Molecules with long preserved magnetic moments are perceived as the smallest units for storing bytes,which could bring a new revolution for information technology.However,the rational design of such molecules remains ...Molecules with long preserved magnetic moments are perceived as the smallest units for storing bytes,which could bring a new revolution for information technology.However,the rational design of such molecules remains challenging.Here two rigid adamantanol ligand based dysprosium(III)complexes([Dy(1-AdO)_(2)(py)_(5)]BPh_(4)-1 and[Dy(2-AdO)_(2)(py)_(5)]BPh_(4)-2)with pentagonal-bipyramidal coordination geometry and local D5h symmetry were successfully prepared,which display excellent single-molecule magnet(SMM)behavior(U_(eff)≈1835 K,T_(B)_(ZFC)≈24 K,T_(B)^(100s)≈17 K and T_(B)^(H)=23 K for 1;U_(eff)≈1756 K,T_(B)^(ZFC)≈20 K,T_(B)^(100s)≈16 K and T_(B)^(H)=23 K for 2)due to the much weakened vibration in low energy regimes.Remarkably,the large energy barriers and high blocking temperatures for these two complexes in solid states are well preserved in solution.This is never observed in previous studies of SMMs,indicating that the adamantanol is rigid and can be introduced to make the composed molecules stable enough to maintain the solid state magnetic property in solution.展开更多
A new family of isostructural 3 d-4 f polymetallic complexes,formulated as [Cu_(6)Ln_(5)(μ_(3)OH)_(9)(C_(4)H_(8)O_(2)N)_(6)(C_(5)H_(4)ON)_(6)(H_(2)O)_(9)]·(ClO_(4))_(6)·(H_(2)O)_(22)(Ln=Pr,1;Nd,2;Sm,3;Eu,4;...A new family of isostructural 3 d-4 f polymetallic complexes,formulated as [Cu_(6)Ln_(5)(μ_(3)OH)_(9)(C_(4)H_(8)O_(2)N)_(6)(C_(5)H_(4)ON)_(6)(H_(2)O)_(9)]·(ClO_(4))_(6)·(H_(2)O)_(22)(Ln=Pr,1;Nd,2;Sm,3;Eu,4;Gd,5),was successfully isolated through the simple hydrolysis reaction of 2-aminoisobutyric acid,2-hydroxypyridine,Cu(CH_(3)COO)_(2)·H_(2)O,and Ln(ClO_(4))_(3)·6 H_(2)O.Notably,the [Cu_(6)Ln_(5)] clusters with high molecular symmetry of D_(3h) are rare examples of2-aminoisobutyric acid-based 3 d-4 f clusters.The successful theoretical modeling of 5 yielded that the Gd-Gd exchange is of order 0.2 K,whereas the Gd-Cu exchange is an order of magnitude larger.Magnetization data collected for comp lex 5 yield a magnetic entropy change(-ΔSm) of 19.6 J kg^(-1) K^(-1)<1 at 3 K and 7 T,which may be attributed to the weak magnetic interactions between the component metal ions.展开更多
Hybrids composed of biocompatible polymers reinforced with inorganic nanomaterials are useful for many biomedical applications including implantation and tissue regeneration and engineering.In this work,we report a ne...Hybrids composed of biocompatible polymers reinforced with inorganic nanomaterials are useful for many biomedical applications including implantation and tissue regeneration and engineering.In this work,we report a new type of hybrid prepared by doping ultrathin nanowires of lanthanide hydroxycarbonates into classical biocompatible poly(citrates-siloxane).The doping of the inorganic nanowires imparts the hybrids with excellent miscibility with the polymeric matrix,producing hybrids with high elasticity and high tensile strength.The hybrids containing Eu(III)and Gd(III)display their respective luminescence and magnetic properties and thus,offer opportunities to monitor the fate of such hybrids when used in vivo.Insignificant degradation and excellent biocompatibility of these hybrids have also been demonstrated.Together,these favorable traits portend useful applications of the newly developed hybrid elastomers.展开更多
基金This work was supported by the National Natural Science Foundation of China(Nos.21773130,21871219 and 21971203)the Key Laboratory Construction Program of Xi'an Municipal Bu-reau of Science and Technology(No.201805056ZD7CG40)+1 种基金the Key Scientific and Technological Innovation Team of Shaanxi Province(No.2020TD-001)the Fundamental Research Funds for Central Universities。
文摘Molecules with long preserved magnetic moments are perceived as the smallest units for storing bytes,which could bring a new revolution for information technology.However,the rational design of such molecules remains challenging.Here two rigid adamantanol ligand based dysprosium(III)complexes([Dy(1-AdO)_(2)(py)_(5)]BPh_(4)-1 and[Dy(2-AdO)_(2)(py)_(5)]BPh_(4)-2)with pentagonal-bipyramidal coordination geometry and local D5h symmetry were successfully prepared,which display excellent single-molecule magnet(SMM)behavior(U_(eff)≈1835 K,T_(B)_(ZFC)≈24 K,T_(B)^(100s)≈17 K and T_(B)^(H)=23 K for 1;U_(eff)≈1756 K,T_(B)^(ZFC)≈20 K,T_(B)^(100s)≈16 K and T_(B)^(H)=23 K for 2)due to the much weakened vibration in low energy regimes.Remarkably,the large energy barriers and high blocking temperatures for these two complexes in solid states are well preserved in solution.This is never observed in previous studies of SMMs,indicating that the adamantanol is rigid and can be introduced to make the composed molecules stable enough to maintain the solid state magnetic property in solution.
