Crystalline complexes that exhibited light switchable proton conductivity are of great interest but still a challenge in material science.Herein,a terbium phosphonate chain complex was synthesized through assembly of ...Crystalline complexes that exhibited light switchable proton conductivity are of great interest but still a challenge in material science.Herein,a terbium phosphonate chain complex was synthesized through assembly of electron-rich phosphonate units,electron-deficient polypyridine components and paramagnetic Tb^(3+)ions.Via light irradiation and heat treatment,the photogenerated radicals could simultaneously and reversibly tune the photochromic,luminescent and magnetic properties.Originating from the abundant hydrogen bonding networks formed between PO_3 groups and lattice water molecules,proton conductive behaviour was explored with high proton conductivity of(1.74±0.19)×10^(-3)S cm^(-1)at 80°C and 100%relative humidity.Importantly,accompanied with the colorless sample changed to blue,the proton conductivity increased about 20%after room temperature light illumination,implying that light irradiation could act as an external stimulus to enhance the conductive properties of original material.This work innovatively realized the light responsive conductive property in the electron transfer photochromic materials,providing a novel strategy for the construction of smart materials.展开更多
Azulene, one of representative nonbenzenoid aromatic hydrocarbons, exhibits unique molecular structure and distinctive physical and chemical properties. Herein, azulenoisoindigo(Az II), an azulene-based isoindigo anal...Azulene, one of representative nonbenzenoid aromatic hydrocarbons, exhibits unique molecular structure and distinctive physical and chemical properties. Herein, azulenoisoindigo(Az II), an azulene-based isoindigo analogue, is designed and synthesized, which has a twisted molecular backbone and R/Sisomers in single crystals. Interestingly, Az II shows the characteristics of both isoindigo and azulene,such as reversible redox behavior and reversible proton responsiveness. UV-vis-NIR,^(1)H NMR and electron paramagnetic resonance(EPR) measurements were carried out to get insights into the possible mechanism of the proton-responsive property of Az II. The results demonstrated that only one azulenyl moiety of molecule of Az II was protonated and deprotonated, and the protonated Az II can be further oxidized to form azulenium cation radicals.展开更多
Stable organic luminescent radicals are a special class of compounds integrating optical,electrical,and magnetic properties.Luminescent radicals not only have potential applications in the field of the organic light-e...Stable organic luminescent radicals are a special class of compounds integrating optical,electrical,and magnetic properties.Luminescent radicals not only have potential applications in the field of the organic light-emitting diodes(OLEDs)but can also be applied in the fields of fluorescence sensing,bioimaging,and so forth.Nevertheless,due to the adverse effects of solvent polarity on the luminescent performance of radicals,no feasible approaches have been found in the literature toward fluorescent sensing.In this work,we report two luminescent radicals,2αPyID-TTM and 2δPyID-TTM,whose emissions show high efficiency and less dependence on solvent polarity.Both radicals show remarkable protonation–deprotonation properties.Besides,2αPyID-TTM exhibits significant fluorescence quenching and colorimetric response toward Fe^(3+)in aqueous solution.This suggests the possibility of a fluorometric/colorimetric dual-channel probe for Fe^(3+).Moreover,an optimized OLED using 2δPyID-TTM as an emissive dopant shows pure red emission and a maximum external quantum efficiency(EQE)of 10.6%.These results show promise for luminescent radicals as fluorescent probes and electroluminescent emitters.展开更多
基金supported by the National Natural Science Foundation of China(21901133,22071125,22071126,21571111)Key Research and Development Project of Shandong Province(2019GGX102006)。
文摘Crystalline complexes that exhibited light switchable proton conductivity are of great interest but still a challenge in material science.Herein,a terbium phosphonate chain complex was synthesized through assembly of electron-rich phosphonate units,electron-deficient polypyridine components and paramagnetic Tb^(3+)ions.Via light irradiation and heat treatment,the photogenerated radicals could simultaneously and reversibly tune the photochromic,luminescent and magnetic properties.Originating from the abundant hydrogen bonding networks formed between PO_3 groups and lattice water molecules,proton conductive behaviour was explored with high proton conductivity of(1.74±0.19)×10^(-3)S cm^(-1)at 80°C and 100%relative humidity.Importantly,accompanied with the colorless sample changed to blue,the proton conductivity increased about 20%after room temperature light illumination,implying that light irradiation could act as an external stimulus to enhance the conductive properties of original material.This work innovatively realized the light responsive conductive property in the electron transfer photochromic materials,providing a novel strategy for the construction of smart materials.
基金financially supported by the National Natural Science Foundation of China (Nos. 21790362, 22075310 and21522209)the “Strategic Priority Research Program of Chinese Academy of Sciences”(No. XDB12010100)+1 种基金the Science and Technology Commission of Shanghai Municipality (Nos. 19XD1424700 and18JC1410600)SIOC. An early preprint of this work appeared on Chem Rxiv [47]。
文摘Azulene, one of representative nonbenzenoid aromatic hydrocarbons, exhibits unique molecular structure and distinctive physical and chemical properties. Herein, azulenoisoindigo(Az II), an azulene-based isoindigo analogue, is designed and synthesized, which has a twisted molecular backbone and R/Sisomers in single crystals. Interestingly, Az II shows the characteristics of both isoindigo and azulene,such as reversible redox behavior and reversible proton responsiveness. UV-vis-NIR,^(1)H NMR and electron paramagnetic resonance(EPR) measurements were carried out to get insights into the possible mechanism of the proton-responsive property of Az II. The results demonstrated that only one azulenyl moiety of molecule of Az II was protonated and deprotonated, and the protonated Az II can be further oxidized to form azulenium cation radicals.
基金This research was made possible by a generous grant from the National Natural Science Foundation of China(grant nos.51925303,21875083,and 91833304)the China Postdoctoral Science Foundation(grant nos.2020TQ0117 and 2020M681033)the program“JLUSTIRT”(grant no.2019TD-33).
文摘Stable organic luminescent radicals are a special class of compounds integrating optical,electrical,and magnetic properties.Luminescent radicals not only have potential applications in the field of the organic light-emitting diodes(OLEDs)but can also be applied in the fields of fluorescence sensing,bioimaging,and so forth.Nevertheless,due to the adverse effects of solvent polarity on the luminescent performance of radicals,no feasible approaches have been found in the literature toward fluorescent sensing.In this work,we report two luminescent radicals,2αPyID-TTM and 2δPyID-TTM,whose emissions show high efficiency and less dependence on solvent polarity.Both radicals show remarkable protonation–deprotonation properties.Besides,2αPyID-TTM exhibits significant fluorescence quenching and colorimetric response toward Fe^(3+)in aqueous solution.This suggests the possibility of a fluorometric/colorimetric dual-channel probe for Fe^(3+).Moreover,an optimized OLED using 2δPyID-TTM as an emissive dopant shows pure red emission and a maximum external quantum efficiency(EQE)of 10.6%.These results show promise for luminescent radicals as fluorescent probes and electroluminescent emitters.