Stability against oxygen is an important factor affecting the performance of organic semiconductor devices.Improving photooxidation stability can prolong the service life of the device and maintain the mechanical and ...Stability against oxygen is an important factor affecting the performance of organic semiconductor devices.Improving photooxidation stability can prolong the service life of the device and maintain the mechanical and photoelectric properties of the device.Generally,various encapsulation methods from molecular structure to macroscopic device level are used to improve photooxidation stability.Here,we adopted a crystallization strategy to allow 14H-spiro[dibenzo[c,h]acridine-7,9′-fluorene](SFDBA)to pack tightly to resist fluorescence decay caused by oxidation.In this case,the inert group of SFDBA acts as a“steric armor”,protecting the photosensitive group from being attacked by oxygen.Therefore,compared with the fluorescence quenching of SFDBA powder under 2 h of sunlight,SFDBA crystal can maintain its fluorescence emission for more than 8 h under the same conditions.Furthermore,the photoluminescence quantum yields(PLQYs)of the crystalline film is 327%higher than that of the amorphous film.It shows that the crystallization strategy is an effective method to resist oxidation.展开更多
A novel type of A-type nanogrids(AGs)with axial and central chirality was synthesized via Friedel-Crafts gridization of thiophenes and difluorenyl biaromatic derivatives,yielding 9%-30%.Additionally,the effect of ster...A novel type of A-type nanogrids(AGs)with axial and central chirality was synthesized via Friedel-Crafts gridization of thiophenes and difluorenyl biaromatic derivatives,yielding 9%-30%.Additionally,the effect of stereoisomers of 1,1'-binaphthyl difluorenols(BINDFOH)was investigated to demonstrate that R/S-BINDFOH is more advantageous for the synthesis of AGs than Mix-BINDFOH.Furthermore,tests on OFET memory devices showed that AGs have a larger storage window,indicating potential for data storage applications.展开更多
Precisely optimizing the morphology of functional hybrid polymeric systems is crucial to improve its photophysical property and further extend their optoelectronic applications. The physic-chemical property of polymer...Precisely optimizing the morphology of functional hybrid polymeric systems is crucial to improve its photophysical property and further extend their optoelectronic applications. The physic-chemical property of polymeric matrix in electrospinning (ES) processing is a key factor to dominate the condensed structure of these hybrid microstructures and further improve its functionality. Herein, we set a flexible poly(ethylene oxide) (PEO) as the matrix to obtain a series of polydiarylfluorenes (including PHDPF, PODPF and PNDPF) electrospun hybrid microfibers with a robust deep-blue emission. Significantly different from the rough morphology of their poly(N-vinylcarbazole) (PVK) ES hybrid fibers, polydiarylfluorenes/PEO ES fibers showed a smooth morphology and small size with a diameter of 1∼2 µm. Besides, there is a relatively weak phase separation under rapid solvent evaporation during the ES processing, associated with the hydrogen-bonded-assisted network of PEO in ES fibers. These relative “homogeneous” ES fibers present efficient deep-blue emission (PLQY>50%), due to weak interchain aggregation. More interestingly, low fraction of planar (β) conformation appears in the uniform PODPF/PEO ES fibers, induced by the external traction force in ES processing. Meanwhile, PNDPF/PEO ES fibers present a highest sensitivity than those of other ES fibers, associated with the smallest diameter and large surface area. Finally, compared to PODPF/PVK fibers and PODPF/PEO amorphous ES fibers, PODPF/PEO ES fibers obtained from DCE solution exhibit an excellent quenching behavior toward a saturated DNT vapor, mainly due to the synergistic effect of small size, weak separation, β-conformation formation and high deep-blue emission efficiency.展开更多
Two-dimensional(2D)organic nanomaterials are attracting increasing research interest and expected to be the ideal candidate for futureproofed flexible electronics and biotechnologies.Owing to the complex molecular str...Two-dimensional(2D)organic nanomaterials are attracting increasing research interest and expected to be the ideal candidate for futureproofed flexible electronics and biotechnologies.Owing to the complex molecular structures and multiple intermolecular interactions in organic systems,deeper understanding of rational molecular design and assembly principles is urgently required.In this review,a collection of molecular packing mode in the 2D organic nanomaterials via supramolecular assembly is presented,so as to help explicit the relationship among molecular structures,supramolecular interactions and molecular packing motifs in 2D assembly systems.We also provide a rational and accessible schematic model to demonstrate several typical kinds of molecular packing motifs for the prediction of the 2D morphology.展开更多