基金supported by Shenzhen Science and Technology Program (No.JCYJ20180306170859634)National Natural Science Foundation of China (Nos.21773130,21801202,21871219, 21971203 and 21620102002)+4 种基金Shaanxi National Science Foundation (No.2019JQ-016)China Postdoctoral Science Foundation (Nos. 2019T120891 and 2018M643615)Key Laboratory Construction Program of Xi’an Municipal Bureau of Science and Technology (No. 201805056ZD7CG40)Cyrus Chung Ying Tang Foundation and Fundamental Research Funds for Central Universitiessupported by the Deutsche Forschungsgemeinschaft DFG (Nos.314331397,SCHN 615/23-1)。
文摘A new family of isostructural 3 d-4 f polymetallic complexes,formulated as [Cu_(6)Ln_(5)(μ_(3)OH)_(9)(C_(4)H_(8)O_(2)N)_(6)(C_(5)H_(4)ON)_(6)(H_(2)O)_(9)]·(ClO_(4))_(6)·(H_(2)O)_(22)(Ln=Pr,1;Nd,2;Sm,3;Eu,4;Gd,5),was successfully isolated through the simple hydrolysis reaction of 2-aminoisobutyric acid,2-hydroxypyridine,Cu(CH_(3)COO)_(2)·H_(2)O,and Ln(ClO_(4))_(3)·6 H_(2)O.Notably,the [Cu_(6)Ln_(5)] clusters with high molecular symmetry of D_(3h) are rare examples of2-aminoisobutyric acid-based 3 d-4 f clusters.The successful theoretical modeling of 5 yielded that the Gd-Gd exchange is of order 0.2 K,whereas the Gd-Cu exchange is an order of magnitude larger.Magnetization data collected for comp lex 5 yield a magnetic entropy change(-ΔSm) of 19.6 J kg^(-1) K^(-1)<1 at 3 K and 7 T,which may be attributed to the weak magnetic interactions between the component metal ions.
基金supported by the National Natural Science Foundation of China(grant nos.21971117,21522106,and 51872224)China Postdoctoral Science Foundation(grant no.2018M642133)+4 种基金the National Key R&D Program of China(grant no.2017YFA0208000)the Fundamental Research Funds for the Central Universities,Nankai University(grant nos.63201071 and ZB19500202)State Key Laboratory of Rare Earth Resource Utilization(grant no.RERU2019001)the 111 Project(grant no.B18030)from ChinaBeijing-Tianjin-Hebei Collaborative Innovation Project(grant no.63201058).
文摘Hybrids composed of biocompatible polymers reinforced with inorganic nanomaterials are useful for many biomedical applications including implantation and tissue regeneration and engineering.In this work,we report a new type of hybrid prepared by doping ultrathin nanowires of lanthanide hydroxycarbonates into classical biocompatible poly(citrates-siloxane).The doping of the inorganic nanowires imparts the hybrids with excellent miscibility with the polymeric matrix,producing hybrids with high elasticity and high tensile strength.The hybrids containing Eu(III)and Gd(III)display their respective luminescence and magnetic properties and thus,offer opportunities to monitor the fate of such hybrids when used in vivo.Insignificant degradation and excellent biocompatibility of these hybrids have also been demonstrated.Together,these favorable traits portend useful applications of the newly developed hybrid elastomers.
