Geometric structures of 135 polychlorinated fluorene （PCFR） molecules were optimized using density functional theory （DFT） at the B3LYP/6-311G＊＊ level and their thermodynamic properties in the ideal gas state we...Geometric structures of 135 polychlorinated fluorene （PCFR） molecules were optimized using density functional theory （DFT） at the B3LYP/6-311G＊＊ level and their thermodynamic properties in the ideal gas state were calculated. The relations of these thermodynamic properties with the number and position of chlorine atoms were also explored, from which the relative stability of PCFR congeners was theoretically proposed according to the magnitude of the relative standard Gibbs free energy of formation （Δr,fGθ）. The results show that the geometric configuration of PCFR isomers is determined by the position of chlorine atoms. There exist two types of intramolecular weak interactions, i.e., C–H···Cl and Cl···Cl interactions in PCFR molecules. The change of ΔfHθ and ΔfGθ of most stable PCFR isomers with increasing the number of chlorine atoms is different from that in most unstable PCFR congeners. The values of ΔfHθ and ΔfGθ for PCFR isomers with the same number of chlorine atoms strongly depend on the position of chlorine atoms and the relative stability of PCFR congeners is mainly determined by intramolecular delocalized π bond and Cl···Cl nuclear repulsive interaction.展开更多
Oxidation kinetics of fluorene (Fl) and its halogenated derivatives, namely, 2,7-dichlorofluorene (Fl-Cl), 2,7-dibromofluorene (Fl-Br) and 2,7-diiodofluorene (Fl-I), by permanganate ion in both perchloric and sulfuric...Oxidation kinetics of fluorene (Fl) and its halogenated derivatives, namely, 2,7-dichlorofluorene (Fl-Cl), 2,7-dibromofluorene (Fl-Br) and 2,7-diiodofluorene (Fl-I), by permanganate ion in both perchloric and sulfuric acid media have been investigated using conventional spectrophotometric technique. In both acidic media, the reactions manifested first order kineticsin [permanganate] and less than unit order each in [reductants] and [acid]. Increasing ionic strength had no effect on the oxidation rates. Oxidation rates of fluorenes in perchloric acid were higher than those in sulfuric acid and the order of the oxidation rates was: Fl > Fl-I > Fl-Br > Fl-Cl. Final oxidation products were identified by GC/MS and FT-IR analyses in all cases as 9H-fluorenone derivatives. Reaction constants as well as activation parameters of the second order rate constants were also evaluated.展开更多
π-Conjugated polymers(CPs)represent one of the quite important and rapidly growing branches of flexible electrochromic materials.Electrosynthesized hybrid CPs employing dibenzo pentacycles(fluorenes,carbazoles,dibenz...π-Conjugated polymers(CPs)represent one of the quite important and rapidly growing branches of flexible electrochromic materials.Electrosynthesized hybrid CPs employing dibenzo pentacycles(fluorenes,carbazoles,dibenzothiophenes,and dibenzofuran)as the backbones have received considerable attention owing to their special structures and interesting electrochromic performances.Recent studies show that polymers from these structures exhibit decent contrast ratios,favorable coloration efficiencies,low switching voltages,fast response time,excellent stability,and color persistence.Intrinsically,their electrochromic properties significantly depend on fine-tailoring of precursor monomer structures,and polymerization techniques and conditions.This review devotes to showing a clear picture of the research progress of dibenzo pentacycle-centered CPs via electrochemical polymerization,including fluorenes,carbazoles,dibenzothiophenes,and dibenzofuran-based hybrid electrochromic polymers.Critical influences of the tailored precursor structures on their electropolymerization and resultant polymer performances are highlighted,aiming at providing an insight for the development of novel fused ring-based polymer electrochromic materials.展开更多
Based on the GC-MS analytical data of aromatic fractions of over forty highly mature coal-bearing source rock samples collected from the Upper Triassic Xujiahe Formation in the northern Sichuan Basin, the thermal evol...Based on the GC-MS analytical data of aromatic fractions of over forty highly mature coal-bearing source rock samples collected from the Upper Triassic Xujiahe Formation in the northern Sichuan Basin, the thermal evolution of aromatic hydrocarbons during late-mature to over-mature stage （R0=1.13%-2.85%） was characterized, and aromatic indicators suitable for recognizing the organic source and sedimentary environment of high maturity source rocks were discussed. The results indicated that the concentrations of low carbon-cycle naphthalene as well phenanthrene series reduce gradually with increasing Ro at the highly mature levels. However, some high-cyclic components such as chrysene, benzofluoranthene, and benzo[e]pyrene are relatively enriched, in companying an enhancement of parent aromatic compounds. The variations are attributed to thermal cracking and polymerization reactions due to continuous dehydrogenation under enhanced burial temperature. As thermal maturity rises, MPI1 （Methylphenanthrene Index） values display a two-modal varying trend, namely, increasing when Ro is below 1.80% and decreasing above 1.8% Ro. The relationships between Ro and MPI1 are Ro=0.98MPI1＋0.37 for R0〈1.80% and R0=-0.90MPI1＋3.02 at R0〉1.8%, being different from the previous research. The amount of dibenzofurans declines sharply at Ro higher than 1.1%, leading to a significant change of relative composition among dibenzothiophenes, dibenzofurans and fluorenes （referred as three-fluorenes series composition）. Thus, this parameter appears to be unsuitable for identifying the sedimentary environment of the highly matured source rocks. 