In this paper, the synthetic method for making 7,7’-dimethyl-2,5-bis(trimethylsilyl)-dithieno[2,3-b:3’,2’-d] silole (1) was developed by using 2,2’-dibromo-5,5’-bis-trimethyl-silanyl[3,3’]bithiophenyl as startin...In this paper, the synthetic method for making 7,7’-dimethyl-2,5-bis(trimethylsilyl)-dithieno[2,3-b:3’,2’-d] silole (1) was developed by using 2,2’-dibromo-5,5’-bis-trimethyl-silanyl[3,3’]bithiophenyl as starting material in one pot reaction. In the presence of NXS (X = Cl, Br, I), a novel ring-opening reation was occurred on the silole ring of 1 in DMF or THF. By using such kind of reaction, two types of ring opened products, (2’-halo-5,5’-bis(trimethylsilanyl)[3,3’]bithiophenyl-2-yl)-dimethylsilanols and 2,2’-dihalo-5,5’-bis(trimethylsi- lanyl)[3,3’]bithiophenyls were obtained efficiently.展开更多
The theoretical calculation of the charge mobility of 2,5-bis(trialkylsilylethynyl)-1,1,3,4-tetraphenylsiloles is presented.B3LYP/6-31* calculations demonstrated that these silole molecules possessed large coupling ma...The theoretical calculation of the charge mobility of 2,5-bis(trialkylsilylethynyl)-1,1,3,4-tetraphenylsiloles is presented.B3LYP/6-31* calculations demonstrated that these silole molecules possessed large coupling matrix elements and reorganization energies for electron and hole transfers and high electron mobilities.The bulkiness of the trialkyl substituents influenced the charge mobility of the silole molecules,with the smaller trimethyl group imparting higher charge mobility than triethyl and triisopropyl substituents.展开更多
A new silole derivative, 2,5-bis（7-（dimesitylboranyl）-9,9-dimethylfluoren-2-yl）- 1 -methyl- 1,3,4-triphenylsilole （（MesBF）2MTPS）, is synthesized and characterized. （MesBF）2MTPS shows a good fluorescence effi...A new silole derivative, 2,5-bis（7-（dimesitylboranyl）-9,9-dimethylfluoren-2-yl）- 1 -methyl- 1,3,4-triphenylsilole （（MesBF）2MTPS）, is synthesized and characterized. （MesBF）2MTPS shows a good fluorescence efficiency of 15% in THF solution and a higher efficiency of 86% in solid film, presenting an aggregation-enhanced emission charac- teristic. It is thermally and morphologically stable, with high decomposition and glass-transition temperatures of 257 and 171 ℃, respectively. The LUMO energy level （-2.96 eV） of （MesBF）zMTPS is lower than that of TPBi, revealing its electron-transporting potential. Efficient organic light-emitting diodes （OLEDs） are fabricated using （MesBF）2MTPS as emitter, which radiates yellow light at 554 nm, and affords high maximum luminance, current efficiency, and external quantum efficiency of 48348 cd·m^-2, 12.3 cd·A^-1, and 4.1%, respectively.展开更多
Luminogenic molecules with aggregation-induced emission(AIE) property are free of aggregationcaused quenching and thus have great potential in the fabrication of efficient non-doped OLEDs. Herein, a series of new carb...Luminogenic molecules with aggregation-induced emission(AIE) property are free of aggregationcaused quenching and thus have great potential in the fabrication of efficient non-doped OLEDs. Herein, a series of new carbazole-substituted siloles have been synthesized and characterized. Their crystal and electronic structures, thermal stabilities, electrochemical behaviors, and photophysical properties are thoroughly investigated. These silole derivatives exhibit prominent AIE characteristics with high emission efficiencies in solid films. They can function as light-emitting layers in non-doped OLEDs,affording eminent electroluminescence efficiencies of 17.59 cd/A, 12.55 Im/W and 5.63%, amongst the most efficient non-doped OLEDs based on fluorescent emitters, indicating their promising applications in OLEDs.展开更多
Two copolymers,poly(1,1-dimethyl-3,4-diphenylsilole-alt-N-hexyl-3,6-diethynylcarbazole)(PS-DyCz)and poly-(1,1-dimethyl-3,4-diphenylsilole-alt-2,7-diethynyl-9,9'-dihexylfluorene)(PS-DyF),were synthesized by Sonogas...Two copolymers,poly(1,1-dimethyl-3,4-diphenylsilole-alt-N-hexyl-3,6-diethynylcarbazole)(PS-DyCz)and poly-(1,1-dimethyl-3,4-diphenylsilole-alt-2,7-diethynyl-9,9'-dihexylfluorene)(PS-DyF),were synthesized by Sonogashira coupling reaction of 2,5-dibromo-1,1-dimethyl-3,4-diphenylsilole and N-hexyl-3,6-diethynylcarbazole or 2,7-diethynyl-9,9'-dihexylfluorene,respectively.The chemical structures of the copolymers were characterized by NMR,FT-IR techniques.Their thermal and photophysical properties were evaluated by TGA,DSC,UV-Vis and fluorescence spectroscopy,respectively.The weight-averaged molecular weights(Mw)of PS-DyCz and PS-DyF are 1.20×10^(4) and 3.83×10^(4) Da,respectively.The degree of polymerization is 8 and 22 units.Theseπ-conjugated polymers exhibited lower band-gap of 2.25 and 2.70 eV due to the presence of silole rings and C≡C triple bonds in their backbone,the results were consistent with the density functional(DFT)calculations at the B3LYP/6-31G^(*)level.展开更多
