Lanthanide single-molecule magnets(Ln-SMMs)have attracted scientific attention due to their potential application in data storage and spintronics.On the other hand,stimuli-responsive molecular materials are considered...Lanthanide single-molecule magnets(Ln-SMMs)have attracted scientific attention due to their potential application in data storage and spintronics.On the other hand,stimuli-responsive molecular materials are considered for chemical sensors thanks to their solvato-and vapochromism.Aiming at advanced multifunctionality,the Ln-SMMs can be functionalized toward various physical properties,e.g.,luminescence or ferroelectricity.We present an approach toward the conjunction of molecular nanomagnetism with solvatochromism in solution and vapochromism in the solid state.Our concept is based on combining Dy^(III)complexes bearing O-donor ligands,i.e.,4-pyridone(4-pyone),responsible for the SMM property,with dicyanido-bis(1,10-phenanthroline)iron(II)metalloligands inducing a chemochromic response.We report tetranuclear molecules,{[Dy^(III)(4-pyone)_(5)]_(2)[Fe^(II)(CN)_(2)(phen)_(2)]_(2)}(CF_(3)SO_(3))_(6)(1)containing(4-pyone)-bridged{Dy^(III)2}6+units which exhibit pronounced SMM characteristics due to the axial alignment of 4-pyone ligands within a pentagonal bipyramidal geometry and the weakening of quantum tunneling of magnetization(QTM)achieved by ligand-mediated exchange coupling.The{Dy^(III)_(2)}SMMs are cyanidobridged to Fe^(II)complexes and the resulting{Dy^(III)2 Fe^(II)_(2)}^(6+)cations could be dissolved in various solvents providing distinct solvatochromism achieved by tunable charge-transfer absorption of dicyanidometallates.The optical sensitivity of 1 to solvent molecules was also found in the solid state unveiling efficient vapochromism related to the incorporation of solvent vapors into the crystals of 1.The variously solvated phases of 1 were isolated from alcohol solutions giving a series of compounds,namely 1·MeOH,1·EtOH,1·PrOH,and 1·BuOH,differing not only in light absorption but also in SMM features,including the level of quenching of the QTM.展开更多
The first simultaneous redox and solvato-magnetic switching was achieved.The dinuclear complex[Dy_(2)(hfac)_(6)(H_(2)SQ)]·CH_(2)Cl_(2)(Dy_(2)H_(2)SQ)(where hfac=1,1,1,5,5,5-hexafluoroacetylacetonate and H_(2)SQ=...The first simultaneous redox and solvato-magnetic switching was achieved.The dinuclear complex[Dy_(2)(hfac)_(6)(H_(2)SQ)]·CH_(2)Cl_(2)(Dy_(2)H_(2)SQ)(where hfac=1,1,1,5,5,5-hexafluoroacetylacetonate and H_(2)SQ=2,2’-benzene-1,4-diylbis(6-hydroxy-4,7-di-tert-butyl-1,3-benzodithiol-2-ylium-5-olate)was reversibly oxidized into the dinuclear complex[Dy_(2)(hfac)_(6)(H_(2)O)_(2)(Q)](Dy_(2)Q)(where Q=2,2’-cyclohexa-2,5-diene-1,4-diylidenebis(4,7-di-tert-butyl-1,3-benzodithiole-5,6-dione))inducing the reversible coordination of water molecules to the DyIII ion.Magnetic susceptibility measurements and ab initio CASSCF/SI-SO calculations,confirmed by Cantilever Torque Magnetometry measurements,demonstrated that Dy_(2)H_(2)SQ is a Single-Molecule Magnet with a magnetic relaxation 7000 times slower than Dy_(2)Q(at 3 K)allowing a“ON-OFF”switching of the magnetic bistability.展开更多
Water-soluble N,N-dimethyl[60]fulleropyrro-lidinium iodide (C60(C4H10N+)I-), when dissolved in binarymixtures of tetrahydrofuran and water, was found to exhibit remarkable solvatochromism. Correspondingly, the UV-vis ...Water-soluble N,N-dimethyl[60]fulleropyrro-lidinium iodide (C60(C4H10N+)I-), when dissolved in binarymixtures of tetrahydrofuran and water, was found to exhibit remarkable solvatochromism. Correspondingly, the UV-vis spectra showed obvious changes by variation of the solventcomposition of tetrahydrofuran and water. It was found that both concentration and temperature had strong influence on the stability of monomer-state C60(C4H10N+)I-, while theyhad little effect on the stability of aggregated C60(C4H10N+) I-The formation of cluster was confirmed by TEM and AFMmeasurements.展开更多
