Three new chromophores with triphenylamine as molecular focal point bearing one, two, or three 4-(n-butyloxystyryl) group(s) at the periphery respectively, (named as T1, T2, and T3) have been synthesized and character...Three new chromophores with triphenylamine as molecular focal point bearing one, two, or three 4-(n-butyloxystyryl) group(s) at the periphery respectively, (named as T1, T2, and T3) have been synthesized and characterized. It is interesting to find that the fluorescence quantum yield increases from T1 (0.489), to T3 (0.535), and to T2 (0.628) in cyclohexane, meanwhile the lifetime for T3 is shorter than T1 and T2, which is an important characteristic for applications in light emitting diode. Also PMMA (polymethyl methacrylate) film doped with T3 gives stronger fluorescence than T1, and T2. Cyclic voltammetry showed that T3 exhibited lowest oxidation potential of 0.52 V vs SCE, suggesting its better hole-transport property.展开更多
以对氨基酚、对硝基氯苯、8-羟基喹啉、4-硝基邻苯二甲腈以及醋酸锌为主要原料,合成了不对称2(3)-[二(对硝基苯基)氨基苯氧基]-9(10),16(17),23(24)-三(8-喹啉氧)锌酞菁(TQPc).用核磁、红外、元素分析等表征TQPc以及前驱化合物结构,TQP...以对氨基酚、对硝基氯苯、8-羟基喹啉、4-硝基邻苯二甲腈以及醋酸锌为主要原料,合成了不对称2(3)-[二(对硝基苯基)氨基苯氧基]-9(10),16(17),23(24)-三(8-喹啉氧)锌酞菁(TQPc).用核磁、红外、元素分析等表征TQPc以及前驱化合物结构,TQPc的电子吸收光谱表现出了强烈的π-π*跃迁现象.利用紫外光谱研究了其N,N-二甲基甲酰胺(DMF)和CH2Cl2溶液的吸收光谱性质,结果表明在DMF中主要以单体的形式存在,浓度在0.223×10-5～2.587×10-5mol/L时,TQPc在CH2Cl2溶液中有二聚体的存在,经计算得到平衡常数为0.24×105L/mol.用循环伏安法研究了TQPc的氧化还原行为,结合差分伏安数据计算了能级结构,LUMO(-1.04 V vs SCE)和HOMO(0.78 V vs SCE)与纳米TiO2导带能级匹配,可作为性能较好的电荷传输材料用于染料敏化太阳能电池.展开更多
Functional organic dyes have promising prospect in dye-sensitized solar cells as a crucial element, of which sensitizers based on donor-π-acceptor are the most important dyes. On the basis of the structures of the ar...Functional organic dyes have promising prospect in dye-sensitized solar cells as a crucial element, of which sensitizers based on donor-π-acceptor are the most important dyes. On the basis of the structures of the aromatic amine donors such as triphenylamine and indoline, this paper reviews the photoelectric conversion properties of organic sensitizers since 2008, and highlights research work in our laboratory in this area.展开更多
The photocatalytic oxidative coupling of thiols is one of the most popular methods to synthesize the disulfides.Triphenylamine and its derivatives(TPAs)are promising for the above reaction,but suffer from the easy pol...The photocatalytic oxidative coupling of thiols is one of the most popular methods to synthesize the disulfides.Triphenylamine and its derivatives(TPAs)are promising for the above reaction,but suffer from the easy polymerization and difficult separation.To overcome these obstacles while controlling the photogenerated electrons transfer directly to target substrates,herein,we constructed one TPA-based metal-organic framework(MOF),(Me_(2)NH_(2))[Sr(TCBPA)]·DMA·3H_(2)O(1),by direct self-assembly of tris(4′-carboxybiphenyl)amine(H_(3)TCBPA)and photoredox inert strontium ion(Sr^(2+)).DFT calculations revealed that the valence band maximum(VBM)and the conduction band minimum(CBM)are mainly located on TCBPA^(3-),successfully inhibiting the undesirable electron migration to metal nodes.Experimental results indicated that 1 displays superior performance than homogeneous H_(3)TCBPA,which may result from the abundant π…π and C—H…π interactions between the well-arranged TCBPA^(3-)and the build-in electric field between the anionic framework and the Me_(2)NH^(2+).This work highlights that immobilizing TPAs into MOFs is one promising approach to designing heterogeneous photocatalysts for the synthesis of disulfides by oxidative coupling of thiols.展开更多
基金supported by the National Natural Science Foundation of China(Grant No.50273024)the Natural Foundation of Jiangsu Province(Grant No.BK2002041)the Foundation of Jiangsu Province Education Committee(Grant No.02KJB430001)
文摘Three new chromophores with triphenylamine as molecular focal point bearing one, two, or three 4-(n-butyloxystyryl) group(s) at the periphery respectively, (named as T1, T2, and T3) have been synthesized and characterized. It is interesting to find that the fluorescence quantum yield increases from T1 (0.489), to T3 (0.535), and to T2 (0.628) in cyclohexane, meanwhile the lifetime for T3 is shorter than T1 and T2, which is an important characteristic for applications in light emitting diode. Also PMMA (polymethyl methacrylate) film doped with T3 gives stronger fluorescence than T1, and T2. Cyclic voltammetry showed that T3 exhibited lowest oxidation potential of 0.52 V vs SCE, suggesting its better hole-transport property.
