We report in this article new magneto-plasmonic core@satellite Prussian Blue Analogue(PBA)@Au-Ag nanoheterostructures obtained by post-synthetic adsorption of a bimetallic[Au^(I)_(2)Ag^(I)_(2)(C_(6)F_(5))_(4)(OEt_(2))...We report in this article new magneto-plasmonic core@satellite Prussian Blue Analogue(PBA)@Au-Ag nanoheterostructures obtained by post-synthetic adsorption of a bimetallic[Au^(I)_(2)Ag^(I)_(2)(C_(6)F_(5))_(4)(OEt_(2))_(2)]_(n)molecular complex with ferromagnetic K^(+)/Ni^(2+)/[Cr(CN)_(6)]^(3-)PBA nanoparticles.While the size,shape and structural integrity of the PBA nanoparticles are preserved upon the formation of the core@satellite heterostructures,a dramatic change in the magnetic properties is observed due to the presence of ultrasmall gold-silver nanosatellites.Moreover,the nanoarchitectures behave also as multicatalysts towards the reduction of 4-nitrophenol with enhanced activity as compared to the pristine K^(+)/Ni^(2+)/[Cr(CN)_(6)]^(3-)PBA.Remarkably,these performances are found to be heightened upon light irradiation due to a plasmon-assisted catalytic effect.Such original PBA core@Au-Ag satellite architectures constitute a rare example in which an interplay between the two constituting materials leads to a reshaping of the magnetic and catalytic features.展开更多
The first air-stable Ln(III)organometallic mixed-ligand sandwich complexes TPPLnCp^(*)(Ln=Y(1),Tb(2),Dy(3),Ho(4),and Er(5))bearing both 5,10,15,20-tetraphenylporphyrinate(TPP)and pentamethylcyclopentadienide(Cp^(*))li...The first air-stable Ln(III)organometallic mixed-ligand sandwich complexes TPPLnCp^(*)(Ln=Y(1),Tb(2),Dy(3),Ho(4),and Er(5))bearing both 5,10,15,20-tetraphenylporphyrinate(TPP)and pentamethylcyclopentadienide(Cp^(*))ligands were synthesized by the reactions of half-sandwich bis(o-N,N-dimethylaminobenzyl)precursors Cp^(*)Ln(CH_(2)C_(6)H_(4)NMe_(2-o))_(2)with equimolar amounts of 5,10,15,20-tetraphenylporphyrin(TPPH2)in toluene at ambient temperature and isolated in 62%–74%yields.X-ray analysis revealed the linear Cnt(Cp^(*))–Ln–Cnt(TPP)geometry with a bond angle close to 180°,a Cnt(Cp^(*))–Ln bond distance ranging from 2.325 to 2.365Åand a Cnt(TPP)–Ln distance ranging from 1.012 to 1.063Å.These complexes demonstrated remarkable thermal and oxidative stability,being sublimable under vacuum above 290°C without decomposition(∼5×10^(−2)Torr).Magnetic studies revealed field-induced single-molecule magnet(SMM)behavior for the Tb^(3+),Dy^(3+),and Er^(3+)derivatives.Theoretical investigations revealed the presence of only moderately axial g tensors,a small splitting within the ground multiplet,and significant mixing between different projections of the total angular momentum,all of which contribute to the disappointing SMM behavior.A quasi-spherical Ln^(3+)coordination environment created by the tetradentate TPP ligand and appreciable orbital interactions of itsπ-conjugated system with the dysprosium 4f orbitals could introduce transverse components to the crystal field.展开更多
Chiral separation is of critical importance in many areas spanning from pharmaceutics and agriculture to catalysis.Coordination polymers and metal-organic frameworks have been envisaged for such a purpose.In this stud...Chiral separation is of critical importance in many areas spanning from pharmaceutics and agriculture to catalysis.Coordination polymers and metal-organic frameworks have been envisaged for such a purpose.In this study,the post-synthetic functionalization of the two-dimensional Hofmann clathrate[Ni(H_(2)O)_(2)][Ni(CN)_(4)]with enantiopure phenylethylamines yielding hydrostable chiral clathrates is reported.展开更多
