The heterotrinuclear complex [PtCu2(m-dppm)2(dmbpy)2(m-h1,h2 C CPhCH3-4)2] (ClO4)21.5CH2Cl2 1 (dmbpy = 4,4-dimethyl-2,2?bipyridine, dppm = bis(diphenylphosphino)meth- ane) has been prepared and characterized by X-ray...The heterotrinuclear complex [PtCu2(m-dppm)2(dmbpy)2(m-h1,h2 C CPhCH3-4)2] (ClO4)21.5CH2Cl2 1 (dmbpy = 4,4-dimethyl-2,2?bipyridine, dppm = bis(diphenylphosphino)meth- ane) has been prepared and characterized by X-ray crystallography. The complex crystallizes in the triclinic system, space group P with a = 12.9359(3), b = 14.3908(2), c = 15.2121(3) ? α = 107.370(1), β = 93.539(1), γ = 108.207(1), V = 2529.59(8) ?, Mr = 2015.96, Z = 1, Dc = 1.323 g/cm3, F(000) = 1019, m(MoKa) = 2.042 mm-1, the final R = 0.0604 and wR = 0.1529 for 8002 observed reflections with I > 2σ(I). The 4-methylphenylacetylides are bonded to the PtII and CuI centers in η1 (s) and η2 (p) coordination modes, respectively. The PtII atom is linked by one dppm bridge to adopt a square planar environment and CuI by one alkynyl ligand to assume a distorted tetrahedral geometry.展开更多
Understanding the quantum effect in the cross-conjugated system is of fundamental significance in molecular electronics.In this study,four molecules Xa-O,Xa,BP and BP-O were synthesized to investigate the destructive ...Understanding the quantum effect in the cross-conjugated system is of fundamental significance in molecular electronics.In this study,four molecules Xa-O,Xa,BP and BP-O were synthesized to investigate the destructive quantum interference(DQI)of a carbonyl bridge.The single-molecule conductance measured by the scanning tunneling microscope break junction(STM-BJ)technique demonstrates an increase in the conductance from molecule BP-O to molecule Xa-O as the cross-conjugated system is extended.Theoretical calculations show that the explicit DQI feature is presented in BP-O but absent in Xa-O,which indicates the removal of DQI in the restrained structures and results in the conductance enhancement in Xa-O.展开更多
A new sulfonylcalixarene-based coordination container 1 was designed and synthesized from the self-assembly reaction of p-tert-butylsulfonylcalix[4]arene (TBSC),Co(II) ion,and 2,6-naphthalenedicarboxylic acid (NDC).It...A new sulfonylcalixarene-based coordination container 1 was designed and synthesized from the self-assembly reaction of p-tert-butylsulfonylcalix[4]arene (TBSC),Co(II) ion,and 2,6-naphthalenedicarboxylic acid (NDC).It crystallizes in tetragonal system,space group I4/m with a=b=30.9119(19)A,c=43.565(3)A,V=41628(6)A^(3),D_(c)=0.731 g/cm^(3),M_(r)=9162.36,C_(384)H_(348)Co_(24)O_(126)S_(24),Z=2,F(000)=9384,μ=0.566 mm^(–1),the final GOOF=1.027,R=0.0987 and w R=0.2474 for 7240 observed reflections with I>2σ(I).Structural analyses indicate that 1 adopts an edge-directed octahedral geometry and consists of six TBSC-supported Co_(4) tetranuclear units locating on the vertices and twelve NDC bridging ligands occupying the edges.The new compound exhibits outstanding performance for the C_(2) hydrocarbons separation over CH_(4).展开更多
Sulfonylcalix[4]arenes-based coordination containers,namely metal-organic supercontainers(MOSCs),are a new class of coordination containers constructed from the self-assembly of divalent metal ions,suitable carboxylat...Sulfonylcalix[4]arenes-based coordination containers,namely metal-organic supercontainers(MOSCs),are a new class of coordination containers constructed from the self-assembly of divalent metal ions,suitable carboxylate linkers,and sulfonylcalix[4]arenes container precursor.MOSCs feature both endo cavity surrounded by carboxylate linkers and exo cavities originated from the upper rim of sulfonylcalix[4]arenes.The molecular topologies and endo cavity of MOSCs are tuneable via judicious design of carboxylate linkers,while the modulation of endo cavity are accessible by chemical modification on the para substituent group of the sulfonylcalix[4]arenes.In this paper,recent advances and typical examples of design and functionalization of MOSCs are presented.展开更多
基金NNSFC(No.20171044 and 20273074)NSF of Fujian Province (E0310029).
