Ordered polyiodide networks have recently gathered considerable attention as electronic materials,a topic historically dominated by metals.Could we incorporate metal cations into polyiodide frameworks in a controlled ...Ordered polyiodide networks have recently gathered considerable attention as electronic materials,a topic historically dominated by metals.Could we incorporate metal cations into polyiodide frameworks in a controlled manner to simultaneously boost electronic properties and robustness of these materials?Herein we present a first principles study featuring three analogous polyazacyclophanes(L,L-Me,L-Me_(3)),differing only in the extent of N-methylation.We demonstrate(potentiometry,ITC)how they all form the same CuL^(2+)(L=L,L-Me,L-Me_(3))complex as prevalent species in solution,so that a level playing field exists where only N-methylation distinguishes them.Then we use them as countercations for polyiodide growth.XRD analysis of the resulting crystals clearly shows that methylation is a valuable tool to gradually shift directional control of subtending pairing preferences from H-bond to I…I interactions:this affects global packing and actively incorporates metal centres into polyiodide chains,setting the scene for further developments.展开更多
In photomagnetic materials,changes in the molecular structure or electron distribution caused by light illumination may result in changes in magnetism,enabling regulation of the magnetic behavior of materials.Herein w...In photomagnetic materials,changes in the molecular structure or electron distribution caused by light illumination may result in changes in magnetism,enabling regulation of the magnetic behavior of materials.Herein we report a 1,8-dihydroxyanthraquinone-based hexanuclear dysprosium cluster[Dy_(6)O_(2)(L^(1))_(6)(OCH_(3))_(2)(CH_(3)OH)_(2)(DMSO)_(4)]·DMSO·CH_(3)OH(1)obtained from the solvothermal reaction of Dy(OAc)_(3)·5H_(2)O with 1,8-dihydroxyanthraquinone(H_(2)L^(1)).The six Dy_((III))ions in 1 are linked by twoμ_(4)-O,twoμ_(3)-O and tenμ_(2)-O atoms to construct a rare bicapped tetrahedral Dy_(6) skeleton.Magnetic tests showed that the cluster is a single molecule magnet(SMM)under zero field.Upon light irradiation,the terminally coordinated CH_(3)OH molecules in 1 were partly substituted by lattice DMSO molecules with the SMM performance being significantly tuned by this subtle structural variation.Single molecule magnets with such photomagnetic behavior are rarely reported.展开更多
基金supported by the Spanish MINECO and the FEDER and COST from the European Union(CTQ2016-78499-C6-1-R,CTQ2017-90852-REDC,Unidad de Excelencia María de Maeztu CEX2019-000919-N and NECTAR CA18202 COST Action)A.M.-C.wants to thank Spanish Ministry of Science,Research and Universities for the PhD grants FPU14/05098 and EST17/00666.
文摘Ordered polyiodide networks have recently gathered considerable attention as electronic materials,a topic historically dominated by metals.Could we incorporate metal cations into polyiodide frameworks in a controlled manner to simultaneously boost electronic properties and robustness of these materials?Herein we present a first principles study featuring three analogous polyazacyclophanes(L,L-Me,L-Me_(3)),differing only in the extent of N-methylation.We demonstrate(potentiometry,ITC)how they all form the same CuL^(2+)(L=L,L-Me,L-Me_(3))complex as prevalent species in solution,so that a level playing field exists where only N-methylation distinguishes them.Then we use them as countercations for polyiodide growth.XRD analysis of the resulting crystals clearly shows that methylation is a valuable tool to gradually shift directional control of subtending pairing preferences from H-bond to I…I interactions:this affects global packing and actively incorporates metal centres into polyiodide chains,setting the scene for further developments.
基金supported by the National Natural Science Foundation of China(No.12064002,22261007 and 22361005)the Guangxi Technology Base and Talent Subject(grant no.GUIKE AD23026067).
文摘In photomagnetic materials,changes in the molecular structure or electron distribution caused by light illumination may result in changes in magnetism,enabling regulation of the magnetic behavior of materials.Herein we report a 1,8-dihydroxyanthraquinone-based hexanuclear dysprosium cluster[Dy_(6)O_(2)(L^(1))_(6)(OCH_(3))_(2)(CH_(3)OH)_(2)(DMSO)_(4)]·DMSO·CH_(3)OH(1)obtained from the solvothermal reaction of Dy(OAc)_(3)·5H_(2)O with 1,8-dihydroxyanthraquinone(H_(2)L^(1)).The six Dy_((III))ions in 1 are linked by twoμ_(4)-O,twoμ_(3)-O and tenμ_(2)-O atoms to construct a rare bicapped tetrahedral Dy_(6) skeleton.Magnetic tests showed that the cluster is a single molecule magnet(SMM)under zero field.Upon light irradiation,the terminally coordinated CH_(3)OH molecules in 1 were partly substituted by lattice DMSO molecules with the SMM performance being significantly tuned by this subtle structural variation.Single molecule magnets with such photomagnetic behavior are rarely reported.