Organic semiconductor materials with low reorganization energy have various applications such as in organic light-emitting diodes (OLEDs),organic field-effect transistor (OFETs) and organic solar cells (OSCs).In this ...Organic semiconductor materials with low reorganization energy have various applications such as in organic light-emitting diodes (OLEDs),organic field-effect transistor (OFETs) and organic solar cells (OSCs).In this work,we have designed a new class of gridspiroarenes (GS-SFX and GS-SITF) with #-shaped structures,which have novel crisscross geometrical structures compared to widely used spirocyclic arenes-SFX and SITF.The structure electronic properties,adiabatic ionization potentials (IPa),adiabatic electron affinities (EAa) and reorganization energies (λ) of GS-SFX and GS-SITF have been calculated using density functional theory (DFT) method.The calculated HOMO and LUMO spatial distributions suggest that GS-SFX and GS-SITF have better transport properties.The noncovalent interaction analysis shows the weak intramolecular interactions between their arms.The results indicate that the reorganization energies of GS-SFX and GS-SITF are significantly reduced compared to the dimer structures-DSFX and DSITF.Furthermore,the GS-SITF1 which is one of the isomers of GS-SITF exhibits the lowest values for λ(h)(0.067 eV) and λ(e)(0.153 eV).Therefore,we believe the predicted structure,electronic property,and reorganization energy are good indicator for transport materials.This work has systematically studied the effect of gridization,which provides insights to design organic semiconductor materials with excellent charge transport properties.展开更多
As a novel class of spirofluorenes,spirobifluorene(SBF)and spiro[fluo-rene-9,9'-xanthene]derivatives(SFXs)have orthogonal geometric config-uration,spiro-conjugation effect,and rigid steric hindrance,which can be w...As a novel class of spirofluorenes,spirobifluorene(SBF)and spiro[fluo-rene-9,9'-xanthene]derivatives(SFXs)have orthogonal geometric config-uration,spiro-conjugation effect,and rigid steric hindrance,which can be widely used in the fields of synthetic chemistry,materials chemistry and supramolecular chemistry.Due to their facile one-pot synthetic route,and to the variety of molecular designs,SFXs are expected to become new spiro functional materials that replace SBF.In this review,we present the history,development and expansion of SFXs synthesis in one-pot methods,and the advantages and limitations of one-pot synthesis are also dis-cussed.展开更多
A type of novel electrospun supramolecular hybrid microfibers comprising poly(9-(4-(octyloxy)-phenyl)-2,7-fluoren-9-ol)(PPFOH)and poly(A/-vinylcarbazole)(PVK)are successfully prepared for intriguing multi-color emissi...A type of novel electrospun supramolecular hybrid microfibers comprising poly(9-(4-(octyloxy)-phenyl)-2,7-fluoren-9-ol)(PPFOH)and poly(A/-vinylcarbazole)(PVK)are successfully prepared for intriguing multi-color emission properties.The supramolecular tunable PPFOH aggregation in PVK matrix endows the complex with a smart energy transfer behavior to obtain the multi-color emissions.In stark contrast to PVK fibers,the emission color of PPFOH/PVK fibers with an efficient dispersion of PPFOH fluorophores at a proper dope ratio can be tuned in a wide spectrum of blue(0.1%),sky blue(0.5%),nearly white(1%),cyan(2%),green(5%)and yellow(10%).Besides,conductive behaviors of the microfiber were demonstrated in accompany with the increment of the doping ratio of PPFOH to PVK.Successful fabrication of polymer light-emitting diode(PLED)based on the blended electrospun fiber provided a further evidence of its excellent electrical property for potential applications in optoelectronic devices.展开更多
Molecular aggregates in conjugated polymer（CP） solution can propagate into mesoscale morphology of the relevant film and further dominate the optoelectronic property. Herein, we probed the aggregation behavior of p...Molecular aggregates in conjugated polymer（CP） solution can propagate into mesoscale morphology of the relevant film and further dominate the optoelectronic property. Herein, we probed the aggregation behavior of poly（9,9-dioctylfluorene-2,7-diyl）（PFO） and studied its influence on the photophysical property in 1,2-dichloroethane（DCE） solution, where the contents of β-phase or-aggregates increased with prolonged aging time. Thereinto, high quality β-film was fabricated from DCE solution with critical aggregate time of 6 min. The film exhibited excellent surface morphology and characteristic emission of β-phase. Meanwhile, films prepared from aged DCE solutions exhibited high crystallinity, which was promising to obtain higher photoluminance efficiency and charge transport ability simultaneously. Therefore, it is significant to get deep insight into the aggregation behavior of CP, which is involved not only with the solution-processing technology of plastic device, but also with the optoelectronic property of CP.展开更多
