Two low-dimensional Cu(I)boron imidazolate frameworks(BIFs),[CuBH(bim)_(3)]_(n)(BIF-40;bim=benzimidazolate)and[CuBH(im)_(3)]_(n)(BIF-6,im=imidazolate),have been synthesized and both of them display unique mechanochrom...Two low-dimensional Cu(I)boron imidazolate frameworks(BIFs),[CuBH(bim)_(3)]_(n)(BIF-40;bim=benzimidazolate)and[CuBH(im)_(3)]_(n)(BIF-6,im=imidazolate),have been synthesized and both of them display unique mechanochromism.In addition,BIF-40 showed reducing activity due to the rich B–H bonds in the structure,and it was employed to load AuPd bimetal nanoparticles through a one-step process for further catalysis.The corresponding mechanism involving a grinding process between chains or layers is discussed in detail.This work not only provides compelling evidence for designing and applying coordination polymers as mechanochromic materials,but also develops an eco-friendly strategy for loading bimetallic NPs into BIFs.展开更多
Comparison of well-determined single crystal data for stoichiometric, or near-stoichiometric, metal hexaborides confirms previously identified lattice parameter trends using powder diffraction. Trends for both divalen...Comparison of well-determined single crystal data for stoichiometric, or near-stoichiometric, metal hexaborides confirms previously identified lattice parameter trends using powder diffraction. Trends for both divalent and trivalent forms suggest that potential new forms for synthesis include Sc and Mn hexaborides. Density Functional Theory (DFT) calculations for KB6, CaB6, YB6, LaB6, boron octahedral clusters and Sc and Mn forms show that the shapes of bonding orbitals are defined by the boron framework. Inclusion of metal into the boron framework induces a reduction in energy ranging from 1 eV to 6 eV increasing with ionic charge. For metals with d1 character, such a shift in energy brings a doubly degenerate band section along with the G-M reciprocal space direction within the conduction bands tangential to the Fermi surface. ScB6 band structure and density of states calculations show directions and gap characteristics similar to those of YB6 and LaB6. These calculations for ScB6 suggest that it may be possible to realize superconductivity in this compound if synthesized.展开更多
Two new boron imidazolate frameworks(BIFs),Zn2[HBH(2-mim)3]2(1,2-PEA)2(EG)2(BIF-120,EG=ethylene glycol)and Zn[BH(2-mim)3](1,2-HPEA)(BIF-121),were successfully synthesized by mixing the KBH(2-mim)3 ligand and the semir...Two new boron imidazolate frameworks(BIFs),Zn2[HBH(2-mim)3]2(1,2-PEA)2(EG)2(BIF-120,EG=ethylene glycol)and Zn[BH(2-mim)3](1,2-HPEA)(BIF-121),were successfully synthesized by mixing the KBH(2-mim)3 ligand and the semirigid aromatic dicarboxylate ligand 1,2-benzenediacetic acid(1,2-H2PEA)under solvothermal conditions.In this paper,the two samples were structurally characterized by single-crystal X-ray diffraction and tested by infrared spectroscopy(IR),UV-visible spectroscopy(UV-Vis),thermogravimetric analysis TGA and X-ray powder diffractions.In addition,the solid-state luminescent properties of these crystals were also investigated.展开更多
基金support of this work by the 973 program(2012CB821705)NSFC(21221001,21203196,21425102)CAS(XDA07070200).
文摘Two low-dimensional Cu(I)boron imidazolate frameworks(BIFs),[CuBH(bim)_(3)]_(n)(BIF-40;bim=benzimidazolate)and[CuBH(im)_(3)]_(n)(BIF-6,im=imidazolate),have been synthesized and both of them display unique mechanochromism.In addition,BIF-40 showed reducing activity due to the rich B–H bonds in the structure,and it was employed to load AuPd bimetal nanoparticles through a one-step process for further catalysis.The corresponding mechanism involving a grinding process between chains or layers is discussed in detail.This work not only provides compelling evidence for designing and applying coordination polymers as mechanochromic materials,but also develops an eco-friendly strategy for loading bimetallic NPs into BIFs.
文摘Comparison of well-determined single crystal data for stoichiometric, or near-stoichiometric, metal hexaborides confirms previously identified lattice parameter trends using powder diffraction. Trends for both divalent and trivalent forms suggest that potential new forms for synthesis include Sc and Mn hexaborides. Density Functional Theory (DFT) calculations for KB6, CaB6, YB6, LaB6, boron octahedral clusters and Sc and Mn forms show that the shapes of bonding orbitals are defined by the boron framework. Inclusion of metal into the boron framework induces a reduction in energy ranging from 1 eV to 6 eV increasing with ionic charge. For metals with d1 character, such a shift in energy brings a doubly degenerate band section along with the G-M reciprocal space direction within the conduction bands tangential to the Fermi surface. ScB6 band structure and density of states calculations show directions and gap characteristics similar to those of YB6 and LaB6. These calculations for ScB6 suggest that it may be possible to realize superconductivity in this compound if synthesized.
基金We gratefully acknowledge the National Key Research and Development Program of China(No.2018YFA0208600)。
文摘Two new boron imidazolate frameworks(BIFs),Zn2[HBH(2-mim)3]2(1,2-PEA)2(EG)2(BIF-120,EG=ethylene glycol)and Zn[BH(2-mim)3](1,2-HPEA)(BIF-121),were successfully synthesized by mixing the KBH(2-mim)3 ligand and the semirigid aromatic dicarboxylate ligand 1,2-benzenediacetic acid(1,2-H2PEA)under solvothermal conditions.In this paper,the two samples were structurally characterized by single-crystal X-ray diffraction and tested by infrared spectroscopy(IR),UV-visible spectroscopy(UV-Vis),thermogravimetric analysis TGA and X-ray powder diffractions.In addition,the solid-state luminescent properties of these crystals were also investigated.
