By aminothermal treatment of ternary CsxHgySez phases,or of Cs_(2)Se with HgSO4,respectively,in 1,2-diaminoethane(en)and en/water mixtures at 150℃,four new cesium selenido mercurate compounds Cs_(2)[HgSe_(2)](1),[Cs_...By aminothermal treatment of ternary CsxHgySez phases,or of Cs_(2)Se with HgSO4,respectively,in 1,2-diaminoethane(en)and en/water mixtures at 150℃,four new cesium selenido mercurate compounds Cs_(2)[HgSe_(2)](1),[Cs_(2)(H_(2)O)_(2)][HgSe_(2)](2),Cs[Cs_(3)(H_(2)O)0.5][HgSe_(2)](Se_(2))(3)and Cs_(19)(Hen)(H_(2)en)(Se_(2))[HgSe_(2)]_(2)[HgSe3][Hg_(2)Se_(5)]_(2)(4)were synthesized.The precursor phases were prepared by fusion of Cs_(2)Se and HgSe at 600℃.2 comprises an unprecedented 1D anionic selenido mercurate substructure.3 and 4 are rare examples of mercurate compounds with different anions,one of which comprises a new type of a dinuclear chalcogenido mercurate anion.The structures of all four compounds were identified by single crystal X-ray diffraction.Micro X-ray fluorescence spectroscopy(μ-XFS)was used to confirm the heavy atom compositions,and optical absorption measurements were performed to determine the optical band gaps.展开更多
Two diphosphine-protected superatom gold selenido nanoclusters,[Au_(8)Se_(2)(dppm)4]^(2+)(SD/Au_(8)a,dppm=Ph_(2)PCH_(2)PPh_(2))and[Au_(8)Se_(2)(dppe)4]^(2+)(SD/Au_(8)b,dppe=Ph_(2)P(CH_(2))2PPh_(2)),were obtained by th...Two diphosphine-protected superatom gold selenido nanoclusters,[Au_(8)Se_(2)(dppm)4]^(2+)(SD/Au_(8)a,dppm=Ph_(2)PCH_(2)PPh_(2))and[Au_(8)Se_(2)(dppe)4]^(2+)(SD/Au_(8)b,dppe=Ph_(2)P(CH_(2))2PPh_(2)),were obtained by the reduction of[Au(SMe2)Cl]in the presence of Ph3PSe as the selenium ion releasing agents.Both can be regarded as“superatoms”with 1S^(2)configuration based on the spherical Jellium model.Despite the same metal-ligand binding motifs on the surface and the intrinsic C_(2)molecular symmetry,the configurations of Au_(8)Se_(2)kernels in them are different in terms of Au-Au bonded metallic frameworks.SD/Au_(8)a displays a heart-shaped[core+exo]type structure(Au4 tetrahedron core+two exo Au2Se units),whereas the two exo Au_(2)Se counterparts in SD/Au_(8)b are additionally locked by an obvious Au-Au bond,forming a distorted hexagonal Au6 ring with two capping AuSe units appended above and below it.Consequently,they showed different photophysical properties as reflected by their electronic absorption and emission spectra.Especially,both SD/Au_(8)a and SD/Au_(8)b exhibit blue-shifted thermochromic luminescence upon cooling from 293 to 83 K but the latter exhibits anomalous emission intensity evolution trends due to the occurrence of temperature-induced phase transition as revealed by varied-temperature crystallographic analyses.This work not only clearly illustrates the significance of ligands on tuning the kernel structure but also provides two rarely comparable examples for better understanding of the structure-property relationship of gold nanoclusters.展开更多
基金supported by the Deutsche Forschungsgemeinschaft(DFG)within the framework of SPP1708.
文摘By aminothermal treatment of ternary CsxHgySez phases,or of Cs_(2)Se with HgSO4,respectively,in 1,2-diaminoethane(en)and en/water mixtures at 150℃,four new cesium selenido mercurate compounds Cs_(2)[HgSe_(2)](1),[Cs_(2)(H_(2)O)_(2)][HgSe_(2)](2),Cs[Cs_(3)(H_(2)O)0.5][HgSe_(2)](Se_(2))(3)and Cs_(19)(Hen)(H_(2)en)(Se_(2))[HgSe_(2)]_(2)[HgSe3][Hg_(2)Se_(5)]_(2)(4)were synthesized.The precursor phases were prepared by fusion of Cs_(2)Se and HgSe at 600℃.2 comprises an unprecedented 1D anionic selenido mercurate substructure.3 and 4 are rare examples of mercurate compounds with different anions,one of which comprises a new type of a dinuclear chalcogenido mercurate anion.The structures of all four compounds were identified by single crystal X-ray diffraction.Micro X-ray fluorescence spectroscopy(μ-XFS)was used to confirm the heavy atom compositions,and optical absorption measurements were performed to determine the optical band gaps.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.91961105,21822107,22001139,and 21827801)the Natural Science Foundation of Shandong Province(Nos.ZR2019ZD45,ZR2020ZD35,ZR2019BB058,JQ201803,and ZR2017MB061)+1 种基金the Taishan Scholar Project of Shandong Province of China(Nos.tsqn201812003 and ts20190908)the Project for Scientific Research Innovation Team of Young Scholar in Colleges and Universities of Shandong Province(No.2019KJC028).
文摘Two diphosphine-protected superatom gold selenido nanoclusters,[Au_(8)Se_(2)(dppm)4]^(2+)(SD/Au_(8)a,dppm=Ph_(2)PCH_(2)PPh_(2))and[Au_(8)Se_(2)(dppe)4]^(2+)(SD/Au_(8)b,dppe=Ph_(2)P(CH_(2))2PPh_(2)),were obtained by the reduction of[Au(SMe2)Cl]in the presence of Ph3PSe as the selenium ion releasing agents.Both can be regarded as“superatoms”with 1S^(2)configuration based on the spherical Jellium model.Despite the same metal-ligand binding motifs on the surface and the intrinsic C_(2)molecular symmetry,the configurations of Au_(8)Se_(2)kernels in them are different in terms of Au-Au bonded metallic frameworks.SD/Au_(8)a displays a heart-shaped[core+exo]type structure(Au4 tetrahedron core+two exo Au2Se units),whereas the two exo Au_(2)Se counterparts in SD/Au_(8)b are additionally locked by an obvious Au-Au bond,forming a distorted hexagonal Au6 ring with two capping AuSe units appended above and below it.Consequently,they showed different photophysical properties as reflected by their electronic absorption and emission spectra.Especially,both SD/Au_(8)a and SD/Au_(8)b exhibit blue-shifted thermochromic luminescence upon cooling from 293 to 83 K but the latter exhibits anomalous emission intensity evolution trends due to the occurrence of temperature-induced phase transition as revealed by varied-temperature crystallographic analyses.This work not only clearly illustrates the significance of ligands on tuning the kernel structure but also provides two rarely comparable examples for better understanding of the structure-property relationship of gold nanoclusters.
