Some reactions of R3SnM（CO）5 （M = Mn, Re） with CH3CN or pyridine were investigated to give complexes R3SnMn（CO）3LL＇ or R3SnMn（CO）4L by a facile mild method. X-ray diffractions analyses show that, in contrast ...Some reactions of R3SnM（CO）5 （M = Mn, Re） with CH3CN or pyridine were investigated to give complexes R3SnMn（CO）3LL＇ or R3SnMn（CO）4L by a facile mild method. X-ray diffractions analyses show that, in contrast to the phosphine ligand occupying in axial position, nitrogen ligands occupy equatorial position.展开更多
A d-f heteronuclear metal-organic framework（MOF）,{[Tm3Zn6（bipy2）2（mimda）7（H2O）3]·（H2O）5}n（1,H3 mimda = 2-methyl-1-H-imidazole-4,5-dicarboxylic acid,and bipy = 4,4？-bipyridine）,has been synthesized un...A d-f heteronuclear metal-organic framework（MOF）,{[Tm3Zn6（bipy2）2（mimda）7（H2O）3]·（H2O）5}n（1,H3 mimda = 2-methyl-1-H-imidazole-4,5-dicarboxylic acid,and bipy = 4,4？-bipyridine）,has been synthesized under solvothermal conditions,and structurally characterized by elemental analysis,IR spectra and X-ray single-crystal diffraction.It crystallizes in orthorhombic system,space group Pnma with a = 16.1102（9）,b = 33.5805（19）,c = 16.8593（10） ？,β = 97.344（11）°,V = 9120.7（9） ？-3,Z = 4,F（000） = 5184,the final R = 0.0530 and w R = 0.1306.In complex 1,the Tm（Ⅲ） ions adopt two types of coordination fashions.Complex 1 shows onedimensional（1-D） Tm-Zn heteronuclear zigzag chains,and these chains are further linked by H3 mimda ligands into Tm-Zn heteronuclear 2-D lattice-like arrays.The 2-D heteronuclear units were connected through [Zn6（mimda）6] rings to give rise to the Tm-Zn heteronuclear cages.Finally,H3 mimda ligands connected the cages into a 3-D heterometallic framework by the combination of [TmO7]n and Tm-Zn heteronuclear cages.In addition,the thermal stability and luminescent property have been investigated.展开更多
Emission tunable d-f transition lanthanide complexes have wide applications in many fields such as lighting and photoredox catalysis.Compared with Ce(Ⅲ)and Eu(Ⅱ)complexes,which have achieved near-unity photoluminesc...Emission tunable d-f transition lanthanide complexes have wide applications in many fields such as lighting and photoredox catalysis.Compared with Ce(Ⅲ)and Eu(Ⅱ)complexes,which have achieved near-unity photoluminescence quantum yields(PLQYs),Yb(Ⅱ)complexes still suffer from low reported PLQYs not exceeding 10%.In this work,two luminescent Yb(Ⅱ)-containing azacryptates YbI_(2)-N8M6(N8M6=4,7,13,16,21,24-hexamethyl-1,4,7,10,13,16,21,24-octaazabicyclo[8.8.8]hexacosane)and YbI2-N8E6(N8E6=4,7,13,16,21,24-hexaethyl-1,4,7,10,13,16,21,24-octaazabicyclo[8.8.8]hexacosane)were synthesized and characterized.YbI2-N8M6 in solid powder exhibits blue emission with a maximum emission wavelength(λm)of 464 nm and a PLQY of 76%,while YbI_(2)-N8E6 in solid powder exhibits green emission with a λ_(m) of 537 nm and a PLQY up to93%.Moreover,YbI_(2)-N8M6 exhibits mechanochromic property,showing an emission color change from deep-blue to cyan under mechanical grinding.These results will inspire the studies about luminescent Yb(Ⅱ)complexes and their further applications.展开更多
Hydrogenases are enzymes that can reversibly split molecular hydrogen. Study on the structure of the active site and the mechanism of catalysis has drawn great attention because the results may be useful for the desig...Hydrogenases are enzymes that can reversibly split molecular hydrogen. Study on the structure of the active site and the mechanism of catalysis has drawn great attention because the results may be useful for the design of cheap biomimetic hydrogen catalysts for fuel cells, or as model for the photoproduction of H\-2. At one time the active site was generally considered to be composed of mononuclear nickel complex with ligands from the polypeptide. A breakthrough in the understanding of the structure of Hases occurred with the resolution crystal structure of D. gigas Hases in 1995. The unexpected result challenged the previously reported spectroscopic studies and caused some academic arguments. Some methods and results used for insight into Hases have to be reconsidered. Different viewpoints concerning the structure of active site of Hases in different periods and some remaining questions will be presented.展开更多
基金supported by the National Natural Science Foundation of China(No.29672018).
