A new copper iodide/organic hybrid incorporated with methyl viologen, [（MV）（Cu2I4）·H2O]n（1, MV = methyl viologen）, has been solvothermally synthesized and structurally determined by X-ray diffraction method...A new copper iodide/organic hybrid incorporated with methyl viologen, [（MV）（Cu2I4）·H2O]n（1, MV = methyl viologen）, has been solvothermally synthesized and structurally determined by X-ray diffraction method. 1 crystallizes in tetragonal system, space group P42212 with Mr = 838.95, a = 12.4721（18）, c = 6.5892（13A, V = 1025.0（3） A3, Z = 2, Dc = 2.7125 g/cm3, F（000） = 756, μ（Mo Kα） = 8.097 mm–1, the final R = 0.0273 and wR = 0.0665 for 1062 observed reflections with I 〉 2σ（I）. In 1, the（Cu2I4）n2n- chain was constructed from edge-sharing of distorted Cu I4 tetrahedra. Its absorption spectrum and photoluminescence were investigated, and energy band gap of 1.76 e V indicates its semiconductor nature. Interestingly, 1 exhibits photocatalytic activity for the degradation of rhodamine B.展开更多
The combination of D-π-A stilbazolium-type chromophores bearing ortho-N-alkyl substituents with iodocuprate resulted in three novel hybrids,these were,[(CMAMP)_(2)(CuI_(3))(acetone)_(0.5)]_(n)(1),[(HMAMP)(Cu_(3)I_(4)...The combination of D-π-A stilbazolium-type chromophores bearing ortho-N-alkyl substituents with iodocuprate resulted in three novel hybrids,these were,[(CMAMP)_(2)(CuI_(3))(acetone)_(0.5)]_(n)(1),[(HMAMP)(Cu_(3)I_(4))]n(2),and[(HMAHP)_(2)(Cu_(5)I_(7))]n(3),which present natural quantum-well architectures with void spaces of quasi-2-D organic layers occupied by iodocuprate anions via C-H⋯I hydrogen bonds.The D-π-A stilbazolium dyes exhibit head-to-tail arranged H-aggregations with face-to-faceπ⋯πstacking interactions.Theoretical calculations suggest that the charge densities on the benzenes can be strengthened from the electron-withdrawing group(-CN)to the electron-donating group(-OH),and the-C_(2)H_(5)OH substituents on the ortho-N of the pyridines not only help to open up the band gaps,but also provide a steric effect for better face-to-faceπ⋯πstacking interactions.Therefore,HMAHP^(+)in 3 possesses the strongest face-to-faceπ⋯πstacking interactions owing to the presence of a longer-C_(2)H_(5)OH group in the ortho-N position,and consequently,blue-shifted photoluminescence,a stronger photocurrent(0.28 mA),and a higher ON/OFF ratio(1.6×10^(4))can be observed in 3.In particular,electrical bistability performances can be observed in ITO/hybrids/poly(methyl methacrylate)(PMMA)/Ag devices,which are explained using Schottky emission,space-charge-limited current effect(SCLC)and Ohmic mechanisms.According to theoretical calculations,the band gap switching from the semi-conductor to the conductor(high resistance state(HRS)to low resistance state(LRS))after trapping electrons is exclusively dominated by theπbonding and anti-bonding orbitals of the stilbazolium dyes,which indicates a future direction for the design of stilbazolium-containingmemory devices.展开更多
A remarkable effect of solvents on the reaction outcome has been discovered in the synthesis of halocuprates,as exemplified by the reaction of CuI with 1-methyl-2-methylthiopyridinium iodide,(Me–PySMe)I.When performe...A remarkable effect of solvents on the reaction outcome has been discovered in the synthesis of halocuprates,as exemplified by the reaction of CuI with 1-methyl-2-methylthiopyridinium iodide,(Me–PySMe)I.When performed in acetonitrile,the reaction results in the selective self-assembly of iodocuprate(Me–PySMe)n[Cu_(2)I_(3)]_(n)(1)featuring 1D double-stranded[Cu_(2)I_(3)]_(n) ribbons.Surprisingly,upon exploiting acetone as a medium under other conditions being similar,isomeric 1D iodocuprate 2 containing one-stranded[Cu_(2)I_(3)]_(n) chains is quantitatively formed.Iodocuprate 1 displays outstanding dual luminescence expressed by two emission bands at λ_(max)=680 and 550 nm,probably originating from the excited states of the cluster-centered(^(3)CC)type and iodocuprate-to-cation charge transfer one,respectively.The resulting emission color of 1,being defined by the ratio of these bands,reversibly varies as a function of temperature spanning from deep-red(300 K)to yellow(77 K).Isomer 2,being also dual emissive,does not exhibit prominent thermochromic luminescence.展开更多
文摘A new copper iodide/organic hybrid incorporated with methyl viologen, [（MV）（Cu2I4）·H2O]n（1, MV = methyl viologen）, has been solvothermally synthesized and structurally determined by X-ray diffraction method. 1 crystallizes in tetragonal system, space group P42212 with Mr = 838.95, a = 12.4721（18）, c = 6.5892（13A, V = 1025.0（3） A3, Z = 2, Dc = 2.7125 g/cm3, F（000） = 756, μ（Mo Kα） = 8.097 mm–1, the final R = 0.0273 and wR = 0.0665 for 1062 observed reflections with I 〉 2σ（I）. In 1, the（Cu2I4）n2n- chain was constructed from edge-sharing of distorted Cu I4 tetrahedra. Its absorption spectrum and photoluminescence were investigated, and energy band gap of 1.76 e V indicates its semiconductor nature. Interestingly, 1 exhibits photocatalytic activity for the degradation of rhodamine B.
