Quantum-chemical calculations on some derivatives of [n]-prismanes expanded by ethynyl or ethenyl groups have been performed using density functional theory （DFT） method.Their geometric structures,electronic structu...Quantum-chemical calculations on some derivatives of [n]-prismanes expanded by ethynyl or ethenyl groups have been performed using density functional theory （DFT） method.Their geometric structures,electronic structures,vertical ionization potentials and vertical electron affinities have been obtained at the B3LYP/6-31G＊＊ level of theory.Meanwhile,the total strain energy has been investigated in detail and compared with [n]-prismane and other derivatives.The present paper has also computed the enthalpies of formation for different isomers so as to evaluate their thermal stabilities.展开更多
The first cyclic molecule formation reactions from ethyne （C2H2）, initiated by ethynyl radical （C2H）, were studied by theoretical quantum mechanic. The study included the competition reaction between structure re-...The first cyclic molecule formation reactions from ethyne （C2H2）, initiated by ethynyl radical （C2H）, were studied by theoretical quantum mechanic. The study included the competition reaction between structure re-arrangement for the favourable ring-closure mechanism and ethyne addition in each step. The analysis was done by evaluating the energy difference of activation （AE）, entalphy （AH）, Gibbs （AG） of the optimized stable and transition molecules. The reaction temperatures were set at normal （T = 298 K） and combustion （T = 1200 K） condition.展开更多
To develop efficient sensitizers for dye-sensitized solar cells(DSSCs),we recently reported doubly concerted companion(DCC)dye XW83 with a wrapped porphyrin sub-dye unit linked to an organic sub-dye unit through a fle...To develop efficient sensitizers for dye-sensitized solar cells(DSSCs),we recently reported doubly concerted companion(DCC)dye XW83 with a wrapped porphyrin sub-dye unit linked to an organic sub-dye unit through a flexible chain,which exhibits panchromatic absorption and excellent anti-aggregation ability.To further improve the absorption,we herein report XW87 and XW88 by inserting an ethynyl group into the organic sub-dye unit of XW83 near the donor and acceptor,respectively.For the corresponding organic dyes Z3 and Z4,the introduced ethynyl group improves their absorption,but induces aggravated charge recombination,leading to lowered power conversion efficiencies(PCEs).Similar to the organic dyes,the introduced ethynyl group improves the absorption of DCC dyes XW87 and XW88 as well.In addition,the ethynyl group near the acceptor of the organic sub-dye unit can be well protected by the long wrapping chains from the porphyrin unit.As a result,XW88 affords the highest JSC(21.84 mA/cm^(2)),V_(OC)(782 mV)and PCE(12.2%)among the DCC dyes.These results provide an effective method for developing efficient DSSC dyes by inserting an ethynyl group at a suitable position of a DCC dye.展开更多
Two copolymers of P1 and P2 comprising benzothiadiazole, 1,4-bis（dodecyloxy）-benzene units were synthesized by Sonogashira coupling polymerization based on ethynyl-linked 1,2,5,6-naphthalenediimide. Their thermal, o...Two copolymers of P1 and P2 comprising benzothiadiazole, 1,4-bis（dodecyloxy）-benzene units were synthesized by Sonogashira coupling polymerization based on ethynyl-linked 1,2,5,6-naphthalenediimide. Their thermal, optical, electrochemical as well as charge transport properties were studied. Bottom-gate top-contact organic field-effect transistors （OFETs） measurements of P1 and P2 thin films showed different charge transport behaviors. P1 displayed pure electron transport behaviors in OFETs with electron mobility up to 10^-3 cm^2·V-1·s^-1, while P2 exhibited hole transport features. The molecular structure analysis revealed that the structure of P1 has the acceptor-linker-acceptor＇ （A-L-A＇） characteristic, and P2 possesses the donor-linker-acceptor （D-L-A） structure feature. The results demonstrate that different molecular structures lead them to have distinct charge transport behaviors. In particular, the first pure electron transport copolymer in OFETs based on 1,2,5,6-naphthalenediimide is achieved.展开更多
