlphosphene Mes"P=PMes"(1,Mes*=tBu3C6H2)was investigated in detail.The reaction of 1 with Ag(Al(ORF)4)(ORF=OC[CF3]3)in the ratios of 2:1,3:2 and 1:2 led to the formation of the first cationic silver linked diphos-phene complexes 2-4.Complexes 2 and 3 contain two and three diphosphene molecules linked by the linear Ag(Ⅰ)cation,respectively,and they feature unusual zig-ag topologies.Complex 4 is a dinuclear silver complex,and each Ag(Ⅰ)center features a tetrahedral geometry,coordinated by one phospho-rus atom of diphosphene 1 and three chloro atoms of two CH2Cl molecules.
