The crystal engineering of octacyanidomolybdate(Ⅳ)ions and copper(Ⅱ)complexes with two types of chelating ligands:multidentate blocking ligand,tren=(tris(2 aminoethyl)amine),and bidentate ligand capable of forming u...The crystal engineering of octacyanidomolybdate(Ⅳ)ions and copper(Ⅱ)complexes with two types of chelating ligands:multidentate blocking ligand,tren=(tris(2 aminoethyl)amine),and bidentate ligand capable of forming unusual organic bridges,tn=1,3-diaminopropane,resulted in the formation of{[Cu(tren)]2(μ-tn)}·[Mo(CN)8]·7.5H2O(1)and{[Cu(tren)]2(μ-tn)}·[Mo(CN)8]·{[Cu(tren)]2[Mo(CN)8]}·9H2O(2).The crystal structure of 1 comprises isolated anions[Mo(CN)8]4-wrapped with charge-compensating units{[Cu(tren)]2(μ-tn)}^(4+)stabilised by extensive H-bond networks.Compound 2 forms alternating layers consisting of the same ions as 1 and neutral cyanido-bridged V-shaped trinuclear molecules{[Cu(tren)]2[Mo(CN)8]}.Additionally,two previously reported V-shaped trinuclear reference systems were synthesised:[Cu(tn)2]2[Mo(CN)_(8)]·2H_(2)O(3)and[Cu(tren)]2[Mo(CN)8]·5.25H2O(4).UV–Vis–NIR absorption spectroscopy,supported by quantum chemical calculations(DFT and TD-DFT),confirmed the presence of Mo(Ⅳ)to Cu(Ⅱ)charge transfer bands centred on trinuclear molecules(2–4)and their absence for the ionic sample 1 without CN^(-)-bridges.Additionally,detailed descriptions of the energy level diagrams of 1–4 with the frontier molecular orbitals and possible optical transitions were made.Magnetic studies indicated paramagnetic behaviour with weak antiferromagnetic interactions at low temperature.Finally,photomagnetic studies of 1–3 showed the increase of magnetization after irradiation with 473 and 410 nm light at 10 K.Comparative analysis of all data suggests that the photomagnetic effect in 1 is well described by the lightinduced excited spin-state trapping(LIESST)effect in the Mo(Ⅳ)centre,while other cyanido-bridged compounds prefer the metal-to-metal charge transfer with minor contribution of LIESST effects.展开更多
Molecular materials are playing a pivotal role in the advancement of prospective THz technologies.Herein,we have prepared nine isostructural coordination complexes of general formula[Ln^(Ⅲ)(H_(2)O)_(3)][AgI(CN)_(2)]_...Molecular materials are playing a pivotal role in the advancement of prospective THz technologies.Herein,we have prepared nine isostructural coordination complexes of general formula[Ln^(Ⅲ)(H_(2)O)_(3)][AgI(CN)_(2)]_(3)(LnAg,Ln=La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,and Dy).Vibrational spectroscopy has unveiled gradual changes in theν(CuN)stretching frequencies within both infrared(IR)and Raman spectra from LaAg to DyAg,stemming from incremental alterations in crystallographic unit cell parameters and volumes.Similarly,the THz spectra manifest pronounced absorption signals between 1.0 to 1.2 THz,which can be judiciously tuned by varying lanthanide(^(Ⅲ))ion and measurement temperature.Ab initio density-functional theory(DFT)calculations of THz spectra elucidate the primary contribution from opposite translational vibrations of Ag atoms and O atoms from H_(2)O around Ln(^(Ⅲ))atoms.Furthermore,thin films of LnAg can achieve a large return loss in a broad bandwidth in impedance-matching simulations.展开更多
Thermal desolvation is a very attractive method for the post-synthetic modification of the physicochemical properties of switchable materials.In this field of research,special attention has been paid to the possibilit...Thermal desolvation is a very attractive method for the post-synthetic modification of the physicochemical properties of switchable materials.In this field of research,special attention has been paid to the possibility of modifying the thermo-and photo-induced spin crossover(SCO)properties of metal complexes as they can act as solvent sensors.Two new[Fe(3-bpp)_(2)](ClO_(4))_(2)·2.5H_(2)O·MeOH(1·sol)and[Fe(3-bpp)_(2)](ReO_(4))_(2)·3H_(2)O(_(2)·sol)compounds.展开更多
基金supported in part by a JSPS Grant-in-Aid for Scientific Research(A)(Grant Number JP20H00369)a Grantin-Aid for Scientific Research on Innovative Area Soft Crystals(Area No.2903,JP17H06367)+4 种基金Grant-in-Aid for Specially Promoted Research(Grant Number JP15H05697)IM–LED LIA(CNRS)and CNRS-University of Tokyo“Excellence Science”Joint Research ProgramWe also acknowledge the Cryogenic Research Center,The University of Tokyo,the Center for Nano Lithography&Analysis,The University of Tokyo supported by MEXT,and the MEXT Quantum Leap Flagship Program(Grant Number JPMXS0118068681)for supportK.K.is grateful for a Grant in-Aid for JSPS fellows(Grant Number JP20J20245)O.S.is grateful for JSPS KAKENHI Grant Number JP21K14582.