基金supported by the National Natural Science Foundation of China(No.:21771038)the National Natural Science Foundation of Fujian Province(2018J01684).
文摘The combination of D-π-A stilbazolium-type chromophores bearing ortho-N-alkyl substituents with iodocuprate resulted in three novel hybrids,these were,[(CMAMP)_(2)(CuI_(3))(acetone)_(0.5)]_(n)(1),[(HMAMP)(Cu_(3)I_(4))]n(2),and[(HMAHP)_(2)(Cu_(5)I_(7))]n(3),which present natural quantum-well architectures with void spaces of quasi-2-D organic layers occupied by iodocuprate anions via C-H⋯I hydrogen bonds.The D-π-A stilbazolium dyes exhibit head-to-tail arranged H-aggregations with face-to-faceπ⋯πstacking interactions.Theoretical calculations suggest that the charge densities on the benzenes can be strengthened from the electron-withdrawing group(-CN)to the electron-donating group(-OH),and the-C_(2)H_(5)OH substituents on the ortho-N of the pyridines not only help to open up the band gaps,but also provide a steric effect for better face-to-faceπ⋯πstacking interactions.Therefore,HMAHP^(+)in 3 possesses the strongest face-to-faceπ⋯πstacking interactions owing to the presence of a longer-C_(2)H_(5)OH group in the ortho-N position,and consequently,blue-shifted photoluminescence,a stronger photocurrent(0.28 mA),and a higher ON/OFF ratio(1.6×10^(4))can be observed in 3.In particular,electrical bistability performances can be observed in ITO/hybrids/poly(methyl methacrylate)(PMMA)/Ag devices,which are explained using Schottky emission,space-charge-limited current effect(SCLC)and Ohmic mechanisms.According to theoretical calculations,the band gap switching from the semi-conductor to the conductor(high resistance state(HRS)to low resistance state(LRS))after trapping electrons is exclusively dominated by theπbonding and anti-bonding orbitals of the stilbazolium dyes,which indicates a future direction for the design of stilbazolium-containingmemory devices.
文摘A remarkable effect of solvents on the reaction outcome has been discovered in the synthesis of halocuprates,as exemplified by the reaction of CuI with 1-methyl-2-methylthiopyridinium iodide,(Me–PySMe)I.When performed in acetonitrile,the reaction results in the selective self-assembly of iodocuprate(Me–PySMe)n[Cu_(2)I_(3)]_(n)(1)featuring 1D double-stranded[Cu_(2)I_(3)]_(n) ribbons.Surprisingly,upon exploiting acetone as a medium under other conditions being similar,isomeric 1D iodocuprate 2 containing one-stranded[Cu_(2)I_(3)]_(n) chains is quantitatively formed.Iodocuprate 1 displays outstanding dual luminescence expressed by two emission bands at λ_(max)=680 and 550 nm,probably originating from the excited states of the cluster-centered(^(3)CC)type and iodocuprate-to-cation charge transfer one,respectively.The resulting emission color of 1,being defined by the ratio of these bands,reversibly varies as a function of temperature spanning from deep-red(300 K)to yellow(77 K).Isomer 2,being also dual emissive,does not exhibit prominent thermochromic luminescence.
