Two new crystals of chlorovanadates,Ba_8Cs_5V_8O_(24)Cl_(13)(1) and MgCsV_2O_6Cl(2),were grown in the molten salt media. 1 crystallizes in tetragonal,space group P4/mmm(No. 123),with a = 14.801(2),c = 12....Two new crystals of chlorovanadates,Ba_8Cs_5V_8O_(24)Cl_(13)(1) and MgCsV_2O_6Cl(2),were grown in the molten salt media. 1 crystallizes in tetragonal,space group P4/mmm(No. 123),with a = 14.801(2),c = 12.341(3) ?,V = 2703.5(8) ?~3,Z = 2,Mr = 3015.56,F(000) = 2640,μ = 11.044 mm-1,Dc = 3.704 g/cm3,the final R = 0.0380 and wR = 0.0937 for 1654 observed reflections with I 〉 2σ(I). 2 crystallizes in a monoclinic space group C2/c(No. 15) with a = 11.128(2),b = 10.540(2),c = 6.9892(14) ?,β = 118.38(3)°,V = 721.2(2) ?~3,Z = 4,M_r = 390.55,F(000) = 712,μ = 7.997 mm-1,D_c = 3.597 g/cm^3,the final R = 0.0537 and w R = 0.1363 for 740 observed reflections with I 〉 2σ(I). 1 exhibits a novel 8-membered-ring [V_8O_(24)] consisting of 8 corner-shared VO_4 tetrahetra,but in 2,an infinite ladder-like [VO_3]_∞ chain is formed by VO_5 square pyramids through sharing the edges.展开更多
Four pillar[5]arene-based bicyclic compounds,so-called molecular universal joint(MUJ),were synthesized by incorporating a bisamide ring containing N,O,or S-heteroatom groups,which served as stimuli-responsive chiropti...Four pillar[5]arene-based bicyclic compounds,so-called molecular universal joint(MUJ),were synthesized by incorporating a bisamide ring containing N,O,or S-heteroatom groups,which served as stimuli-responsive chiroptical molecular devices.The structure of MUJ was confirmed by 1H NMR spectra and single-crystal X-ray diffraction analysis,and their planar-chiral enantiomers were successfully separated.Chiroptical inversion behaviors from in to out configurations triggered by temperature,solvent,and guest complexation were investigated by circular dichroism spectra.Chiroptical inversion could be realized in the presence of adiponitrile in certain solvents due to the solvation effects on the side ring and the threading of the guest into the pillar[5]arene cavity.However,the stronger self-included interactions between the cavity and the inside ring of certain MUJs led to inhibition of the switching.展开更多
基金supported by the National Natural Science Foundation of China(No.21541009)
文摘Two new crystals of chlorovanadates,Ba_8Cs_5V_8O_(24)Cl_(13)(1) and MgCsV_2O_6Cl(2),were grown in the molten salt media. 1 crystallizes in tetragonal,space group P4/mmm(No. 123),with a = 14.801(2),c = 12.341(3) ?,V = 2703.5(8) ?~3,Z = 2,Mr = 3015.56,F(000) = 2640,μ = 11.044 mm-1,Dc = 3.704 g/cm3,the final R = 0.0380 and wR = 0.0937 for 1654 observed reflections with I 〉 2σ(I). 2 crystallizes in a monoclinic space group C2/c(No. 15) with a = 11.128(2),b = 10.540(2),c = 6.9892(14) ?,β = 118.38(3)°,V = 721.2(2) ?~3,Z = 4,M_r = 390.55,F(000) = 712,μ = 7.997 mm-1,D_c = 3.597 g/cm^3,the final R = 0.0537 and w R = 0.1363 for 740 observed reflections with I 〉 2σ(I). 1 exhibits a novel 8-membered-ring [V_8O_(24)] consisting of 8 corner-shared VO_4 tetrahetra,but in 2,an infinite ladder-like [VO_3]_∞ chain is formed by VO_5 square pyramids through sharing the edges.
基金the National Natural Science Foundation of China(Nos.92056116,21871194,21971169)National Key Research and Development Program of China(No.2017YFA0505903).
文摘Four pillar[5]arene-based bicyclic compounds,so-called molecular universal joint(MUJ),were synthesized by incorporating a bisamide ring containing N,O,or S-heteroatom groups,which served as stimuli-responsive chiroptical molecular devices.The structure of MUJ was confirmed by 1H NMR spectra and single-crystal X-ray diffraction analysis,and their planar-chiral enantiomers were successfully separated.Chiroptical inversion behaviors from in to out configurations triggered by temperature,solvent,and guest complexation were investigated by circular dichroism spectra.Chiroptical inversion could be realized in the presence of adiponitrile in certain solvents due to the solvation effects on the side ring and the threading of the guest into the pillar[5]arene cavity.However,the stronger self-included interactions between the cavity and the inside ring of certain MUJs led to inhibition of the switching.