Synthesis, Characterization and Photoelectric Property of Flexible Covalently Linked Porphyrin-Fullerene

共价键连给-受体(D-A)化合物因在模拟自然界光合作用、光物理、电化学等方面具有优越的性能，而成为当今世界的研究热点。由于C60具有高度共轭的三维结构，较小的重组能、合适的还原电势等特点，使其成为良好的电子受体(A)。卟啉是一类共轭大环富电子化合物，是理想的电子给予体(D)。卟啉类化合物在半导体、光敏化、光电功能材料、生物等方面都有重要的应用。本文以共价键的方式合成了卟啉-富勒烯化合物，并研究其光化学性能和光电转换性能。通过修饰的卟啉醛、C60和肌氨酸在甲苯中发生1,3偶极环加成反应，合成了不同电子效应取代基(-H，-OCH3)的4种卟啉-富勒烯配体，采用饱和金属醋酸盐的甲醇溶液与配体的氯仿溶...One approach to mimicking energy conversion via photosynthesis involves the construction of synthetic systems containing chromophores, electron donors (D) and electron acceptors (A) linked by covalent bonds. Fullerenes, C60 in particular, have been found to make ideal acceptors in model photosynthetic system, due to their unique three-dimensional structure, the remarkably small reorganization ener...学位：理学硕士院系专业：化学化工学院化学系_无机化学学号：20032500

Synthesis, Characterization and Photovoltaic Effect of Porphyrin-fullerene Compounds MP-C_(60)(M=Zn,Cu,Co)

采用1,3-偶极环加成反应,合成了共价键连卟啉-富勒烯配体(H2P-C60)及配合物MP-C60(M=Zn,Cu,Co)。利用红外光谱、元素分析、紫外-可见光谱、核磁共振氢谱及质谱等手段对产物进行表征。同时对产物的光电转换性能进行了研究。光伏效应结果表明,产物具有优良的光电转换性能。尤其在O2/H2O介质电对中,光生电压值最大可达到195mV,镀层厚度在1μm时,光伏效应值最大。The covalently linked porphyrin-fullerene ligand was synthesized through 1,3-dipolar cycloaddition reaction. The metalloporphyrin-fullerene was prepared by metalation of H_2P-C_ 60 and M(Ac)_2·nH_2O (M=Zn,Cu,Co). They were characterized by methods of FT-IR, Uv-Vis, ~1H NMR, ESI-MS and elemental analysis. The photovoltaic of the compounds was studied. The result showed that heterojunction electrode formed by MP-C_ 60 /GaAs was good, especially in the O_2/H_2O redox couple, and the greatest value of photovoltaic potential was 195mV. MP-C_ 60 /GaAs electrode at 1μm for thinckness of MP-C_ 60 film was the best one.福建省自然科学基金(E0410001);; 厦门大学自选课题基金(0040-Y07008)资助项

Synthesis and Characterization of Covalently Linked Porphyrin-fullerene Compounds

The covalently linked porphyrin-fullerene dyads were synthesized. The ligand 5-[4′-(4″-Phenoxybutoxy)phenyl]-N-(2-methyl)fulleropyrrolidine-10,15,20-tri-(p-methoxyphenyl)porphyrin (H2P-C60) was synthesized by 1,3 dipolar cycloaddition reaction with C60, sarcosine and H2P-CHO. The zinc porphyrin-fullerene was prepared by metalation of H2P-C60 and zinc acetate. The compounds were characterized by meams of IR, UV-Vis, ESI-MS, elemental analysis, and 1H NMR.福建省自然科学基金项目(No.E0410001);; 厦门大学自选课题基金项目(No.0040-Y07008

Synthesis, Characterization and Photovoltaic Effect of Porphyrin-Fullerene Compounds MP-C_(60)

The convalently linked porphyrin-fullerene ligand was synthesized by 1,3 dipolar cycloaddition reaction. The ligand and complexes were characterized by means of FT-IR, Uv-Vis, ~1HNMR, ESI-MS and elemental analysis. The photoelectricity transform performance of the compounds was studied.The result indicated that the photovoltaic effect of (n+n) heterojunction electrode formed by MP-C_(60)/GaAs was super, especially in the I_2/I_3~- and O_2/H_2O redox couples, and photovoltaic potential was preferable.The photovoltaic performance of a MP-C_(60)/GaAs electrode at 1-2 μm thinck MP-C_(60) film of appeared peak value.ProjectsupportedbytheNatureScienceFoundationofFujianprovince(E0410001)andSelf-selectProgramofXiamenUniversity(0040-Y07008)

Synthesis and characterization of covalently linked porphyrin-fullerene compounds

The covalently linked porphyrin-fullerene dyads were synthesized. The ligand 5-[4-(4"-Phenoxybutoxy) phenyl]-N-(2-methyl)fulleropyrrolidine-10,15,20-tri-(p-methoxyphenyl)porphyrin (H2P-C-60) was synthesized by 1,3 dipolar cycloaddition reaction with C-60, sarcosine and H2P-CHO. The zinc porphyrin-fullerene was prepared by metalation of H2P-C-60 and zinc acetate. The compounds were characterized by meams of IR, UV-Vis, ESI-MS, elemental analysis, and H-1 NMR