4-/1-MDBT （methyldibenzothiophene） ratio could be served as an effective indicator for organic facies, and can distinguish coals from mudstones at over-maturity in this case. The ratios of 2,6-/2,10-DMP （dimethylphenanthrene） and 1,7-/1,9-DMP and relative abundance of triaromatic steroids in these highly mature rocks could be considered as biological source parameters for relati展开更多
The refining process of fluorene by melt crystallization was experimentally studied.The effects of the cooling rate,final temperature in the crystallization process,heating rate and final temperature in the sweating p...The refining process of fluorene by melt crystallization was experimentally studied.The effects of the cooling rate,final temperature in the crystallization process,heating rate and final temperature in the sweating process on the purity and yield of the product were investigated.The optimum conditions of the refining process of fluorene by melt crystallization were determined and a product with purity of 97.4% was obtained.The binary solid-liquid equilibrium phase diagram for fluorene and 2-methyl-diphenylene oxide is analyzed according to the experimental results.展开更多
A diamine(WuFDA) containing vertical rigid non-planar conjugated fluorene moiety and low polarizability group(C―F)was designed and synthesized through three steps of reactions(halogenated reaction, Suzuki coupling re...A diamine(WuFDA) containing vertical rigid non-planar conjugated fluorene moiety and low polarizability group(C―F)was designed and synthesized through three steps of reactions(halogenated reaction, Suzuki coupling reaction, and reduction reaction).Four kinds of high performance functional polyimides(WuFPI-6 F, WuFPI-BP, WuFPI-BT, and WuFPI-PM) were thus prepared by the condensation polymerization of WuFDA with four commercial dianhydride 6 FDA, BPDA, BTDA, and PMDA, respectively. The polyimides exhibited low dielectric constant, excellent thermal stability, outstanding solubility, good film-forming property, and mechanical properties. The dielectric constants of the polyimides were in the range of 2.28-2.88(f = 10~4 Hz). The 5% weight-loss temperatures(Td 5%)in nitrogen were in the range of 555-584 °C, and the glass transition temperatures(T_g) were in the range of 408-448 °C. The weight loss of WuFPI-BP maintaining at 450 and 500 °C for half an hour was only 0.33% and 1.26%, respectively. All the WuFPIs could be dissolved in almost all organic solvents, even chloroform. The tensile strength and tensile modulus of these films were in the ranges of 78.6-85.7 MPa and 3.1-3.2 GPa, respectively. In addition, the polyimides displayed light color with special fluorescent and resistive switching(ON-OFF) characteristics; the maximum fluorescence emission was observed at 422-424 nm in NMP solution and at 470-548 nm in film state. The memory devices with the configuration of indium tin oxide/WuFPIs/aluminum(ITO/WuFPIs/Al) exhibited distinct volatile memory characteristics of static random access memory(SRAM), with an ON/OFF current ratio of 10~5-10~6. These functional polyimides showed attractive potential applications in the field of high performance flexible polymer photoelectronic devices or polymer memory devices.展开更多
基金supported by the Natural Science Research Program of Henan Provincial Department of Education (No. 2009A150022)the Young Talented Teacher Foundation of Xinyang Normal University
文摘Geometric structures of 135 polychlorinated fluorene （PCFR） molecules were optimized using density functional theory （DFT） at the B3LYP/6-311G＊＊ level and their thermodynamic properties in the ideal gas state were calculated. The relations of these thermodynamic properties with the number and position of chlorine atoms were also explored, from which the relative stability of PCFR congeners was theoretically proposed according to the magnitude of the relative standard Gibbs free energy of formation （Δr,fGθ）. The results show that the geometric configuration of PCFR isomers is determined by the position of chlorine atoms. There exist two types of intramolecular weak interactions, i.e., C–H···Cl and Cl···Cl interactions in PCFR molecules. The change of ΔfHθ and ΔfGθ of most stable PCFR isomers with increasing the number of chlorine atoms is different from that in most unstable PCFR congeners. The values of ΔfHθ and ΔfGθ for PCFR isomers with the same number of chlorine atoms strongly depend on the position of chlorine atoms and the relative stability of PCFR congeners is mainly determined by intramolecular delocalized π bond and Cl···Cl nuclear repulsive interaction.