文摘The heterotrinuclear complex [PtCu2(m-dppm)2(dmbpy)2(m-h1,h2 C CPhCH3-4)2] (ClO4)21.5CH2Cl2 1 (dmbpy = 4,4-dimethyl-2,2?bipyridine, dppm = bis(diphenylphosphino)meth- ane) has been prepared and characterized by X-ray crystallography. The complex crystallizes in the triclinic system, space group P with a = 12.9359(3), b = 14.3908(2), c = 15.2121(3) ? α = 107.370(1), β = 93.539(1), γ = 108.207(1), V = 2529.59(8) ?, Mr = 2015.96, Z = 1, Dc = 1.323 g/cm3, F(000) = 1019, m(MoKa) = 2.042 mm-1, the final R = 0.0604 and wR = 0.1529 for 8002 observed reflections with I > 2σ(I). The 4-methylphenylacetylides are bonded to the PtII and CuI centers in η1 (s) and η2 (p) coordination modes, respectively. The PtII atom is linked by one dppm bridge to adopt a square planar environment and CuI by one alkynyl ligand to assume a distorted tetrahedral geometry.
基金National Natural Science Foundation of China(No.92061117)Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB20000000)+1 种基金Project of the Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(No.2021ZR129)Natural Science Foundation of Fujian Province,China(No.2020J01110).
文摘Understanding the quantum effect in the cross-conjugated system is of fundamental significance in molecular electronics.In this study,four molecules Xa-O,Xa,BP and BP-O were synthesized to investigate the destructive quantum interference(DQI)of a carbonyl bridge.The single-molecule conductance measured by the scanning tunneling microscope break junction(STM-BJ)technique demonstrates an increase in the conductance from molecule BP-O to molecule Xa-O as the cross-conjugated system is extended.Theoretical calculations show that the explicit DQI feature is presented in BP-O but absent in Xa-O,which indicates the removal of DQI in the restrained structures and results in the conductance enhancement in Xa-O.
基金supported by the National Natural Science Foundation of China(21673239 and 21501179)。
文摘A new sulfonylcalixarene-based coordination container 1 was designed and synthesized from the self-assembly reaction of p-tert-butylsulfonylcalix[4]arene (TBSC),Co(II) ion,and 2,6-naphthalenedicarboxylic acid (NDC).It crystallizes in tetragonal system,space group I4/m with a=b=30.9119(19)A,c=43.565(3)A,V=41628(6)A^(3),D_(c)=0.731 g/cm^(3),M_(r)=9162.36,C_(384)H_(348)Co_(24)O_(126)S_(24),Z=2,F(000)=9384,μ=0.566 mm^(–1),the final GOOF=1.027,R=0.0987 and w R=0.2474 for 7240 observed reflections with I>2σ(I).Structural analyses indicate that 1 adopts an edge-directed octahedral geometry and consists of six TBSC-supported Co_(4) tetranuclear units locating on the vertices and twelve NDC bridging ligands occupying the edges.The new compound exhibits outstanding performance for the C_(2) hydrocarbons separation over CH_(4).
基金supported by the National Natural Science Foundation of China(21673239 and 21501179)。
文摘Sulfonylcalix[4]arenes-based coordination containers,namely metal-organic supercontainers(MOSCs),are a new class of coordination containers constructed from the self-assembly of divalent metal ions,suitable carboxylate linkers,and sulfonylcalix[4]arenes container precursor.MOSCs feature both endo cavity surrounded by carboxylate linkers and exo cavities originated from the upper rim of sulfonylcalix[4]arenes.The molecular topologies and endo cavity of MOSCs are tuneable via judicious design of carboxylate linkers,while the modulation of endo cavity are accessible by chemical modification on the para substituent group of the sulfonylcalix[4]arenes.In this paper,recent advances and typical examples of design and functionalization of MOSCs are presented.