Rare attention has been paid to the comparison between a monomer and its corresponding polymer in terms of the optoelectronic characteristics. In this article, a model H-shaped molecule and its corresponding polymer, ...Rare attention has been paid to the comparison between a monomer and its corresponding polymer in terms of the optoelectronic characteristics. In this article, a model H-shaped molecule and its corresponding polymer, both of which exhibited similar properties including blue emission and solution processing, were designed and synthesized. Optoelectronic properties and various kinds of stability features, including the thermostabilities, spectral stabilities and amplified spontaneous emission characteristic of the monomer and polymer were investigated. In general, the corresponding polymer PH exhibited similar optoelectronic properties but deteriorated stabilities compared with its H-shaped monomer H-1 probably owing to the similar chemical structure but the wider molecular weight distribution and metal catalyst residue. Importantly, monomer H-1 displayed a comparable ASE threshold value with its polymer PH,suggesting that H-shaped fluorene-based small molecules may be more promising optical gain media in solid state amplifers and lasers.展开更多
基金supported by the Natural Science Foundation of Nanjing University of Posts and Telecommunications(NY222157,NY221085)State Key Laboratory of Organic Electronics and Information Display(GZR2022010008)+5 种基金Key Laboratory of Low-dimensional Materials Chemistry of Jiangsu Province(JSKC20022)General Program of China Postdoctoral Science Foundation(2022M711684)General Program of Basic Science(Natural Science)of Colleges and Universities of Jiangsu Province(22KJB430036)National Overseas Study Fund(202008320051)National Key Laboratory(2009DS690095)the National Natural Science Foundation of China(62288102).
文摘Stability against oxygen is an important factor affecting the performance of organic semiconductor devices.Improving photooxidation stability can prolong the service life of the device and maintain the mechanical and photoelectric properties of the device.Generally,various encapsulation methods from molecular structure to macroscopic device level are used to improve photooxidation stability.Here,we adopted a crystallization strategy to allow 14H-spiro[dibenzo[c,h]acridine-7,9′-fluorene](SFDBA)to pack tightly to resist fluorescence decay caused by oxidation.In this case,the inert group of SFDBA acts as a“steric armor”,protecting the photosensitive group from being attacked by oxygen.Therefore,compared with the fluorescence quenching of SFDBA powder under 2 h of sunlight,SFDBA crystal can maintain its fluorescence emission for more than 8 h under the same conditions.Furthermore,the photoluminescence quantum yields(PLQYs)of the crystalline film is 327%higher than that of the amorphous film.It shows that the crystallization strategy is an effective method to resist oxidation.
基金supported by the National Natural Science Foundation of China(22071112 and 22275098)the Project of State Key Laboratory of Organic Electronics and Information Displays,Nanjing University of Posts and Telecommunications(GDX2022010005 and GZR2022010011).
文摘A novel type of A-type nanogrids(AGs)with axial and central chirality was synthesized via Friedel-Crafts gridization of thiophenes and difluorenyl biaromatic derivatives,yielding 9%-30%.Additionally,the effect of stereoisomers of 1,1'-binaphthyl difluorenols(BINDFOH)was investigated to demonstrate that R/S-BINDFOH is more advantageous for the synthesis of AGs than Mix-BINDFOH.Furthermore,tests on OFET memory devices showed that AGs have a larger storage window,indicating potential for data storage applications.
基金supported by the National Natural Science Foundation of China(Nos.22075136 and 61874053)the open research fund from Anhui Province Key Laboratory of Environment-friendly Polymer Materials,Anhui Province Key Laboratory of Optoelectronic Materials Science and Technologythe State Key Laboratory of Luminescent Materials and Devices(South China University of Technology).
