In order to obtain high efficiency of organic light-emitting diodes and organic solar cells,a series of DPP-based four-coordinate organoboron compounds have been designed for photoelectric functional materials.The eff...In order to obtain high efficiency of organic light-emitting diodes and organic solar cells,a series of DPP-based four-coordinate organoboron compounds have been designed for photoelectric functional materials.The effects of electron-donating and-withdrawing substituent on the electronic and optical properties have been investigated by using density functional theory(DFT)and time-dependent DFT(TD-DFT)approaches systematically.It turned out that electron-donating and-withdrawing groups can tune effectively the frontier molecular orbital(FMO)energy level,energy gap,and absorption and fluorescence spectra.The introduction of electron-withdrawing groups for the parent molecule HBDPP(2,5-bis(diphenylboryl)-3,6-bis(pyridin-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione)favors the decrease for the FMO energy(E_(LUMO)and E_(HOMO)),HOMO-LUMO gaps(E_(g)),and the downhill energetic driving force(ΔEL-L),while the electron-donating groups can increase E_(LUMO),E_(HOMO),E_(g),andΔEL-L compared with that of HBDPP,respectively.The absorption and fluorescence spectra of the electron-withdrawing substituted derivatives exhibit bathochromic shifts,while the absorption and fluorescence spectra of the electrondonating substituted derivatives show hypsochromic shifts compared with the parent molecule HBDPP,respectively.Furthermore,the stronger the electron-withdrawing/donating ability of group is,the more significant the effect in the optoelectronic properties.展开更多
Molecular simulations are widely used to model molecularly imprinted polymers(MIPs)in order to enliance their adsorption and selectivity.In this study,chloramphenicol(CAP)and acrylamide(AM)were used as the template an...Molecular simulations are widely used to model molecularly imprinted polymers(MIPs)in order to enliance their adsorption and selectivity.In this study,chloramphenicol(CAP)and acrylamide(AM)were used as the template and flinctional monomer,respectively,and pentaenlhritol triacrylate(PETA),ethylene glycol dimethacrylate(EGDMA),and trimethvlolpropane trimethvlacrylate(TRIM)were used as cross-linking agents.The 6oB97XD/6-31 density functional theory method was employed to simulate binding sites,binding energy,the number of hydrogen bonds,the imprinted molar ratio,which produced the most stable complex,and the interaction mechanism.The cross-linking agent was optimized based on the binding energy.The atoms in molecules theory were used to study the nature of the imprinting effects.The theoretical calculations revealed that CAP and AM fonned ordered complexes via hydrogen bonding interactions when the molar ratio between CAP and AM was 1:7 using TRIM as the cross-linking agent.The CAP-AM complex(molar ratio 1:7)had the most stable structure,the largest number of hydrogen bonds,and the smallest AE.The experimental results indicate that the CAP-MIPs ionncd perfect microspheres with an average particle size of 314 nm.Scat chard plot analysis showed that the CAP-MIPs had only one type of binding site over thestudied concentration ranges.The dissociation equilibriinn constant and maximum apparent adsorption capacities were 1887.35 mg/L(5.84 mmol/L)and 155.56 mg/g(0.482 mmol/g),respectively.展开更多
The different interactions between a chemosensor, 1-（naphthalen-2-yl）-3-（6-nitrobenzothiazol-2-yl）-thiourea （1）, and F, acetate （AcO-）, Cl-, and Br- anions have been investigated theoretically at the B3LYP/6-3...The different interactions between a chemosensor, 1-（naphthalen-2-yl）-3-（6-nitrobenzothiazol-2-yl）-thiourea （1）, and F, acetate （AcO-）, Cl-, and Br- anions have been investigated theoretically at the B3LYP/6-31＋G（d,p） level with the basis set superposition error （BSSE） correction. It was found that the high selectivity of compound 1 for F- can be ascribed to the ability of the anion to deprotonate the N-H fragment of the host sensor, while the chemosensor also has a strong affinity for AcO- by virtue of the formation of a hydrogen-bonded complex. Intramolecular charge transfer （ICT） causes the colorimetric signaling of compound 1 after interaction with F-/AcO. A study of substituent effects suggested that the O/NH- and O/S-substituted derivatives are also expected to be promising candidates for chromogenic F3AcO chemosensors.展开更多