文摘Some reactions of R3SnM（CO）5 （M = Mn, Re） with CH3CN or pyridine were investigated to give complexes R3SnMn（CO）3LL＇ or R3SnMn（CO）4L by a facile mild method. X-ray diffractions analyses show that, in contrast to the phosphine ligand occupying in axial position, nitrogen ligands occupy equatorial position.
基金Supported by the Foundation for Science&Technology Innovation Talents in Henan Province(Nos.14HASTIT014,and 16410010012)Natural Science Foundation of China(Nos.21671114)the Foundation of Education Committee of Henan province,China(No.14B150033)
文摘A d-f heteronuclear metal-organic framework（MOF）,{[Tm3Zn6（bipy2）2（mimda）7（H2O）3]·（H2O）5}n（1,H3 mimda = 2-methyl-1-H-imidazole-4,5-dicarboxylic acid,and bipy = 4,4？-bipyridine）,has been synthesized under solvothermal conditions,and structurally characterized by elemental analysis,IR spectra and X-ray single-crystal diffraction.It crystallizes in orthorhombic system,space group Pnma with a = 16.1102（9）,b = 33.5805（19）,c = 16.8593（10） ？,β = 97.344（11）°,V = 9120.7（9） ？-3,Z = 4,F（000） = 5184,the final R = 0.0530 and w R = 0.1306.In complex 1,the Tm（Ⅲ） ions adopt two types of coordination fashions.Complex 1 shows onedimensional（1-D） Tm-Zn heteronuclear zigzag chains,and these chains are further linked by H3 mimda ligands into Tm-Zn heteronuclear 2-D lattice-like arrays.The 2-D heteronuclear units were connected through [Zn6（mimda）6] rings to give rise to the Tm-Zn heteronuclear cages.Finally,H3 mimda ligands connected the cages into a 3-D heterometallic framework by the combination of [TmO7]n and Tm-Zn heteronuclear cages.In addition,the thermal stability and luminescent property have been investigated.
基金supported by the National Natural Science Foundation of China(22071003,92156016,21621061)the National Key R&D Program of China(2021YFB3501800)Beijing Natural Science Foundation(2202015)。
文摘Emission tunable d-f transition lanthanide complexes have wide applications in many fields such as lighting and photoredox catalysis.Compared with Ce(Ⅲ)and Eu(Ⅱ)complexes,which have achieved near-unity photoluminescence quantum yields(PLQYs),Yb(Ⅱ)complexes still suffer from low reported PLQYs not exceeding 10%.In this work,two luminescent Yb(Ⅱ)-containing azacryptates YbI_(2)-N8M6(N8M6=4,7,13,16,21,24-hexamethyl-1,4,7,10,13,16,21,24-octaazabicyclo[8.8.8]hexacosane)and YbI2-N8E6(N8E6=4,7,13,16,21,24-hexaethyl-1,4,7,10,13,16,21,24-octaazabicyclo[8.8.8]hexacosane)were synthesized and characterized.YbI2-N8M6 in solid powder exhibits blue emission with a maximum emission wavelength(λm)of 464 nm and a PLQY of 76%,while YbI_(2)-N8E6 in solid powder exhibits green emission with a λ_(m) of 537 nm and a PLQY up to93%.Moreover,YbI_(2)-N8M6 exhibits mechanochromic property,showing an emission color change from deep-blue to cyan under mechanical grinding.These results will inspire the studies about luminescent Yb(Ⅱ)complexes and their further applications.
文摘Hydrogenases are enzymes that can reversibly split molecular hydrogen. Study on the structure of the active site and the mechanism of catalysis has drawn great attention because the results may be useful for the design of cheap biomimetic hydrogen catalysts for fuel cells, or as model for the photoproduction of H\-2. At one time the active site was generally considered to be composed of mononuclear nickel complex with ligands from the polypeptide. A breakthrough in the understanding of the structure of Hases occurred with the resolution crystal structure of D. gigas Hases in 1995. The unexpected result challenged the previously reported spectroscopic studies and caused some academic arguments. Some methods and results used for insight into Hases have to be reconsidered. Different viewpoints concerning the structure of active site of Hases in different periods and some remaining questions will be presented.