In this work, star-shaped perylene bisimide（PBI） derivatives with spiro-aromatic cores linked with ethynyl units were developed as electron acceptors for non-fullerene organic solar cells. The ethynyl linkers were f...In this work, star-shaped perylene bisimide（PBI） derivatives with spiro-aromatic cores linked with ethynyl units were developed as electron acceptors for non-fullerene organic solar cells. The ethynyl linkers were found to enhance the planarity of the conjugated backbone, resulting in high electron mobilities and near-infrared absorption. The ethynyl-linked PBI acceptors showed high power conversion efficiencies（PCEs） up to 4.27% due to the high short-circuit current density（Jsc） of 8.52 mA/cm^2 and fill factor（FF） of 0.59, while the PBI acceptor without ethynyl units provided a low PCE of 3.57% in nonfullerene solar cells. The results demonstrate that ethynyl units can be applied into designing new PBI electron acceptors with improved charge transport properties and photovoltaic performance.展开更多
The aim of this paper was to test the thermal and environmental stability of poly（4-ethynyl-p-xylylene- co-p-xylylene） thin films prepared by chemical vapor deposition （CVD） and to optimize the reaction conditions...The aim of this paper was to test the thermal and environmental stability of poly（4-ethynyl-p-xylylene- co-p-xylylene） thin films prepared by chemical vapor deposition （CVD） and to optimize the reaction conditions of the polymer. Fourier transformed infrared spectroscopy （FTIR）, thermogravimetric analysis （TGA） and fluorescence microscopy were employed to investigate the stability of the reactive polymer coatings in various environmental conditions. Chemical reactivity of the thin films were then tested by Huisgen 1,3-dipolar cycloaddition reaction （＂click＂ reaction）. The alkyne functional groups on poly（4- ethynyl-p-xylylene-co-p-xylylene） thin films were found to be stable under ambient storage conditions and thermally stable up to 100 ℃ when annealed at 0.08 Torr in argon. We also optimized the click reaction conditions of azide-functionalized molecules with poly（4-ethynyl-p-xylylene-co-p-xylylene）. The best reaction result was achieved, when copper concentration was 0.5 retool/L, sodium ascorbate concentration to copper concentration was 5：1. In contrast, the azide concentration and temperature had no obvious effect on the surface reaction.展开更多
合成兼具高热稳定性(Td5%=508℃)和高玻璃化转变温度(Tg=374.2℃)的乙炔基封端的聚酰亚胺低聚物(S1),并将其与双酚A型氰酸酯树脂(BCE)进行共混,以提高氰酸酯包括热性能在内的综合性能,制备了S1/BCE互穿网络结构树脂体系。采用差示扫描...合成兼具高热稳定性(Td5%=508℃)和高玻璃化转变温度(Tg=374.2℃)的乙炔基封端的聚酰亚胺低聚物(S1),并将其与双酚A型氰酸酯树脂(BCE)进行共混,以提高氰酸酯包括热性能在内的综合性能,制备了S1/BCE互穿网络结构树脂体系。采用差示扫描量热分析、傅里叶变换红外光谱,利用Kissinger-Crane法和T-β外推法研究了BCE和S1的固化动力学行为和固化机理。并对固化后材料的热性能、力学性能和表面形貌进行了研究。结果表明,从红外及动力学分析,S1/BCE体系的固化工艺参数为200℃/2 h+260℃/2 h,2种方法测得的以质量比1∶1混合的树脂体系CS11平均表观活化能为88.9 k J/mol,反应级数为0.91。不同比例下S1/BCE体系固化后的玻璃化转变温度最高相均超过300℃,且在212℃依然有较高的模量保持,同时从电镜图和力学性能可以看出,材料韧性具有一定程度的提升。相比较而言,以质量比1∶1混合的树脂体系CS11的韧性提升最大,Tg=310.9℃,Td5%=424℃,且具有优良的耐热性能。展开更多
Fluoro-terminated hyperbranched（poly（aryl） ether ketone）（HPOP-PEEK-F） with 4-phenoxyphenyl side groups was prepared from A2（2-（4-phenoxyphenyl）-1,4-diphenol） and B3（1,3,5-tris[4-（4-flourobenzoyl） phenoxy]...Fluoro-terminated hyperbranched（poly（aryl） ether ketone）（HPOP-PEEK-F） with 4-phenoxyphenyl side groups was prepared from A2（2-（4-phenoxyphenyl）-1,4-diphenol） and B3（1,3,5-tris[4-（4-flourobenzoyl） phenoxy]benzene） with a function group ratio of 0.48:1（A2:B3）.The chemical structure of HPOP-PEEK-F was confirmed by FTIR and（）1H-NMR.The degree of branching（DB） of HPOP-PEEK-F was 0.66 determined by（）1H-NMR measurements.The phenyl ethynyl-terminated hyperbranched poly（ether ether ketone）（HPOP-PEEK-PEP） was prepared by the end-capping approach.The HPOP-PEEK-PEP showed high glass transition temperature than HPOP-PEEK-F,but exhibited lower thermal stability.After cross-linking,the glass transition temperature,thermal stability and anti-chemical corrodibility of HPOP-PEEK-PEP were all improved.展开更多
文摘Quantum-chemical calculations on some derivatives of [n]-prismanes expanded by ethynyl or ethenyl groups have been performed using density functional theory （DFT） method.Their geometric structures,electronic structures,vertical ionization potentials and vertical electron affinities have been obtained at the B3LYP/6-31G＊＊ level of theory.Meanwhile,the total strain energy has been investigated in detail and compared with [n]-prismane and other derivatives.The present paper has also computed the enthalpies of formation for different isomers so as to evaluate their thermal stabilities.