文摘Precisely optimizing the morphology of functional hybrid polymeric systems is crucial to improve its photophysical property and further extend their optoelectronic applications. The physic-chemical property of polymeric matrix in electrospinning (ES) processing is a key factor to dominate the condensed structure of these hybrid microstructures and further improve its functionality. Herein, we set a flexible poly(ethylene oxide) (PEO) as the matrix to obtain a series of polydiarylfluorenes (including PHDPF, PODPF and PNDPF) electrospun hybrid microfibers with a robust deep-blue emission. Significantly different from the rough morphology of their poly(N-vinylcarbazole) (PVK) ES hybrid fibers, polydiarylfluorenes/PEO ES fibers showed a smooth morphology and small size with a diameter of 1∼2 µm. Besides, there is a relatively weak phase separation under rapid solvent evaporation during the ES processing, associated with the hydrogen-bonded-assisted network of PEO in ES fibers. These relative “homogeneous” ES fibers present efficient deep-blue emission (PLQY>50%), due to weak interchain aggregation. More interestingly, low fraction of planar (β) conformation appears in the uniform PODPF/PEO ES fibers, induced by the external traction force in ES processing. Meanwhile, PNDPF/PEO ES fibers present a highest sensitivity than those of other ES fibers, associated with the smallest diameter and large surface area. Finally, compared to PODPF/PVK fibers and PODPF/PEO amorphous ES fibers, PODPF/PEO ES fibers obtained from DCE solution exhibit an excellent quenching behavior toward a saturated DNT vapor, mainly due to the synergistic effect of small size, weak separation, β-conformation formation and high deep-blue emission efficiency.
基金the National Natural Science Foundation of China(61604081)Excellent science and technology innovation team of Jiangsu Higher Education Institutions(2013),Natural Science Foundation of Jiangsu Provinee,China(BM2012010)+2 种基金the Six Talent Peaks Project of Jiangsu Province(XCL-CXTD-009)Project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions,PAPD(YX03002)the Funding of Jiangsu Innovation Program for Graduate Education(46030CX17758).
文摘Two-dimensional(2D)organic nanomaterials are attracting increasing research interest and expected to be the ideal candidate for futureproofed flexible electronics and biotechnologies.Owing to the complex molecular structures and multiple intermolecular interactions in organic systems,deeper understanding of rational molecular design and assembly principles is urgently required.In this review,a collection of molecular packing mode in the 2D organic nanomaterials via supramolecular assembly is presented,so as to help explicit the relationship among molecular structures,supramolecular interactions and molecular packing motifs in 2D assembly systems.We also provide a rational and accessible schematic model to demonstrate several typical kinds of molecular packing motifs for the prediction of the 2D morphology.
基金This work was supported by the National Natural Science Foundation of China (Nos. 21503114, 21774061, 61605090, 91833306)Synergetic Innovation Centre for Organic Electronics and In formation Displays, Nanji ng Un iversity of Posts a nd Telecommunications Scientific Foundation NUPTSF (NY215056, NY21417& NY215172, 2016XSG03)the Six Peak Talents Foundation of Jiangsu Province (XCL-CXTD-009), and the High Performanee Computing Center of Nanjing Tech University.
文摘Organic semiconductor materials with low reorganization energy have various applications such as in organic light-emitting diodes (OLEDs),organic field-effect transistor (OFETs) and organic solar cells (OSCs).In this work,we have designed a new class of gridspiroarenes (GS-SFX and GS-SITF) with #-shaped structures,which have novel crisscross geometrical structures compared to widely used spirocyclic arenes-SFX and SITF.The structure electronic properties,adiabatic ionization potentials (IPa),adiabatic electron affinities (EAa) and reorganization energies (λ) of GS-SFX and GS-SITF have been calculated using density functional theory (DFT) method.The calculated HOMO and LUMO spatial distributions suggest that GS-SFX and GS-SITF have better transport properties.The noncovalent interaction analysis shows the weak intramolecular interactions between their arms.The results indicate that the reorganization energies of GS-SFX and GS-SITF are significantly reduced compared to the dimer structures-DSFX and DSITF.Furthermore,the GS-SITF1 which is one of the isomers of GS-SITF exhibits the lowest values for λ(h)(0.067 eV) and λ(e)(0.153 eV).Therefore,we believe the predicted structure,electronic property,and reorganization energy are good indicator for transport materials.This work has systematically studied the effect of gridization,which provides insights to design organic semiconductor materials with excellent charge transport properties.
基金the National Natural Science Foundation of China(21774061,2207112 and 61935017)Natural Science Foundation major research program integration project(Grant Number 91833306)+1 种基金Six Peak Talents Foundation of Jiangsu Province(XCLCXTD-009)Open Project from State Key Labor-atory of Supramolecular Structure and Materials at Jilin University(No.sklssm202014).
文摘As a novel class of spirofluorenes,spirobifluorene(SBF)and spiro[fluo-rene-9,9'-xanthene]derivatives(SFXs)have orthogonal geometric config-uration,spiro-conjugation effect,and rigid steric hindrance,which can be widely used in the fields of synthetic chemistry,materials chemistry and supramolecular chemistry.Due to their facile one-pot synthetic route,and to the variety of molecular designs,SFXs are expected to become new spiro functional materials that replace SBF.In this review,we present the history,development and expansion of SFXs synthesis in one-pot methods,and the advantages and limitations of one-pot synthesis are also dis-cussed.