文摘The crystal engineering of octacyanidomolybdate(Ⅳ)ions and copper(Ⅱ)complexes with two types of chelating ligands:multidentate blocking ligand,tren=(tris(2 aminoethyl)amine),and bidentate ligand capable of forming unusual organic bridges,tn=1,3-diaminopropane,resulted in the formation of{[Cu(tren)]2(μ-tn)}·[Mo(CN)8]·7.5H2O(1)and{[Cu(tren)]2(μ-tn)}·[Mo(CN)8]·{[Cu(tren)]2[Mo(CN)8]}·9H2O(2).The crystal structure of 1 comprises isolated anions[Mo(CN)8]4-wrapped with charge-compensating units{[Cu(tren)]2(μ-tn)}^(4+)stabilised by extensive H-bond networks.Compound 2 forms alternating layers consisting of the same ions as 1 and neutral cyanido-bridged V-shaped trinuclear molecules{[Cu(tren)]2[Mo(CN)8]}.Additionally,two previously reported V-shaped trinuclear reference systems were synthesised:[Cu(tn)2]2[Mo(CN)_(8)]·2H_(2)O(3)and[Cu(tren)]2[Mo(CN)8]·5.25H2O(4).UV–Vis–NIR absorption spectroscopy,supported by quantum chemical calculations(DFT and TD-DFT),confirmed the presence of Mo(Ⅳ)to Cu(Ⅱ)charge transfer bands centred on trinuclear molecules(2–4)and their absence for the ionic sample 1 without CN^(-)-bridges.Additionally,detailed descriptions of the energy level diagrams of 1–4 with the frontier molecular orbitals and possible optical transitions were made.Magnetic studies indicated paramagnetic behaviour with weak antiferromagnetic interactions at low temperature.Finally,photomagnetic studies of 1–3 showed the increase of magnetization after irradiation with 473 and 410 nm light at 10 K.Comparative analysis of all data suggests that the photomagnetic effect in 1 is well described by the lightinduced excited spin-state trapping(LIESST)effect in the Mo(Ⅳ)centre,while other cyanido-bridged compounds prefer the metal-to-metal charge transfer with minor contribution of LIESST effects.
基金financed in part by a JSPS Grant-in-Aid for Scientific Research(A)(Grant Number 20H00369),IRL DYNACOM(CNRS),the CNRS-University of Tokyo“Excellence Science”Joint Research Program,and the Second CNRS-University of Tokyo PhD Joint ProgramThe authors acknowledge the Cryogenic Research Center,The University of Tokyo,the Center for Nano Lithography&Analysis,The University of Tokyo supported by MEXT,and the MEXT Quantum Leap Flagship Program(Grant Number JPMXS0118068681)for the support.G.L.is grateful to JSPS KAKENHI(Grant Number 23KJ0736)+4 种基金O.S.is thankful to JSPS KAKENHI(Grant Number 21K14582)K.K.acknowledges a Grant-in-Aid for JSPS fellows(Grant Number 23K19238)Y.M.and L.W.thank the JST SPRING(Grant Number JPMJSP2108)K.N.recognizes the Iketani Science and Technology Foundation(Grant Number 0351111-A)M.Y.is grateful to JSPS Grant-in-Aid for Young Scientists(Grant Number JP24K17606)。
文摘Molecular materials are playing a pivotal role in the advancement of prospective THz technologies.Herein,we have prepared nine isostructural coordination complexes of general formula[Ln^(Ⅲ)(H_(2)O)_(3)][AgI(CN)_(2)]_(3)(LnAg,Ln=La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,and Dy).Vibrational spectroscopy has unveiled gradual changes in theν(CuN)stretching frequencies within both infrared(IR)and Raman spectra from LaAg to DyAg,stemming from incremental alterations in crystallographic unit cell parameters and volumes.Similarly,the THz spectra manifest pronounced absorption signals between 1.0 to 1.2 THz,which can be judiciously tuned by varying lanthanide(^(Ⅲ))ion and measurement temperature.Ab initio density-functional theory(DFT)calculations of THz spectra elucidate the primary contribution from opposite translational vibrations of Ag atoms and O atoms from H_(2)O around Ln(^(Ⅲ))atoms.Furthermore,thin films of LnAg can achieve a large return loss in a broad bandwidth in impedance-matching simulations.
基金supported by several sources:the CNRS,the University of Bordeaux,the“Agence Nationale de la Recherche”(ANR project BISTA-MAT:ANR-12-BS07-0030-01 ANR project FEMTOMAT:ANR-13-BS04-0002)the“Region Nouvelle Aquitaine”,a JSPS Grant-in-Aid for Specially Promoted Research(Grant Number JP15H05697)+5 种基金a Grant-inAid for Scientific Research on Innovative Area Soft Crystals(Area No.2903,JP17H06367)a Grant-in-Aid for Scientific Research(A)(Grant Number JP20H00369)IM-LED LIA(CNRS)and the Algerian General Directorate of Scientific Research and Technological Development(DGRSDT)We acknowledge the Cryogenic Research Center,The University of Tokyo,the Center for Nano Lithography&Analysis,The University of Tokyo supported by MEXT,and the MEXT Quantum Leap Flagship Program(MEXT Q-LEAP)(JPMXS0118068681)K.K.is grateful to a Grant in-Aid for JSPS fellows(Grant Number JP20J20245)O.S.is thankful for JSPS KAKENHI Grant Number JP21K14582。
文摘Thermal desolvation is a very attractive method for the post-synthetic modification of the physicochemical properties of switchable materials.In this field of research,special attention has been paid to the possibility of modifying the thermo-and photo-induced spin crossover(SCO)properties of metal complexes as they can act as solvent sensors.Two new[Fe(3-bpp)_(2)](ClO_(4))_(2)·2.5H_(2)O·MeOH(1·sol)and[Fe(3-bpp)_(2)](ReO_(4))_(2)·3H_(2)O(_(2)·sol)compounds.
