Although the past decade has witnessed tremendous progress in the development of covalent organic frameworks(COFs),three-dimensional(3D)COFs fabrications and characterizations are still much less studied compared with...Although the past decade has witnessed tremendous progress in the development of covalent organic frameworks(COFs),three-dimensional(3D)COFs fabrications and characterizations are still much less studied compared with two-dimensional(2D)COFs,due to their complicated topology structures caused by interpenetration and limited choices of node-building blocks.In this work,we constructed a novel 3D COF(SP-3D-COF-BPY)successfully using orthogonal dual-planar spirobifluorene and bipyridine as building blocks.Also,we demonstrated the application of 3D COF-supported Pd(II)catalyst in heterogeneous catalysis.A sevenfold interpenetrated dia structure was revealed for SP-3DCOF-BPY by powder X-ray diffraction(PXRD)in conjunction with structural simulation and Pawley refinement.The bipyridine-linked frameworks bear one-dimensional(1D)unobstructed rigid channels and offer a high density of discrete coordination sites for chelating Pd(II)species.Very high loading of Pd(II)(∼15 wt%)was achieved in the asymmetric(as)-prepared Pd(II)@3D-COF-BYP.The generated highly ordered porous channels and easily accessible catalytic sites,such as COF-supported Pd(II)complex,serves as a highly active and stable microporous heterogeneous catalyst in Suzuki–Miyaura coupling reactions.The observed catalytic efficiency was high and the catalyst could be conveniently reused multiple times without any noticeable decay in catalytic performance.展开更多
The title compound 2-（spirobifluorene-2-yl）-3,4-diaza-spirobifluorene（C48H28N2,Mr = 632.72） has been synthesized and characterized by 1H NMR,13C NMR and single-crystal X-ray diffraction.The crystal crystallizes in...The title compound 2-（spirobifluorene-2-yl）-3,4-diaza-spirobifluorene（C48H28N2,Mr = 632.72） has been synthesized and characterized by 1H NMR,13C NMR and single-crystal X-ray diffraction.The crystal crystallizes in the monoclinic system,space group Cc with a = 13.8523（6）,b = 29.3297（13）,c = 8.6397（4） ,β = 111.8760（10）°,V = 3257.4（3） 3,Z = 4,Dc = 1.290 mg/m^3,μ = 0.075 mm^-1,F（000） = 1320,the final R = 0.0425 and wR = 0.1110 for 5288 observed reflections（Ⅰ 〉 2σ（Ⅰ））.展开更多
In this work,a blue emitter with a 3 D rigid structure composed of multiple spirobifluorene(3-Spiro) has been synthesized and characterized.Through a detailed study of the electrochemical and photophysical properties ...In this work,a blue emitter with a 3 D rigid structure composed of multiple spirobifluorene(3-Spiro) has been synthesized and characterized.Through a detailed study of the electrochemical and photophysical properties of 3-Spiro,we have evidenced that 3-Spiro can be applied as an active component of organic light-emitting diodes(OLEDs).The device with 5% doping rate of 4 CzPNPh exhibits high external quantum efficiency(EQE) of 11%,which proves the potential of 3 D rigid structure emitters for OLEDs.展开更多
基金The work was supported by the National Natural Science Foundation of China(nos.51722302,21674054,and 51972185).
文摘Although the past decade has witnessed tremendous progress in the development of covalent organic frameworks(COFs),three-dimensional(3D)COFs fabrications and characterizations are still much less studied compared with two-dimensional(2D)COFs,due to their complicated topology structures caused by interpenetration and limited choices of node-building blocks.In this work,we constructed a novel 3D COF(SP-3D-COF-BPY)successfully using orthogonal dual-planar spirobifluorene and bipyridine as building blocks.Also,we demonstrated the application of 3D COF-supported Pd(II)catalyst in heterogeneous catalysis.A sevenfold interpenetrated dia structure was revealed for SP-3DCOF-BPY by powder X-ray diffraction(PXRD)in conjunction with structural simulation and Pawley refinement.The bipyridine-linked frameworks bear one-dimensional(1D)unobstructed rigid channels and offer a high density of discrete coordination sites for chelating Pd(II)species.Very high loading of Pd(II)(∼15 wt%)was achieved in the asymmetric(as)-prepared Pd(II)@3D-COF-BYP.The generated highly ordered porous channels and easily accessible catalytic sites,such as COF-supported Pd(II)complex,serves as a highly active and stable microporous heterogeneous catalyst in Suzuki–Miyaura coupling reactions.The observed catalytic efficiency was high and the catalyst could be conveniently reused multiple times without any noticeable decay in catalytic performance.
基金supported by the Natural Science Foundation of Shanghai (09ZR1409400) and Laboratory of Organic Functional Molecules,the Sino-French Institute of ECNU
文摘The title compound 2-（spirobifluorene-2-yl）-3,4-diaza-spirobifluorene（C48H28N2,Mr = 632.72） has been synthesized and characterized by 1H NMR,13C NMR and single-crystal X-ray diffraction.The crystal crystallizes in the monoclinic system,space group Cc with a = 13.8523（6）,b = 29.3297（13）,c = 8.6397（4） ,β = 111.8760（10）°,V = 3257.4（3） 3,Z = 4,Dc = 1.290 mg/m^3,μ = 0.075 mm^-1,F（000） = 1320,the final R = 0.0425 and wR = 0.1110 for 5288 observed reflections（Ⅰ 〉 2σ（Ⅰ））.
基金supported by the National Natural Science Foundation of China(No.51603055)the Natural Science Foundation of Heilongjiang Province(No.QC2017055)+1 种基金the China Postdoctoral Science Foundation(Nos.2016M601424,2017T100236)the Postdoctoral Foundation of Heilongjiang Province(Nos.LBH-Z16059,LBH-TZ10)。
文摘In this work,a blue emitter with a 3 D rigid structure composed of multiple spirobifluorene(3-Spiro) has been synthesized and characterized.Through a detailed study of the electrochemical and photophysical properties of 3-Spiro,we have evidenced that 3-Spiro can be applied as an active component of organic light-emitting diodes(OLEDs).The device with 5% doping rate of 4 CzPNPh exhibits high external quantum efficiency(EQE) of 11%,which proves the potential of 3 D rigid structure emitters for OLEDs.