基金the Six Peak Talents Foundation of Jiangsu Province(Nos.XCL-CXTD-009 and XYDXX-019)the National Natural Science Foundation of China(Nos.22075136,21471082,21472186,61874053 and 21272231)+3 种基金Natural Science Funds of the Education Committee of Jiangsu Province(Nos.18KJA510003 and 18KJA430009)Natural Science Foundation of Jiangsu Province(No.BK20200700)Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD,No.YX030003)the open research fund from Key Laboratory for Organic Electronics and Information Displays and Qing Lan Project of Jiangsu Province.
文摘A type of novel electrospun supramolecular hybrid microfibers comprising poly(9-(4-(octyloxy)-phenyl)-2,7-fluoren-9-ol)(PPFOH)and poly(A/-vinylcarbazole)(PVK)are successfully prepared for intriguing multi-color emission properties.The supramolecular tunable PPFOH aggregation in PVK matrix endows the complex with a smart energy transfer behavior to obtain the multi-color emissions.In stark contrast to PVK fibers,the emission color of PPFOH/PVK fibers with an efficient dispersion of PPFOH fluorophores at a proper dope ratio can be tuned in a wide spectrum of blue(0.1%),sky blue(0.5%),nearly white(1%),cyan(2%),green(5%)and yellow(10%).Besides,conductive behaviors of the microfiber were demonstrated in accompany with the increment of the doping ratio of PPFOH to PVK.Successful fabrication of polymer light-emitting diode(PLED)based on the blended electrospun fiber provided a further evidence of its excellent electrical property for potential applications in optoelectronic devices.
基金financially supported by the National Key Basic Research Program of China(973)(No.2015CB932200)the National Natural Science Funds for Excellent Young Scholar(No.21322402)+6 种基金the National Natural Science Foundation of China(Nos.21504041,21274064 and 61475074)University of Jiangsu Province Natural Science Foundation Project(No.14KJB510027)Natural Science of the Education Committee of Jiangsu Province(No.15KJB430019)Jiangsu Planned Projects for Postdoctoral Research Funds(No.1501019B)China Postdoctoral Science Foundation(No.2015M580419)SICAM Fellowship,Imperial College LondonOpen Project from State Key Laboratory of Supramolecular Structure and Materials at Jilin University(No.sklssm201612)
文摘Molecular aggregates in conjugated polymer（CP） solution can propagate into mesoscale morphology of the relevant film and further dominate the optoelectronic property. Herein, we probed the aggregation behavior of poly（9,9-dioctylfluorene-2,7-diyl）（PFO） and studied its influence on the photophysical property in 1,2-dichloroethane（DCE） solution, where the contents of β-phase or-aggregates increased with prolonged aging time. Thereinto, high quality β-film was fabricated from DCE solution with critical aggregate time of 6 min. The film exhibited excellent surface morphology and characteristic emission of β-phase. Meanwhile, films prepared from aged DCE solutions exhibited high crystallinity, which was promising to obtain higher photoluminance efficiency and charge transport ability simultaneously. Therefore, it is significant to get deep insight into the aggregation behavior of CP, which is involved not only with the solution-processing technology of plastic device, but also with the optoelectronic property of CP.
基金financially supported by the National Natural Science Foundation of China (Nos. 21504047, 21774061)the Six Peak Talents Foundation of Jiangsu Province (No. XCL-CXTD009)+1 种基金Natural Science Foundation of Jiangsu Province (No. BK20150834)Synergetic Innovation Center for Organic Electronics and Information Displays
文摘Rare attention has been paid to the comparison between a monomer and its corresponding polymer in terms of the optoelectronic characteristics. In this article, a model H-shaped molecule and its corresponding polymer, both of which exhibited similar properties including blue emission and solution processing, were designed and synthesized. Optoelectronic properties and various kinds of stability features, including the thermostabilities, spectral stabilities and amplified spontaneous emission characteristic of the monomer and polymer were investigated. In general, the corresponding polymer PH exhibited similar optoelectronic properties but deteriorated stabilities compared with its H-shaped monomer H-1 probably owing to the similar chemical structure but the wider molecular weight distribution and metal catalyst residue. Importantly, monomer H-1 displayed a comparable ASE threshold value with its polymer PH,suggesting that H-shaped fluorene-based small molecules may be more promising optical gain media in solid state amplifers and lasers.