^(201)Tl-labeled Prussian blue and Au core@Prussian blue shell nanoparticles were synthesised and investigated in vivo as nanoprobes by using SPECT-CT scintigraphy.We demonstrate that the size,morphology and nanoparti...^(201)Tl-labeled Prussian blue and Au core@Prussian blue shell nanoparticles were synthesised and investigated in vivo as nanoprobes by using SPECT-CT scintigraphy.We demonstrate that the size,morphology and nanoparticle coating affect the kinetics of the nanoparticle biodistribution.展开更多
We report a new octahedral[Dy(OCPh_(3))_(2)(THF)_(4)][BPh_(4)]luminescent Single-Molecule Magnet(SMM)exhibiting massive crystal-field splitting and an anisotropic barrier of 1385 cm^(−1).Magnetic measurements combined...We report a new octahedral[Dy(OCPh_(3))_(2)(THF)_(4)][BPh_(4)]luminescent Single-Molecule Magnet(SMM)exhibiting massive crystal-field splitting and an anisotropic barrier of 1385 cm^(−1).Magnetic measurements combined with ab initio analysis reveal a novel mechanism behind the high blocking barrier based on the quenching of one-phonon transitions between the three low-lying crystal-field multiplets due to large energy gaps between them exceeding the available phonon energies and forcing the activated relaxation to proceed through the fourth doublet.The observed nonetheless short relaxation time is due to appreciable non-axial anisotropy,which opens a tunnelling relaxation path via interaction with the nuclear spins.Reducing the equatorial crystal-field quenches drastically the quantum tunnelling of magnetization,allowing for full exploitation of the high blocking barrier of the complex as in the best known SMMs.展开更多
Prussian blue(PB)type nanoparticles belong to an exciting family of molecule-based nanomaterials.They combine the possibility of surface engineering with specific advantages related to their porous molecule-based stru...Prussian blue(PB)type nanoparticles belong to an exciting family of molecule-based nanomaterials.They combine the possibility of surface engineering with specific advantages related to their porous molecule-based structures and their fascinating chemical and physical properties including redox,magnetic,photothermal and host–vip features.In this review,we focus on recent advances in the Post-Synthetic Modification(PSM)of nano-sized PB and its analogues(PBA)and compare them with the current strategies used in Metal–Organic Frameworks(MOF)in order to give the outlooks on the future researches in this domain.展开更多
基金D.G.I.MINECO/FEDER(project number PID2019-104379RB-C22(AEI/FEDER,UE))EC support through the FEDER project NUTRIA(EFA 356/19)。
文摘We report in this article new magneto-plasmonic core@satellite Prussian Blue Analogue(PBA)@Au-Ag nanoheterostructures obtained by post-synthetic adsorption of a bimetallic[Au^(I)_(2)Ag^(I)_(2)(C_(6)F_(5))_(4)(OEt_(2))_(2)]_(n)molecular complex with ferromagnetic K^(+)/Ni^(2+)/[Cr(CN)_(6)]^(3-)PBA nanoparticles.While the size,shape and structural integrity of the PBA nanoparticles are preserved upon the formation of the core@satellite heterostructures,a dramatic change in the magnetic properties is observed due to the presence of ultrasmall gold-silver nanosatellites.Moreover,the nanoarchitectures behave also as multicatalysts towards the reduction of 4-nitrophenol with enhanced activity as compared to the pristine K^(+)/Ni^(2+)/[Cr(CN)_(6)]^(3-)PBA.Remarkably,these performances are found to be heightened upon light irradiation due to a plasmon-assisted catalytic effect.Such original PBA core@Au-Ag satellite architectures constitute a rare example in which an interplay between the two constituting materials leads to a reshaping of the magnetic and catalytic features.
基金support of the Russian Science Foundation is highly acknowledged(Project No.24-13-00275)support from the Ministry of Science and Higher Education of the Russian Federation(Contract No.075-00277-24-00).