文摘The first cyclic molecule formation reactions from ethyne （C2H2）, initiated by ethynyl radical （C2H）, were studied by theoretical quantum mechanic. The study included the competition reaction between structure re-arrangement for the favourable ring-closure mechanism and ethyne addition in each step. The analysis was done by evaluating the energy difference of activation （AE）, entalphy （AH）, Gibbs （AG） of the optimized stable and transition molecules. The reaction temperatures were set at normal （T = 298 K） and combustion （T = 1200 K） condition.
基金financially supported by the National Natural Science Foundation of China(Nos.22131005,22201074,22075077 and 21971063)the Fundamental Research Funds for the Central Universities,Program of Shanghai Academic Research Leader(No.20XD1401400)+1 种基金Shanghai Rising-Star Program(No.23QA1402100)Natural Science Foundation of Shanghai(Nos.23ZR1415600,22ZR1416100).
文摘To develop efficient sensitizers for dye-sensitized solar cells(DSSCs),we recently reported doubly concerted companion(DCC)dye XW83 with a wrapped porphyrin sub-dye unit linked to an organic sub-dye unit through a flexible chain,which exhibits panchromatic absorption and excellent anti-aggregation ability.To further improve the absorption,we herein report XW87 and XW88 by inserting an ethynyl group into the organic sub-dye unit of XW83 near the donor and acceptor,respectively.For the corresponding organic dyes Z3 and Z4,the introduced ethynyl group improves their absorption,but induces aggravated charge recombination,leading to lowered power conversion efficiencies(PCEs).Similar to the organic dyes,the introduced ethynyl group improves the absorption of DCC dyes XW87 and XW88 as well.In addition,the ethynyl group near the acceptor of the organic sub-dye unit can be well protected by the long wrapping chains from the porphyrin unit.As a result,XW88 affords the highest JSC(21.84 mA/cm^(2)),V_(OC)(782 mV)and PCE(12.2%)among the DCC dyes.These results provide an effective method for developing efficient DSSC dyes by inserting an ethynyl group at a suitable position of a DCC dye.
基金financially supported by the National Natural Science Foundation of China(No.21674126)the"Strategic Priority Research Program"(No.XDB12010100)the Shanghai Science and Technology Committee(No.16JC1400603)
文摘Two copolymers of P1 and P2 comprising benzothiadiazole, 1,4-bis（dodecyloxy）-benzene units were synthesized by Sonogashira coupling polymerization based on ethynyl-linked 1,2,5,6-naphthalenediimide. Their thermal, optical, electrochemical as well as charge transport properties were studied. Bottom-gate top-contact organic field-effect transistors （OFETs） measurements of P1 and P2 thin films showed different charge transport behaviors. P1 displayed pure electron transport behaviors in OFETs with electron mobility up to 10^-3 cm^2·V-1·s^-1, while P2 exhibited hole transport features. The molecular structure analysis revealed that the structure of P1 has the acceptor-linker-acceptor＇ （A-L-A＇） characteristic, and P2 possesses the donor-linker-acceptor （D-L-A） structure feature. The results demonstrate that different molecular structures lead them to have distinct charge transport behaviors. In particular, the first pure electron transport copolymer in OFETs based on 1,2,5,6-naphthalenediimide is achieved.