文摘Oxidation kinetics of fluorene (Fl) and its halogenated derivatives, namely, 2,7-dichlorofluorene (Fl-Cl), 2,7-dibromofluorene (Fl-Br) and 2,7-diiodofluorene (Fl-I), by permanganate ion in both perchloric and sulfuric acid media have been investigated using conventional spectrophotometric technique. In both acidic media, the reactions manifested first order kineticsin [permanganate] and less than unit order each in [reductants] and [acid]. Increasing ionic strength had no effect on the oxidation rates. Oxidation rates of fluorenes in perchloric acid were higher than those in sulfuric acid and the order of the oxidation rates was: Fl > Fl-I > Fl-Br > Fl-Cl. Final oxidation products were identified by GC/MS and FT-IR analyses in all cases as 9H-fluorenone derivatives. Reaction constants as well as activation parameters of the second order rate constants were also evaluated.
基金the National Natural Science Foundationof China(51303073,51463008,51572117)the Ganpo Outstanding Talents 555 projects(2013)+4 种基金the National Science Fund for Distinguished Young Scholars in Jiangxi Province,Key Project of Jiangxi Educational Committee(GJJ150795)the Natural Science Foundation of Jiangxi Province(20161BAB216130)Scientific Fund of Jiangxi Science & Technology Normal University(2014QNBJRC003)Jiangxi Science & Technology Normal University Program for Scientific Research Innovation Team (2015CXTD001)Scientific Research Foundation for Doctors in Jiangxi Science & Technology
文摘π-Conjugated polymers(CPs)represent one of the quite important and rapidly growing branches of flexible electrochromic materials.Electrosynthesized hybrid CPs employing dibenzo pentacycles(fluorenes,carbazoles,dibenzothiophenes,and dibenzofuran)as the backbones have received considerable attention owing to their special structures and interesting electrochromic performances.Recent studies show that polymers from these structures exhibit decent contrast ratios,favorable coloration efficiencies,low switching voltages,fast response time,excellent stability,and color persistence.Intrinsically,their electrochromic properties significantly depend on fine-tailoring of precursor monomer structures,and polymerization techniques and conditions.This review devotes to showing a clear picture of the research progress of dibenzo pentacycle-centered CPs via electrochemical polymerization,including fluorenes,carbazoles,dibenzothiophenes,and dibenzofuran-based hybrid electrochromic polymers.Critical influences of the tailored precursor structures on their electropolymerization and resultant polymer performances are highlighted,aiming at providing an insight for the development of novel fused ring-based polymer electrochromic materials.
