Correction for‘Anion-driven tetrel bond-induced engineering of lead(Ⅱ)architectures with N’-(1-(2-pyridyl)ethylidene)nicotinohydrazide:experimental and theoretical findings’by Ghodrat Mahmoudi et al.,Inorg.Chem.Fr...Correction for‘Anion-driven tetrel bond-induced engineering of lead(Ⅱ)architectures with N’-(1-(2-pyridyl)ethylidene)nicotinohydrazide:experimental and theoretical findings’by Ghodrat Mahmoudi et al.,Inorg.Chem.Front.,2017,4,171-182,https://doi.org/10.1039/C6QI00477F.展开更多
The evaluation of N’-(1-(2-pyridyl)ethylidene)nicotinohydrazide(HL)as a linker for the Pb^(II)tagged extended structures is described.The reaction of Pb(ClO_(4))_(2)or Pb(OAc)_(2)with HL in MeOH at 60℃and room tempe...The evaluation of N’-(1-(2-pyridyl)ethylidene)nicotinohydrazide(HL)as a linker for the Pb^(II)tagged extended structures is described.The reaction of Pb(ClO_(4))_(2)or Pb(OAc)_(2)with HL in MeOH at 60℃and room temperature,respectively,leads to heteroleptic complexes{[PbL]ClO_(4)}n·nH_(2)O and[PbL(OAc)]_(2),while the same reaction of Pb(ClO_(4))_(2)with HL at 60℃in the presence of two equivalents of NaOAc or NaNO_(2)leads to heteroleptic complexes{[Pb(HL)(OAc)]ClO_(4)}_(n)and[PbL(NO_(2))]n,respectively.Using Pb(NO_(3))_(2)as a source of Pb^(II)in the same reaction with HL and two equivalents of NaN_(3)or NaNCS at room temperature yields[PbLN_(3)]_(n)and[Pb_(2)(HL)_(2)(NO_(3))_(2)(NCS)_(2)],respectively.The room temperature reaction of Pb(NO_(3))_(2)with HL in the presence of two equivalents of NaClO_(4)leads to the transformation of the parent ligand to its perchlorate salt[H_(2)L]ClO_(4).In all the obtained Pb^(II)structures,HL or its deprotonated form L acts both as a chelating and a bridging ligand.The nature of the inorganic anion also influences the final structure.In all complexes the Pb^(II)center exhibits a hemidirected coordination geometry with all the covalent bonds being concentrated on one hemisphere of the coordination sphere with the closest approach of two atoms on the other side varying from 151°to 232°.The sterically available Pb^(II)ion participates in tetrel bonding as evidenced from the detailed structural analysis of the described complexes.As a result of tetrel bonding,the structures of all the six compounds can be extended to a higher dimensional framework,which is further stabilized byπ…πstacking interactions between the aromatic rings.The DFT based charge and energy decomposition(ETS-NOCV)calculations are performed in order to shed light on the nature of non-covalent interactions that determine the stability of the obtained structures.展开更多
Four pairs of homochiral Dy_(2)complexes were directionally prepared using homochiralβ-diketone ligands{D-Htfc/L-Htfc=(+)/(−)-3-trifluoroacetyl camphor,D-Hpfc/L-Hpfc=3-(perfluorobutyryl)-(+)/(−)-camphor}and hydrazone...Four pairs of homochiral Dy_(2)complexes were directionally prepared using homochiralβ-diketone ligands{D-Htfc/L-Htfc=(+)/(−)-3-trifluoroacetyl camphor,D-Hpfc/L-Hpfc=3-(perfluorobutyryl)-(+)/(−)-camphor}and hydrazone Schiff base bridging ligands{H_(2)L1=(E)-N’-(2-hydroxy-3-methoxybenzylidene)pyrazine-2-carbohydrazide,H_(2)L2=(E)-N’-(2-hydroxy-3-methoxybenzylidene)nicotinohydrazide}at room temperature:[Dy_(2)(D-tfc/L-tfc)_(2)(L1)_(2)(H_(2)O)_(2)]·2DMF(D-1/L-1),[Dy_(2)(D-tfc/L-tfc)_(2)(L2)_(2)(H_(2)O)_(2)]·2DMF(D-2/L-2),[Dy_(2)(D-pfc/L-pfc)_(2)(L1)_(2)(DMF)_(2)](D-3/L-3),and[Dy_(2)(D-pfc/L-pfc)_(2)(L2)_(2)(H_(2)O)_(2)]·2DMF(D-4/L-4).These enantiomers show intramolecular ferromagnetic interactions between Dy^(3+)ions and exhibit good single-molecule magnet(SMM)properties at a zero dc field,with Ueff/k values of 47.6 K,152.2 K,173.8 K and 116.2 K for D-1,D-2,D-3 and D-4,respectively.These magnetic properties were explained with ab initio calculations.The magnetic circular dichroism(MCD)investigation revealed that these four pairs of enantiomers have strong magneto-optical Faraday effects.Besides the second harmonic generation(SHG),they exhibit surprisingly strong third harmonic generation(THG).Notably,the magnetic properties,magneto-optical properties and nonlinear optical properties of such homochiral SMMs can be adjusted by the functional groups on the ligands.Among them,D-1/L-1 has the potential for applications in magneto-optical and/or nonlinear optical materials or devices due to its strongest THG intensity(661.8×α-SiO_(2))and strongest magneto-optical Faraday effect.展开更多
文摘Correction for‘Anion-driven tetrel bond-induced engineering of lead(Ⅱ)architectures with N’-(1-(2-pyridyl)ethylidene)nicotinohydrazide:experimental and theoretical findings’by Ghodrat Mahmoudi et al.,Inorg.Chem.Front.,2017,4,171-182,https://doi.org/10.1039/C6QI00477F.