基金the National Natural Science Foundation of China(21563002)the Natural Science Foundation of Inner Mongolia Autonomous Region(2021LHMS02001)the Research Program of Sciences at Universities of Inner Mongolia Autonomous Region(NJZY21175)
文摘In order to obtain high efficiency of organic light-emitting diodes and organic solar cells,a series of DPP-based four-coordinate organoboron compounds have been designed for photoelectric functional materials.The effects of electron-donating and-withdrawing substituent on the electronic and optical properties have been investigated by using density functional theory(DFT)and time-dependent DFT(TD-DFT)approaches systematically.It turned out that electron-donating and-withdrawing groups can tune effectively the frontier molecular orbital(FMO)energy level,energy gap,and absorption and fluorescence spectra.The introduction of electron-withdrawing groups for the parent molecule HBDPP(2,5-bis(diphenylboryl)-3,6-bis(pyridin-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione)favors the decrease for the FMO energy(E_(LUMO)and E_(HOMO)),HOMO-LUMO gaps(E_(g)),and the downhill energetic driving force(ΔEL-L),while the electron-donating groups can increase E_(LUMO),E_(HOMO),E_(g),andΔEL-L compared with that of HBDPP,respectively.The absorption and fluorescence spectra of the electron-withdrawing substituted derivatives exhibit bathochromic shifts,while the absorption and fluorescence spectra of the electrondonating substituted derivatives show hypsochromic shifts compared with the parent molecule HBDPP,respectively.Furthermore,the stronger the electron-withdrawing/donating ability of group is,the more significant the effect in the optoelectronic properties.
基金Supported by tlie National Natural Science Foundation of China(No.21563002)the Science and Teclmology Develop・ment Program Project of Jilin Province,China(No.JJKH20170299KJ).
文摘Molecular simulations are widely used to model molecularly imprinted polymers(MIPs)in order to enliance their adsorption and selectivity.In this study,chloramphenicol(CAP)and acrylamide(AM)were used as the template and flinctional monomer,respectively,and pentaenlhritol triacrylate(PETA),ethylene glycol dimethacrylate(EGDMA),and trimethvlolpropane trimethvlacrylate(TRIM)were used as cross-linking agents.The 6oB97XD/6-31 density functional theory method was employed to simulate binding sites,binding energy,the number of hydrogen bonds,the imprinted molar ratio,which produced the most stable complex,and the interaction mechanism.The cross-linking agent was optimized based on the binding energy.The atoms in molecules theory were used to study the nature of the imprinting effects.The theoretical calculations revealed that CAP and AM fonned ordered complexes via hydrogen bonding interactions when the molar ratio between CAP and AM was 1:7 using TRIM as the cross-linking agent.The CAP-AM complex(molar ratio 1:7)had the most stable structure,the largest number of hydrogen bonds,and the smallest AE.The experimental results indicate that the CAP-MIPs ionncd perfect microspheres with an average particle size of 314 nm.Scat chard plot analysis showed that the CAP-MIPs had only one type of binding site over thestudied concentration ranges.The dissociation equilibriinn constant and maximum apparent adsorption capacities were 1887.35 mg/L(5.84 mmol/L)and 155.56 mg/g(0.482 mmol/g),respectively.
基金supported by the Natural Science Foundation of Inner Mongolia Autonomous Region (2011ZD02)
文摘The different interactions between a chemosensor, 1-（naphthalen-2-yl）-3-（6-nitrobenzothiazol-2-yl）-thiourea （1）, and F, acetate （AcO-）, Cl-, and Br- anions have been investigated theoretically at the B3LYP/6-31＋G（d,p） level with the basis set superposition error （BSSE） correction. It was found that the high selectivity of compound 1 for F- can be ascribed to the ability of the anion to deprotonate the N-H fragment of the host sensor, while the chemosensor also has a strong affinity for AcO- by virtue of the formation of a hydrogen-bonded complex. Intramolecular charge transfer （ICT） causes the colorimetric signaling of compound 1 after interaction with F-/AcO. A study of substituent effects suggested that the O/NH- and O/S-substituted derivatives are also expected to be promising candidates for chromogenic F3AcO chemosensors.