Three routes were designed to synthesize a n-conjugated aryleneethynylenesiloles dendron. With the desilylation of the disilole mono（silylethynyl） derivative in the presence of potassium carbonate （K2CO3）, the sil...Three routes were designed to synthesize a n-conjugated aryleneethynylenesiloles dendron. With the desilylation of the disilole mono（silylethynyl） derivative in the presence of potassium carbonate （K2CO3）, the silole-containing oligomer has been successfully synthesized without impact on the Si-（CH3）2 group. The disilole mono- （silylethynyl） derivative was prepared by means of the Sonogashira heterocoupling reaction between the diacetylene compound and asymmetrical silole, catalyzed by the dichloro bis（triphenylphosphine）palladium, in a divergent synthesis. Due to their steric effect and triethynylbenzene self-coupling Glaser reaction, the endeavour to prepare the dendron by controlling the molar ratio of asymmetrical silole and 1,3,5-triethynylbenzene was failed. The another attempt to prepare the dendron by different desilylation condition of triisopropylsilyl group and trimethylsilyl group was also failed, the desilylation of Si-（CH3）2 group in silacyclopentadiene unit was also easily accomplished in the presence of tetrabutylammonium fluoride（Bu4NF）, whereas no reaction occurred when K2CO3 was used instead of Bu4NF.展开更多
A series of new red fluorescent siloles consisting of a silole core and dimesitylboranyl substituent connected with a furan, thiophene, and selenophene bridges were synthesized and characterized. The optical propertie...A series of new red fluorescent siloles consisting of a silole core and dimesitylboranyl substituent connected with a furan, thiophene, and selenophene bridges were synthesized and characterized. The optical properties, electronic structures, and electroluminescence （EL） performances were investigated. The emission wavelengths were red-shifted from the siloles with furan, to those with thiophene, and then selenophene. The thiophene, and selenophene-containing siloles, （MesB）2DTTPS, and （MesB）zDSTPS, showed the typical aggregation-enhanced emission （AEE） feature, while furan-containing one, （MesB）2DFTPS, showed slight emission decrease as the aggregate formation. Theoretical calculations were carried out to explain the difference in the optical properties. Undoped OLEDs using these red siloles as light-emitting layers were fabricated. The device of （MesB）2DTTPS exhibited the best performance. It radiated red EL emission at 589 nm, and afforded good maximum luminance, current, power, and external quantum efficiency of 13300 cd m^-2, 4.3 cd A^-1, 2.9 lm W^-1, and 1.8%, respectively.展开更多
A new conjugated copolymer （PTST-DyOXD） derived from 1,1-dimethyl-3,4-diphenyl-2,5-bis（5-bromo-2- thienyl）-silole （TST） and 2,5-bis（4-ethynylphenyl）-l,3,4-oxadiazole （DyOXD） was synthesized by Pd（0）-cataly...A new conjugated copolymer （PTST-DyOXD） derived from 1,1-dimethyl-3,4-diphenyl-2,5-bis（5-bromo-2- thienyl）-silole （TST） and 2,5-bis（4-ethynylphenyl）-l,3,4-oxadiazole （DyOXD） was synthesized by Pd（0）-catalyzed Sonogashira coupling reaction. For comparison, another copolymer without acetenyl group （PTST-OXD） was also synthesized by Pd（0）-catalyzed Suzuki coupling reaction. Chemical structures and optoelectronic properties of the copolymers were characterized by IH NMR, 13C NMR, IR, UV-vis absorption, photoluminescence and cyclic voltammetry. The number-average molecular weight （Mn） is 4010 Da for PTST-DyOXD and 3890 Da for PTST-OXD, respectively. The thermogravimetric analysis （TGA） measurements show that they have good thermal stability with decomposition temperature at 312 and 318 ~C, respectively. The optical band gap is 2.21 eV for PTST-DyOXD and 2.10 eV for PTST-OXD based on the absorption onset. CV analysis revealed the LUMO level of PTST-DyOXD is -3.04 eV, lower than that of PTST-OXD （about -2.89 eV）, which is attributed to the introduction of acetylene group in PTST-DyOXD, increasing the system of the conjugate chain length.展开更多
文摘In this paper, the synthetic method for making 7,7’-dimethyl-2,5-bis(trimethylsilyl)-dithieno[2,3-b:3’,2’-d] silole (1) was developed by using 2,2’-dibromo-5,5’-bis-trimethyl-silanyl[3,3’]bithiophenyl as starting material in one pot reaction. In the presence of NXS (X = Cl, Br, I), a novel ring-opening reation was occurred on the silole ring of 1 in DMF or THF. By using such kind of reaction, two types of ring opened products, (2’-halo-5,5’-bis(trimethylsilanyl)[3,3’]bithiophenyl-2-yl)-dimethylsilanols and 2,2’-dihalo-5,5’-bis(trimethylsi- lanyl)[3,3’]bithiophenyls were obtained efficiently.
