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
Rigid trigonal tris(3-pyridylduryl)borane L was synthesized through four steps in good overall yield from readily available 1,2,4,5-tetramethylbenzene and was used to construct two porous cadmium(II) complexes Cd(L)X2...Rigid trigonal tris(3-pyridylduryl)borane L was synthesized through four steps in good overall yield from readily available 1,2,4,5-tetramethylbenzene and was used to construct two porous cadmium(II) complexes Cd(L)X2.G(X = Cl,Br;G = guset molecules),1(Cd(L)Cl2.EtOH.iPrOH.3H2O) and 2(Cd(L)Br2.MeOH.C7H8.3H2O),under mild reaction conditions.1 and 2 are isostructural and featured with 3D porous metal-organoboron framewoks with rtl topology,in which L acts as a 3-connected node while a dicadmium motif serves as 6-connected node.In addition,1 and 2 exhibit strong photoluminescence in the visible region and 1 shows moderate adsorption ability of carbon dioxide at 273 K.展开更多
The interactions between the new organometallic complexes, ferrocenesubstituted dithioocarborane conjugates （denoted as FcSB1, FcSB2 and FcSBCO） and hemoglobin （Hb） are investigated by electrochemistry, fluorescen...The interactions between the new organometallic complexes, ferrocenesubstituted dithioocarborane conjugates （denoted as FcSB1, FcSB2 and FcSBCO） and hemoglobin （Hb） are investigated by electrochemistry, fluorescence and UVvis absorption spectroscopy. The results demonstrate that FcSB1, FcSB2 and FcSBCO can bind to the heme iron center through the replacement of the weakly bound H20/02 in the distal heme pocket of Hb by their sulfur donor atoms, inducing the allosteric change from the R state （oxygenated conformation, relax） to T state （deoxygenated conformation, tense）. The binding affinity is in the order of FcSBCO〉FeSB2〉FeSB1. Moreover, the fluorescence study illustrates that the three ferrocenecarborane conjugates differently affect the quarterly and tertiary structures as well as the polarity in the surrounding of the Trp and Tyr residues in Hb. Typically, FcSB2 mainly induces alterations of the microenvironment around the 1337Trp residue which is located on the cql32 interface of Hb. Such distinct influences are attributed to the structural features of FcSB1, FcSB2 and FcSBCO containing hydrophobic ferrocenyl and carboranyl units as well as C=O group. Screening the proteinbinding behavior can signify the potential bioactivity of such molecules and may be helpful in the future development of promising multifunctional metallodrugs.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 the National Natural Foundation of China (21025103 & 20971085)the National Basic Research Program of China (2007CB209701 & 2009CB930403)+1 种基金Shanghai Science and Technology Committee(10DJ1400100)the Key Project of State Education Ministry
文摘Rigid trigonal tris(3-pyridylduryl)borane L was synthesized through four steps in good overall yield from readily available 1,2,4,5-tetramethylbenzene and was used to construct two porous cadmium(II) complexes Cd(L)X2.G(X = Cl,Br;G = guset molecules),1(Cd(L)Cl2.EtOH.iPrOH.3H2O) and 2(Cd(L)Br2.MeOH.C7H8.3H2O),under mild reaction conditions.1 and 2 are isostructural and featured with 3D porous metal-organoboron framewoks with rtl topology,in which L acts as a 3-connected node while a dicadmium motif serves as 6-connected node.In addition,1 and 2 exhibit strong photoluminescence in the visible region and 1 shows moderate adsorption ability of carbon dioxide at 273 K.
基金supported by the National Basic Research Program of China (2010CB732404, 2010CB923303)the National Natural Science Foundation of China (21175020, 90713023, 20925104)+4 种基金the Project of High Technology Research and Development Program of China (2007AA022007)Gongdong Province (2011B090400357)the Natural Science Foundation of Jiangsu Province (BK2008149, BK2010052)C. W. acknowledges the Fundamental Research Funds for the Central Universities (ZYGX2011J099)the support by the Open Research Fund of State Key Laboratory of Bioelectronics, Southeast University (2011E09)
文摘The interactions between the new organometallic complexes, ferrocenesubstituted dithioocarborane conjugates （denoted as FcSB1, FcSB2 and FcSBCO） and hemoglobin （Hb） are investigated by electrochemistry, fluorescence and UVvis absorption spectroscopy. The results demonstrate that FcSB1, FcSB2 and FcSBCO can bind to the heme iron center through the replacement of the weakly bound H20/02 in the distal heme pocket of Hb by their sulfur donor atoms, inducing the allosteric change from the R state （oxygenated conformation, relax） to T state （deoxygenated conformation, tense）. The binding affinity is in the order of FcSBCO〉FeSB2〉FeSB1. Moreover, the fluorescence study illustrates that the three ferrocenecarborane conjugates differently affect the quarterly and tertiary structures as well as the polarity in the surrounding of the Trp and Tyr residues in Hb. Typically, FcSB2 mainly induces alterations of the microenvironment around the 1337Trp residue which is located on the cql32 interface of Hb. Such distinct influences are attributed to the structural features of FcSB1, FcSB2 and FcSBCO containing hydrophobic ferrocenyl and carboranyl units as well as C=O group. Screening the proteinbinding behavior can signify the potential bioactivity of such molecules and may be helpful in the future development of promising multifunctional metallodrugs.