基金the PL-Grid Infrastructure and resources provided by the ACC Cyfronet AGH(Cracow,Poland).
文摘The evaluation of N’-(1-(2-pyridyl)ethylidene)nicotinohydrazide(HL)as a linker for the Pb^(II)tagged extended structures is described.The reaction of Pb(ClO_(4))_(2)or Pb(OAc)_(2)with HL in MeOH at 60℃and room temperature,respectively,leads to heteroleptic complexes{[PbL]ClO_(4)}n·nH_(2)O and[PbL(OAc)]_(2),while the same reaction of Pb(ClO_(4))_(2)with HL at 60℃in the presence of two equivalents of NaOAc or NaNO_(2)leads to heteroleptic complexes{[Pb(HL)(OAc)]ClO_(4)}_(n)and[PbL(NO_(2))]n,respectively.Using Pb(NO_(3))_(2)as a source of Pb^(II)in the same reaction with HL and two equivalents of NaN_(3)or NaNCS at room temperature yields[PbLN_(3)]_(n)and[Pb_(2)(HL)_(2)(NO_(3))_(2)(NCS)_(2)],respectively.The room temperature reaction of Pb(NO_(3))_(2)with HL in the presence of two equivalents of NaClO_(4)leads to the transformation of the parent ligand to its perchlorate salt[H_(2)L]ClO_(4).In all the obtained Pb^(II)structures,HL or its deprotonated form L acts both as a chelating and a bridging ligand.The nature of the inorganic anion also influences the final structure.In all complexes the Pb^(II)center exhibits a hemidirected coordination geometry with all the covalent bonds being concentrated on one hemisphere of the coordination sphere with the closest approach of two atoms on the other side varying from 151°to 232°.The sterically available Pb^(II)ion participates in tetrel bonding as evidenced from the detailed structural analysis of the described complexes.As a result of tetrel bonding,the structures of all the six compounds can be extended to a higher dimensional framework,which is further stabilized byπ…πstacking interactions between the aromatic rings.The DFT based charge and energy decomposition(ETS-NOCV)calculations are performed in order to shed light on the nature of non-covalent interactions that determine the stability of the obtained structures.
基金generously funded by the National Natural Science Foundation of China(Grant Numbers 22271289,21871274 and 22131003).
文摘Four pairs of homochiral Dy_(2)complexes were directionally prepared using homochiralβ-diketone ligands{D-Htfc/L-Htfc=(+)/(−)-3-trifluoroacetyl camphor,D-Hpfc/L-Hpfc=3-(perfluorobutyryl)-(+)/(−)-camphor}and hydrazone Schiff base bridging ligands{H_(2)L1=(E)-N’-(2-hydroxy-3-methoxybenzylidene)pyrazine-2-carbohydrazide,H_(2)L2=(E)-N’-(2-hydroxy-3-methoxybenzylidene)nicotinohydrazide}at room temperature:[Dy_(2)(D-tfc/L-tfc)_(2)(L1)_(2)(H_(2)O)_(2)]·2DMF(D-1/L-1),[Dy_(2)(D-tfc/L-tfc)_(2)(L2)_(2)(H_(2)O)_(2)]·2DMF(D-2/L-2),[Dy_(2)(D-pfc/L-pfc)_(2)(L1)_(2)(DMF)_(2)](D-3/L-3),and[Dy_(2)(D-pfc/L-pfc)_(2)(L2)_(2)(H_(2)O)_(2)]·2DMF(D-4/L-4).These enantiomers show intramolecular ferromagnetic interactions between Dy^(3+)ions and exhibit good single-molecule magnet(SMM)properties at a zero dc field,with Ueff/k values of 47.6 K,152.2 K,173.8 K and 116.2 K for D-1,D-2,D-3 and D-4,respectively.These magnetic properties were explained with ab initio calculations.The magnetic circular dichroism(MCD)investigation revealed that these four pairs of enantiomers have strong magneto-optical Faraday effects.Besides the second harmonic generation(SHG),they exhibit surprisingly strong third harmonic generation(THG).Notably,the magnetic properties,magneto-optical properties and nonlinear optical properties of such homochiral SMMs can be adjusted by the functional groups on the ligands.Among them,D-1/L-1 has the potential for applications in magneto-optical and/or nonlinear optical materials or devices due to its strongest THG intensity(661.8×α-SiO_(2))and strongest magneto-optical Faraday effect.
