The diphenyldiacetylene （DPDA） and the corresponding polymers has become one of hot research topics in the field of functional materials, due to its highly π-conjugated system and outstanding electrochemical proper...The diphenyldiacetylene （DPDA） and the corresponding polymers has become one of hot research topics in the field of functional materials, due to its highly π-conjugated system and outstanding electrochemical properties. Compared with routine polydiacetylenes, polydiphenyldiacetylene （PDPDA） has wider π-extension within the whole polymer structure and a larger internlolecular stacking tendency. Since the preorganization of monomers is essential for the topochemical polymerization, we here introduce several self-assembled methods and external-templated methods for the proper alignment of DPDA. From the perspective of morphology, the monomer structures and external templates are two of the important factors towards polymerization. Based on its structure, PDPDA can become a promising intelligent material for various optoelectical applications, and specifically we summarize the application of PDPDA as an effective phtocatalyst in organic pollutants degradation展开更多
Developing and understanding the topochemical polymerization behavior of metal-organic frameworks(MOFs) exhibits great potential for synthesizing crystalline polymers for various applications,however,it is still a cha...Developing and understanding the topochemical polymerization behavior of metal-organic frameworks(MOFs) exhibits great potential for synthesizing crystalline polymers for various applications,however,it is still a challenging task under pressure treatment.Herein,we study the pressure-induced topochemical polymerization of MOFs on their photoluminescence property.The pillar-layered diacetylene MOFs possess favorable stacking orientation and spatial arrangement between the diacetylene ligands.Such orientation and compact arrangements prompt the topochemical polymerization via 1,4-addition reactions,driven by the lattice compression upon pressure.The lattice compression and topochemical polymerization have been demonstrated by in situ high-pressure XRD patterns and Raman spectra.Additionally,three diacetylene MOFs exhibited distinct piezofluorochromic properties,including emission changes and wavelength shifts with increasing pressure.This study not only demonstrates the potential of designing pressure-responsive MOFs based on topochemical polymerization but also provides direct support for elucidating the ambiguous mechanism of pressure response and a new strategy for regulating optical properties.展开更多
Topochemical polymerization of molecular crystals into porous materials is of significance due to their promising applications in the field of adsorption and catalysis,yet rarely reported due to the synthesis difficul...Topochemical polymerization of molecular crystals into porous materials is of significance due to their promising applications in the field of adsorption and catalysis,yet rarely reported due to the synthesis difficulty.Herein,a hydrogen-bonded organic framework(HOF-45)has been fabricated by the crystallization of a cage-like building block containing three alkynyl groups.It exhibits almost mesoporous structure demonstrated by single crystal X-ray diffraction study.Light-driven topochemical polymerization of HOF-45 with ethanedithiol covalently links alkynyl groups in HOF-45,generating a hydrogen-bond and covalentbond cross-linked material(HOF-45C).In contrast to HOF-45,cross-linked HOF-45C retains the crystalline nature and displays improved solution resistence according to the powder X-ray diffraction data.In particular,HOF-45C is able to support the growth of ultrafine palladium nanoparticles with the average size of ca.1.9 nm for rapidly promoting the degradation of nitrophenol,methyl orange,and congo red with the help of NaBH_(4)as well as Suzuki-Miyaura coupling reaction.This work inputs a new idea on the HOFs application in preparing covalent-linked porous organic materials.展开更多
基金supported by the National Natural Science Foundation of China(NSFC, No. 21644005)National Program for Thousand Young Talents of ChinaState Key Project of Research and Development (No. 2016YFC1100300)
文摘The diphenyldiacetylene （DPDA） and the corresponding polymers has become one of hot research topics in the field of functional materials, due to its highly π-conjugated system and outstanding electrochemical properties. Compared with routine polydiacetylenes, polydiphenyldiacetylene （PDPDA） has wider π-extension within the whole polymer structure and a larger internlolecular stacking tendency. Since the preorganization of monomers is essential for the topochemical polymerization, we here introduce several self-assembled methods and external-templated methods for the proper alignment of DPDA. From the perspective of morphology, the monomer structures and external templates are two of the important factors towards polymerization. Based on its structure, PDPDA can become a promising intelligent material for various optoelectical applications, and specifically we summarize the application of PDPDA as an effective phtocatalyst in organic pollutants degradation
基金supported by the National Natural Science Foundation of China (U23A2095,22122307,22073099,12104415)the Youth Innovation Promotion Association of the Chinese Academy of Sciences (Y2022081)+3 种基金the Natural Science Foundation of Fujian Province (2022J06031)the STS Project of Fujian-CAS (2023T3003,2023T3052)the Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China (2021ZR131)the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB1170000,XDB0970302)。
文摘Developing and understanding the topochemical polymerization behavior of metal-organic frameworks(MOFs) exhibits great potential for synthesizing crystalline polymers for various applications,however,it is still a challenging task under pressure treatment.Herein,we study the pressure-induced topochemical polymerization of MOFs on their photoluminescence property.The pillar-layered diacetylene MOFs possess favorable stacking orientation and spatial arrangement between the diacetylene ligands.Such orientation and compact arrangements prompt the topochemical polymerization via 1,4-addition reactions,driven by the lattice compression upon pressure.The lattice compression and topochemical polymerization have been demonstrated by in situ high-pressure XRD patterns and Raman spectra.Additionally,three diacetylene MOFs exhibited distinct piezofluorochromic properties,including emission changes and wavelength shifts with increasing pressure.This study not only demonstrates the potential of designing pressure-responsive MOFs based on topochemical polymerization but also provides direct support for elucidating the ambiguous mechanism of pressure response and a new strategy for regulating optical properties.
基金supported by the Natural Science Foundation of China(22235001,22175020,22131005,22011540002,21631003)the Xiaomi Young Scholar Program+1 种基金the Fundamental Research Funds for the Central UniversitiesUniversity of Science and Technology Beijing
文摘Topochemical polymerization of molecular crystals into porous materials is of significance due to their promising applications in the field of adsorption and catalysis,yet rarely reported due to the synthesis difficulty.Herein,a hydrogen-bonded organic framework(HOF-45)has been fabricated by the crystallization of a cage-like building block containing three alkynyl groups.It exhibits almost mesoporous structure demonstrated by single crystal X-ray diffraction study.Light-driven topochemical polymerization of HOF-45 with ethanedithiol covalently links alkynyl groups in HOF-45,generating a hydrogen-bond and covalentbond cross-linked material(HOF-45C).In contrast to HOF-45,cross-linked HOF-45C retains the crystalline nature and displays improved solution resistence according to the powder X-ray diffraction data.In particular,HOF-45C is able to support the growth of ultrafine palladium nanoparticles with the average size of ca.1.9 nm for rapidly promoting the degradation of nitrophenol,methyl orange,and congo red with the help of NaBH_(4)as well as Suzuki-Miyaura coupling reaction.This work inputs a new idea on the HOFs application in preparing covalent-linked porous organic materials.