基金financed by the National Science Center of Poland,the OPUS-21 project(2021/41/B/ST5/02544)。
文摘Lanthanide single-molecule magnets(Ln-SMMs)have attracted scientific attention due to their potential application in data storage and spintronics.On the other hand,stimuli-responsive molecular materials are considered for chemical sensors thanks to their solvato-and vapochromism.Aiming at advanced multifunctionality,the Ln-SMMs can be functionalized toward various physical properties,e.g.,luminescence or ferroelectricity.We present an approach toward the conjunction of molecular nanomagnetism with solvatochromism in solution and vapochromism in the solid state.Our concept is based on combining Dy^(III)complexes bearing O-donor ligands,i.e.,4-pyridone(4-pyone),responsible for the SMM property,with dicyanido-bis(1,10-phenanthroline)iron(II)metalloligands inducing a chemochromic response.We report tetranuclear molecules,{[Dy^(III)(4-pyone)_(5)]_(2)[Fe^(II)(CN)_(2)(phen)_(2)]_(2)}(CF_(3)SO_(3))_(6)(1)containing(4-pyone)-bridged{Dy^(III)2}6+units which exhibit pronounced SMM characteristics due to the axial alignment of 4-pyone ligands within a pentagonal bipyramidal geometry and the weakening of quantum tunneling of magnetization(QTM)achieved by ligand-mediated exchange coupling.The{Dy^(III)_(2)}SMMs are cyanidobridged to Fe^(II)complexes and the resulting{Dy^(III)2 Fe^(II)_(2)}^(6+)cations could be dissolved in various solvents providing distinct solvatochromism achieved by tunable charge-transfer absorption of dicyanidometallates.The optical sensitivity of 1 to solvent molecules was also found in the solid state unveiling efficient vapochromism related to the incorporation of solvent vapors into the crystals of 1.The variously solvated phases of 1 were isolated from alcohol solutions giving a series of compounds,namely 1·MeOH,1·EtOH,1·PrOH,and 1·BuOH,differing not only in light absorption but also in SMM features,including the level of quenching of the QTM.
基金supported by the CNRS,Universitéde Rennes 1,Agence Nationale de la Recherche(no.ANR-13-BS07-0022-01)France-Russia MULTISWITCH PRC Grant(no.227606)+2 种基金the European Commission through the ERC-CoG 725184 MULTIPROSMM(project no.725184)the Russian Foundation for Basic Research(grant 19-53-15007 NCNI_a)the French GENCI/IDRIS-CINES centres for high-performance computing resources.V.K.and V.C.thank“Analytical Center IOMC RAS”and Russian Federal Program for development of science and technology for 2014-2020(project identifier is RFMEFI62120X0040).
文摘The first simultaneous redox and solvato-magnetic switching was achieved.The dinuclear complex[Dy_(2)(hfac)_(6)(H_(2)SQ)]·CH_(2)Cl_(2)(Dy_(2)H_(2)SQ)(where hfac=1,1,1,5,5,5-hexafluoroacetylacetonate and H_(2)SQ=2,2’-benzene-1,4-diylbis(6-hydroxy-4,7-di-tert-butyl-1,3-benzodithiol-2-ylium-5-olate)was reversibly oxidized into the dinuclear complex[Dy_(2)(hfac)_(6)(H_(2)O)_(2)(Q)](Dy_(2)Q)(where Q=2,2’-cyclohexa-2,5-diene-1,4-diylidenebis(4,7-di-tert-butyl-1,3-benzodithiole-5,6-dione))inducing the reversible coordination of water molecules to the DyIII ion.Magnetic susceptibility measurements and ab initio CASSCF/SI-SO calculations,confirmed by Cantilever Torque Magnetometry measurements,demonstrated that Dy_(2)H_(2)SQ is a Single-Molecule Magnet with a magnetic relaxation 7000 times slower than Dy_(2)Q(at 3 K)allowing a“ON-OFF”switching of the magnetic bistability.
文摘Water-soluble N,N-dimethyl[60]fulleropyrro-lidinium iodide (C60(C4H10N+)I-), when dissolved in binarymixtures of tetrahydrofuran and water, was found to exhibit remarkable solvatochromism. Correspondingly, the UV-vis spectra showed obvious changes by variation of the solventcomposition of tetrahydrofuran and water. It was found that both concentration and temperature had strong influence on the stability of monomer-state C60(C4H10N+)I-, while theyhad little effect on the stability of aggregated C60(C4H10N+) I-The formation of cluster was confirmed by TEM and AFMmeasurements.