基金supported by the Recruitment Program of Global Youth Experts of Chinasupported by the National Natural Science Foundation of China(Nos. 21574138, 51603209 and 91633301)the Strategic Priority Research Program(No. XDB12030200) of the Chinese Academy of Sciences
文摘In this work, star-shaped perylene bisimide（PBI） derivatives with spiro-aromatic cores linked with ethynyl units were developed as electron acceptors for non-fullerene organic solar cells. The ethynyl linkers were found to enhance the planarity of the conjugated backbone, resulting in high electron mobilities and near-infrared absorption. The ethynyl-linked PBI acceptors showed high power conversion efficiencies（PCEs） up to 4.27% due to the high short-circuit current density（Jsc） of 8.52 mA/cm^2 and fill factor（FF） of 0.59, while the PBI acceptor without ethynyl units provided a low PCE of 3.57% in nonfullerene solar cells. The results demonstrate that ethynyl units can be applied into designing new PBI electron acceptors with improved charge transport properties and photovoltaic performance.
基金support from DTRA,under project HDTRA112-1-0039the Army Research Office (ARO) under Grant W911NF-11-1-0251support from the China Scholarship Council (CSC)
文摘The aim of this paper was to test the thermal and environmental stability of poly（4-ethynyl-p-xylylene- co-p-xylylene） thin films prepared by chemical vapor deposition （CVD） and to optimize the reaction conditions of the polymer. Fourier transformed infrared spectroscopy （FTIR）, thermogravimetric analysis （TGA） and fluorescence microscopy were employed to investigate the stability of the reactive polymer coatings in various environmental conditions. Chemical reactivity of the thin films were then tested by Huisgen 1,3-dipolar cycloaddition reaction （＂click＂ reaction）. The alkyne functional groups on poly（4- ethynyl-p-xylylene-co-p-xylylene） thin films were found to be stable under ambient storage conditions and thermally stable up to 100 ℃ when annealed at 0.08 Torr in argon. We also optimized the click reaction conditions of azide-functionalized molecules with poly（4-ethynyl-p-xylylene-co-p-xylylene）. The best reaction result was achieved, when copper concentration was 0.5 retool/L, sodium ascorbate concentration to copper concentration was 5：1. In contrast, the azide concentration and temperature had no obvious effect on the surface reaction.
文摘合成兼具高热稳定性(Td5%=508℃)和高玻璃化转变温度(Tg=374.2℃)的乙炔基封端的聚酰亚胺低聚物(S1),并将其与双酚A型氰酸酯树脂(BCE)进行共混,以提高氰酸酯包括热性能在内的综合性能,制备了S1/BCE互穿网络结构树脂体系。采用差示扫描量热分析、傅里叶变换红外光谱,利用Kissinger-Crane法和T-β外推法研究了BCE和S1的固化动力学行为和固化机理。并对固化后材料的热性能、力学性能和表面形貌进行了研究。结果表明,从红外及动力学分析,S1/BCE体系的固化工艺参数为200℃/2 h+260℃/2 h,2种方法测得的以质量比1∶1混合的树脂体系CS11平均表观活化能为88.9 k J/mol,反应级数为0.91。不同比例下S1/BCE体系固化后的玻璃化转变温度最高相均超过300℃,且在212℃依然有较高的模量保持,同时从电镜图和力学性能可以看出,材料韧性具有一定程度的提升。相比较而言,以质量比1∶1混合的树脂体系CS11的韧性提升最大,Tg=310.9℃,Td5%=424℃,且具有优良的耐热性能。
文摘Fluoro-terminated hyperbranched（poly（aryl） ether ketone）（HPOP-PEEK-F） with 4-phenoxyphenyl side groups was prepared from A2（2-（4-phenoxyphenyl）-1,4-diphenol） and B3（1,3,5-tris[4-（4-flourobenzoyl） phenoxy]benzene） with a function group ratio of 0.48:1（A2:B3）.The chemical structure of HPOP-PEEK-F was confirmed by FTIR and（）1H-NMR.The degree of branching（DB） of HPOP-PEEK-F was 0.66 determined by（）1H-NMR measurements.The phenyl ethynyl-terminated hyperbranched poly（ether ether ketone）（HPOP-PEEK-PEP） was prepared by the end-capping approach.The HPOP-PEEK-PEP showed high glass transition temperature than HPOP-PEEK-F,but exhibited lower thermal stability.After cross-linking,the glass transition temperature,thermal stability and anti-chemical corrodibility of HPOP-PEEK-PEP were all improved.