基金supported by the Research Grants Council of Hong Kong (602707,601608,ITP/008/09NP and 603505)the National Natural Science Foundation of China (20634020)+1 种基金the Ministry of Science and Technology of China (2002CD613401)support from the CAO GuangBiao Foundation of Zhejiang University
文摘The theoretical calculation of the charge mobility of 2,5-bis(trialkylsilylethynyl)-1,1,3,4-tetraphenylsiloles is presented.B3LYP/6-31* calculations demonstrated that these silole molecules possessed large coupling matrix elements and reorganization energies for electron and hole transfers and high electron mobilities.The bulkiness of the trialkyl substituents influenced the charge mobility of the silole molecules,with the smaller trimethyl group imparting higher charge mobility than triethyl and triisopropyl substituents.
文摘A new silole derivative, 2,5-bis（7-（dimesitylboranyl）-9,9-dimethylfluoren-2-yl）- 1 -methyl- 1,3,4-triphenylsilole （（MesBF）2MTPS）, is synthesized and characterized. （MesBF）2MTPS shows a good fluorescence efficiency of 15% in THF solution and a higher efficiency of 86% in solid film, presenting an aggregation-enhanced emission charac- teristic. It is thermally and morphologically stable, with high decomposition and glass-transition temperatures of 257 and 171 ℃, respectively. The LUMO energy level （-2.96 eV） of （MesBF）zMTPS is lower than that of TPBi, revealing its electron-transporting potential. Efficient organic light-emitting diodes （OLEDs） are fabricated using （MesBF）2MTPS as emitter, which radiates yellow light at 554 nm, and affords high maximum luminance, current efficiency, and external quantum efficiency of 48348 cd·m^-2, 12.3 cd·A^-1, and 4.1%, respectively.
基金financially supported by the National Natural Science Foundation of China(Nos. 21788102 and 21673082)the National Basic Research Program of China (973 Program, No. 2015CB655004) founded by MOST+3 种基金the Guangdong Natural Science Funds for Distinguished Young Scholar(No. 2014A030306035)the Science and Technology Program of Guangzhou(No. 201804020027)International Science and Technology Cooperation Program of Guangzhou (No. 201704030069)the Innovation and Technology Commission of Hong Kong (No. ITCCNERC14SC01)
文摘Luminogenic molecules with aggregation-induced emission(AIE) property are free of aggregationcaused quenching and thus have great potential in the fabrication of efficient non-doped OLEDs. Herein, a series of new carbazole-substituted siloles have been synthesized and characterized. Their crystal and electronic structures, thermal stabilities, electrochemical behaviors, and photophysical properties are thoroughly investigated. These silole derivatives exhibit prominent AIE characteristics with high emission efficiencies in solid films. They can function as light-emitting layers in non-doped OLEDs,affording eminent electroluminescence efficiencies of 17.59 cd/A, 12.55 Im/W and 5.63%, amongst the most efficient non-doped OLEDs based on fluorescent emitters, indicating their promising applications in OLEDs.
基金the financial support from the National Natural Science Foundation of China(Nos.20872035,21076078),and the Hangzhou Normal University.
文摘Two copolymers,poly(1,1-dimethyl-3,4-diphenylsilole-alt-N-hexyl-3,6-diethynylcarbazole)(PS-DyCz)and poly-(1,1-dimethyl-3,4-diphenylsilole-alt-2,7-diethynyl-9,9'-dihexylfluorene)(PS-DyF),were synthesized by Sonogashira coupling reaction of 2,5-dibromo-1,1-dimethyl-3,4-diphenylsilole and N-hexyl-3,6-diethynylcarbazole or 2,7-diethynyl-9,9'-dihexylfluorene,respectively.The chemical structures of the copolymers were characterized by NMR,FT-IR techniques.Their thermal and photophysical properties were evaluated by TGA,DSC,UV-Vis and fluorescence spectroscopy,respectively.The weight-averaged molecular weights(Mw)of PS-DyCz and PS-DyF are 1.20×10^(4) and 3.83×10^(4) Da,respectively.The degree of polymerization is 8 and 22 units.Theseπ-conjugated polymers exhibited lower band-gap of 2.25 and 2.70 eV due to the presence of silole rings and C≡C triple bonds in their backbone,the results were consistent with the density functional(DFT)calculations at the B3LYP/6-31G^(*)level.