文摘以对氨基酚、对硝基氯苯、8-羟基喹啉、4-硝基邻苯二甲腈以及醋酸锌为主要原料,合成了不对称2(3)-[二(对硝基苯基)氨基苯氧基]-9(10),16(17),23(24)-三(8-喹啉氧)锌酞菁(TQPc).用核磁、红外、元素分析等表征TQPc以及前驱化合物结构,TQPc的电子吸收光谱表现出了强烈的π-π*跃迁现象.利用紫外光谱研究了其N,N-二甲基甲酰胺(DMF)和CH2Cl2溶液的吸收光谱性质,结果表明在DMF中主要以单体的形式存在,浓度在0.223×10-5～2.587×10-5mol/L时,TQPc在CH2Cl2溶液中有二聚体的存在,经计算得到平衡常数为0.24×105L/mol.用循环伏安法研究了TQPc的氧化还原行为,结合差分伏安数据计算了能级结构,LUMO(-1.04 V vs SCE)和HOMO(0.78 V vs SCE)与纳米TiO2导带能级匹配,可作为性能较好的电荷传输材料用于染料敏化太阳能电池.
基金supported by the National Natural Science Foundation of China (2116110444 and 21172073)National Basic Research Program of China (973 Project, 2011CB808400)+1 种基金the Fundamental Research Funds for the Central Universities (WJ0913001)Scientific Committee of Shanghai (10520709700)
文摘Functional organic dyes have promising prospect in dye-sensitized solar cells as a crucial element, of which sensitizers based on donor-π-acceptor are the most important dyes. On the basis of the structures of the aromatic amine donors such as triphenylamine and indoline, this paper reviews the photoelectric conversion properties of organic sensitizers since 2008, and highlights research work in our laboratory in this area.
基金supported by NSFC(22101160)the"1331"Project of Shanxi ProvinceResearch Project Supported by Shanxi Scholarship Council of China(2020-088).
文摘The photocatalytic oxidative coupling of thiols is one of the most popular methods to synthesize the disulfides.Triphenylamine and its derivatives(TPAs)are promising for the above reaction,but suffer from the easy polymerization and difficult separation.To overcome these obstacles while controlling the photogenerated electrons transfer directly to target substrates,herein,we constructed one TPA-based metal-organic framework(MOF),(Me_(2)NH_(2))[Sr(TCBPA)]·DMA·3H_(2)O(1),by direct self-assembly of tris(4′-carboxybiphenyl)amine(H_(3)TCBPA)and photoredox inert strontium ion(Sr^(2+)).DFT calculations revealed that the valence band maximum(VBM)and the conduction band minimum(CBM)are mainly located on TCBPA^(3-),successfully inhibiting the undesirable electron migration to metal nodes.Experimental results indicated that 1 displays superior performance than homogeneous H_(3)TCBPA,which may result from the abundant π…π and C—H…π interactions between the well-arranged TCBPA^(3-)and the build-in electric field between the anionic framework and the Me_(2)NH^(2+).This work highlights that immobilizing TPAs into MOFs is one promising approach to designing heterogeneous photocatalysts for the synthesis of disulfides by oxidative coupling of thiols.