文摘The first air-stable Ln(III)organometallic mixed-ligand sandwich complexes TPPLnCp^(*)(Ln=Y(1),Tb(2),Dy(3),Ho(4),and Er(5))bearing both 5,10,15,20-tetraphenylporphyrinate(TPP)and pentamethylcyclopentadienide(Cp^(*))ligands were synthesized by the reactions of half-sandwich bis(o-N,N-dimethylaminobenzyl)precursors Cp^(*)Ln(CH_(2)C_(6)H_(4)NMe_(2-o))_(2)with equimolar amounts of 5,10,15,20-tetraphenylporphyrin(TPPH2)in toluene at ambient temperature and isolated in 62%–74%yields.X-ray analysis revealed the linear Cnt(Cp^(*))–Ln–Cnt(TPP)geometry with a bond angle close to 180°,a Cnt(Cp^(*))–Ln bond distance ranging from 2.325 to 2.365Åand a Cnt(TPP)–Ln distance ranging from 1.012 to 1.063Å.These complexes demonstrated remarkable thermal and oxidative stability,being sublimable under vacuum above 290°C without decomposition(∼5×10^(−2)Torr).Magnetic studies revealed field-induced single-molecule magnet(SMM)behavior for the Tb^(3+),Dy^(3+),and Er^(3+)derivatives.Theoretical investigations revealed the presence of only moderately axial g tensors,a small splitting within the ground multiplet,and significant mixing between different projections of the total angular momentum,all of which contribute to the disappointing SMM behavior.A quasi-spherical Ln^(3+)coordination environment created by the tetradentate TPP ligand and appreciable orbital interactions of itsπ-conjugated system with the dysprosium 4f orbitals could introduce transverse components to the crystal field.
文摘Chiral separation is of critical importance in many areas spanning from pharmaceutics and agriculture to catalysis.Coordination polymers and metal-organic frameworks have been envisaged for such a purpose.In this study,the post-synthetic functionalization of the two-dimensional Hofmann clathrate[Ni(H_(2)O)_(2)][Ni(CN)_(4)]with enantiopure phenylethylamines yielding hydrostable chiral clathrates is reported.
文摘^(201)Tl-labeled Prussian blue and Au core@Prussian blue shell nanoparticles were synthesised and investigated in vivo as nanoprobes by using SPECT-CT scintigraphy.We demonstrate that the size,morphology and nanoparticle coating affect the kinetics of the nanoparticle biodistribution.
基金the Russian Science Foundation(grant 17-73-30036)the Natural Science Basic Research Program of Shaanxi(program no.2020JQ-136)+1 种基金the Fundamental Research Funds for the Central Universities(G2020KY0519).funded by the Researchers Supporting Project Number(RSP-2020/267)King Saud University,Riyadh,Saudi Arabia.
文摘We report a new octahedral[Dy(OCPh_(3))_(2)(THF)_(4)][BPh_(4)]luminescent Single-Molecule Magnet(SMM)exhibiting massive crystal-field splitting and an anisotropic barrier of 1385 cm^(−1).Magnetic measurements combined with ab initio analysis reveal a novel mechanism behind the high blocking barrier based on the quenching of one-phonon transitions between the three low-lying crystal-field multiplets due to large energy gaps between them exceeding the available phonon energies and forcing the activated relaxation to proceed through the fourth doublet.The observed nonetheless short relaxation time is due to appreciable non-axial anisotropy,which opens a tunnelling relaxation path via interaction with the nuclear spins.Reducing the equatorial crystal-field quenches drastically the quantum tunnelling of magnetization,allowing for full exploitation of the high blocking barrier of the complex as in the best known SMMs.
文摘Prussian blue(PB)type nanoparticles belong to an exciting family of molecule-based nanomaterials.They combine the possibility of surface engineering with specific advantages related to their porous molecule-based structures and their fascinating chemical and physical properties including redox,magnetic,photothermal and host–vip features.In this review,we focus on recent advances in the Post-Synthetic Modification(PSM)of nano-sized PB and its analogues(PBA)and compare them with the current strategies used in Metal–Organic Frameworks(MOF)in order to give the outlooks on the future researches in this domain.