基金supported by National Natural Science Foundation of China （Nos. 20872035, 21076078）, and Specialized Research Fund for the Doctoral Program of Higher Education （No. 20070251018）.
文摘Three routes were designed to synthesize a n-conjugated aryleneethynylenesiloles dendron. With the desilylation of the disilole mono（silylethynyl） derivative in the presence of potassium carbonate （K2CO3）, the silole-containing oligomer has been successfully synthesized without impact on the Si-（CH3）2 group. The disilole mono- （silylethynyl） derivative was prepared by means of the Sonogashira heterocoupling reaction between the diacetylene compound and asymmetrical silole, catalyzed by the dichloro bis（triphenylphosphine）palladium, in a divergent synthesis. Due to their steric effect and triethynylbenzene self-coupling Glaser reaction, the endeavour to prepare the dendron by controlling the molar ratio of asymmetrical silole and 1,3,5-triethynylbenzene was failed. The another attempt to prepare the dendron by different desilylation condition of triisopropylsilyl group and trimethylsilyl group was also failed, the desilylation of Si-（CH3）2 group in silacyclopentadiene unit was also easily accomplished in the presence of tetrabutylammonium fluoride（Bu4NF）, whereas no reaction occurred when K2CO3 was used instead of Bu4NF.
基金supported by the National Natural Sci-ence Foundation of China (51273053)the National Basic Research Program of China (2015CB655004,2013CB834702)+3 种基金the Guangdong Natural Science Funds for Distinguished Young Scholar (2014A 030306035)the Guangdong Innovative R esearch Team Program o f China (201101C0105067115)ITC-CN ERC14S01the Fundam ental Research Funds for the Central Univer- sities (2015PT020, 2015ZY013)
文摘A series of new red fluorescent siloles consisting of a silole core and dimesitylboranyl substituent connected with a furan, thiophene, and selenophene bridges were synthesized and characterized. The optical properties, electronic structures, and electroluminescence （EL） performances were investigated. The emission wavelengths were red-shifted from the siloles with furan, to those with thiophene, and then selenophene. The thiophene, and selenophene-containing siloles, （MesB）2DTTPS, and （MesB）zDSTPS, showed the typical aggregation-enhanced emission （AEE） feature, while furan-containing one, （MesB）2DFTPS, showed slight emission decrease as the aggregate formation. Theoretical calculations were carried out to explain the difference in the optical properties. Undoped OLEDs using these red siloles as light-emitting layers were fabricated. The device of （MesB）2DTTPS exhibited the best performance. It radiated red EL emission at 589 nm, and afforded good maximum luminance, current, power, and external quantum efficiency of 13300 cd m^-2, 4.3 cd A^-1, 2.9 lm W^-1, and 1.8%, respectively.
基金The authors are grateful to financial support from the National Natural Science Foundation of China，the East China University of Science and Technology
文摘A new conjugated copolymer （PTST-DyOXD） derived from 1,1-dimethyl-3,4-diphenyl-2,5-bis（5-bromo-2- thienyl）-silole （TST） and 2,5-bis（4-ethynylphenyl）-l,3,4-oxadiazole （DyOXD） was synthesized by Pd（0）-catalyzed Sonogashira coupling reaction. For comparison, another copolymer without acetenyl group （PTST-OXD） was also synthesized by Pd（0）-catalyzed Suzuki coupling reaction. Chemical structures and optoelectronic properties of the copolymers were characterized by IH NMR, 13C NMR, IR, UV-vis absorption, photoluminescence and cyclic voltammetry. The number-average molecular weight （Mn） is 4010 Da for PTST-DyOXD and 3890 Da for PTST-OXD, respectively. The thermogravimetric analysis （TGA） measurements show that they have good thermal stability with decomposition temperature at 312 and 318 ~C, respectively. The optical band gap is 2.21 eV for PTST-DyOXD and 2.10 eV for PTST-OXD based on the absorption onset. CV analysis revealed the LUMO level of PTST-DyOXD is -3.04 eV, lower than that of PTST-OXD （about -2.89 eV）, which is attributed to the introduction of acetylene group in PTST-DyOXD, increasing the system of the conjugate chain length.