基金supported by the Key State Science and Technology Project(Grant No.2011ZX05005-03-009HZ)the Specialized Research Fund for the Doctoral Program of Higher Education(Grant No.20130101110051)
文摘Based on the GC-MS analytical data of aromatic fractions of over forty highly mature coal-bearing source rock samples collected from the Upper Triassic Xujiahe Formation in the northern Sichuan Basin, the thermal evolution of aromatic hydrocarbons during late-mature to over-mature stage （R0=1.13%-2.85%） was characterized, and aromatic indicators suitable for recognizing the organic source and sedimentary environment of high maturity source rocks were discussed. The results indicated that the concentrations of low carbon-cycle naphthalene as well phenanthrene series reduce gradually with increasing Ro at the highly mature levels. However, some high-cyclic components such as chrysene, benzofluoranthene, and benzo[e]pyrene are relatively enriched, in companying an enhancement of parent aromatic compounds. The variations are attributed to thermal cracking and polymerization reactions due to continuous dehydrogenation under enhanced burial temperature. As thermal maturity rises, MPI1 （Methylphenanthrene Index） values display a two-modal varying trend, namely, increasing when Ro is below 1.80% and decreasing above 1.8% Ro. The relationships between Ro and MPI1 are Ro=0.98MPI1＋0.37 for R0〈1.80% and R0=-0.90MPI1＋3.02 at R0〉1.8%, being different from the previous research. The amount of dibenzofurans declines sharply at Ro higher than 1.1%, leading to a significant change of relative composition among dibenzothiophenes, dibenzofurans and fluorenes （referred as three-fluorenes series composition）. Thus, this parameter appears to be unsuitable for identifying the sedimentary environment of the highly matured source rocks. 4-/1-MDBT （methyldibenzothiophene） ratio could be served as an effective indicator for organic facies, and can distinguish coals from mudstones at over-maturity in this case. The ratios of 2,6-/2,10-DMP （dimethylphenanthrene） and 1,7-/1,9-DMP and relative abundance of triaromatic steroids in these highly mature rocks could be considered as biological source parameters for relati
文摘The refining process of fluorene by melt crystallization was experimentally studied.The effects of the cooling rate,final temperature in the crystallization process,heating rate and final temperature in the sweating process on the purity and yield of the product were investigated.The optimum conditions of the refining process of fluorene by melt crystallization were determined and a product with purity of 97.4% was obtained.The binary solid-liquid equilibrium phase diagram for fluorene and 2-methyl-diphenylene oxide is analyzed according to the experimental results.
基金financial support by the National 973 Program of China (No. 2014CB643605)the National Natural Science Foundation of China (Nos. 51373204 and 51873239)+3 种基金the Science and Technology Project of Guangdong Province (Nos. 2015B090915003 and 2015B090913003)the China Postdoctoral Science Foundation (No. 2017M612801)the Leading Scientific, Technical and Innovation Talents of Guangdong Special Support Program (No. 2016TX03C295)the Fundamental Research Funds for the Central Universities (No. 161gzd08)
文摘A diamine(WuFDA) containing vertical rigid non-planar conjugated fluorene moiety and low polarizability group(C―F)was designed and synthesized through three steps of reactions(halogenated reaction, Suzuki coupling reaction, and reduction reaction).Four kinds of high performance functional polyimides(WuFPI-6 F, WuFPI-BP, WuFPI-BT, and WuFPI-PM) were thus prepared by the condensation polymerization of WuFDA with four commercial dianhydride 6 FDA, BPDA, BTDA, and PMDA, respectively. The polyimides exhibited low dielectric constant, excellent thermal stability, outstanding solubility, good film-forming property, and mechanical properties. The dielectric constants of the polyimides were in the range of 2.28-2.88(f = 10~4 Hz). The 5% weight-loss temperatures(Td 5%)in nitrogen were in the range of 555-584 °C, and the glass transition temperatures(T_g) were in the range of 408-448 °C. The weight loss of WuFPI-BP maintaining at 450 and 500 °C for half an hour was only 0.33% and 1.26%, respectively. All the WuFPIs could be dissolved in almost all organic solvents, even chloroform. The tensile strength and tensile modulus of these films were in the ranges of 78.6-85.7 MPa and 3.1-3.2 GPa, respectively. In addition, the polyimides displayed light color with special fluorescent and resistive switching(ON-OFF) characteristics; the maximum fluorescence emission was observed at 422-424 nm in NMP solution and at 470-548 nm in film state. The memory devices with the configuration of indium tin oxide/WuFPIs/aluminum(ITO/WuFPIs/Al) exhibited distinct volatile memory characteristics of static random access memory(SRAM), with an ON/OFF current ratio of 10~5-10~6. These functional polyimides showed attractive potential applications in the field of high performance flexible polymer photoelectronic devices or polymer memory devices.