Synthesis, characterization and photovoltaic effect of porphyrin-fullerene compounds MP-C-60

The convalendy linked porphyrin-fullerene ligand was synthesized by 1, 3 dipolar cycloaddition reaction. The ligand and complexes were characterized by means of FT-IR, Uv-Vis, (HNMR)-H-1, ESI-MS and elemental analysis. The photoelectricity transform performance of the compounds was studied. The result indicated that the photovoltaic effect of (n + n) heterojunction electrode formed by MP-C-60/GaAs was super, especially in the I-2/I-3(-) and O-2/H2O redox couples, and photovoltaic potential was preferable. The photovoltaic performance of a MP-C-60/GaAs electrode at 1-2 mu m thinck MP-C-60 film of appeared peak value

Synthesis and Photoelectric Property of Four New D-A Compounds

合成了H2Po-C70,H2Pp-C70,ZnPo-C70和ZnPp-C704种新型的D-A化合物;通过紫外-可见吸收光谱、红外光谱、质谱和元素分析等多种手段对其进行了表征.在光电化学电池中,在GaAs电极上测量了这4种D-A化合物的光伏效应(PVE).研究结果表明,H2P-C70/GaAs和ZnP-C70/GaAs电极的光生电压(ΔV)和光生电流(ΔI)比单纯的GaAs电极大得多,据此能够确定这4种D-A化合物具有优良的光电性能.In the present work, four new D-A compounds, H_2P_o-C_ 70, H_2P_p-C_ 70, ZnP_o-C_ 70 and ZnP_p-C_ 70 were prepared by 1,3 dipolar cycloaddition reaction of C_ 70. The new D-A compounds were characterized by UV-Vis, FTIR, ESI-MS, as well as elemental analysis. The results show that four novel types of covalently linked porphyrin-fullerene dyads were formed. The photovoltaic effect(PVE) of the new D-A compounds on GaAs electrode in electrochemical photovoltaic cell were measured. The results show that the values of ΔV and ΔI for H_2P-C_ 70/GaAs and ZnP-C_ 70/GaAs electrode are much greater than those for pure GaAs electrode. So that the photoelectric properties for the new D-A compounds are excellent. In addition, the photoelectric property of a H_2P-C_ 70/GaAs and ZnP-C_ 70/GaAs electrode is related to the thinkness of the sample film and the media.福建省自然科学基金(批准号:E0410001);; 厦门大学自选课题基金(批准号:0040-Y07008)资助

Studies on Photoelectric Property of Porphyrin-fullerene Compounds MP-C_(60)(M=H_2,Zn)

按文献方法合成了共价键连卟啉-富勒烯化合物,通过荧光光谱和光伏效应测得它们的光化学和光电转换性能,并对卟啉-富勒烯化合物的轴向配位进行了初步探究.结果表明,卟啉键合富勒烯后荧光强度明显减弱,出现荧光猝灭现象,邻位取代锌卟啉-富勒烯化合物的荧光猝灭强于相应的对位取代锌卟啉-富勒烯化合物;光伏效应结果表明化合物具有优良的光电转换性能,尤其在介质电对O2/H2O中,光生电压达到最大,镀层厚度在1μm出现最大值.电子吸收光谱数据表明卟啉-富勒烯化合物轴向配位后谱带发生明显移动,这是吡啶上的氮与锌卟啉-富勒烯中的锌离子发生轴向配位的结果.The porphyrin-fullerene compounds MP-C_(60)(M=H_2,Zn) have been synthesized by 1,3-dipolar cycloaddition reaction.The characterization of photochemistry and photoelectricity transform have been investigated by fluorescene and photovoltaic effect.The axial coordination of porphyrin-fullerene compounds also has been researched primarily.The results show that the porphyrin emission bands quenched and the quenching for the ortho-substituted derivations is higher than the para-substituted ones.Futhermore,excellent photoelectric property of MP-C_(60)has been showen by the result of photovoltaic effect;especially when in the O_2/H_2O redox couple and at 1 μm for thickness of MP-C_(60) film.In addition,the electronic absorption band has been obviously shifted after the axial coordination with ZnP-C_(60),and this attributed to the electrionic effect caused by the N atom of the pyridine axial coordinated to the Zinc ion in the central ZnP-C_(60).福建省自然科学基金(E0410001);; 厦门大学自选课题基金(0040-Y07008)资

Synthesis and Characterization of Novel Covalently Linked Fullerene-porphyrin Compouds

为了构造一个具有有效电荷转移的给-受体体系,通过1,3-偶极加成反应,由5-[2-′(4″-醛基苯氧丙氧苯基)]-10,15,20-三苯基卟啉(H2P-CHO)、肌氨酸和C60首次合成了一种新的以共价键相连的富勒烯-卟啉配体(H2P-C60),同时用该配体制备了其锌配合物(ZnP-C60),并用红外光谱、元素分析、电子光谱、核磁共振氢谱和质谱等方法进行了表征.In order to construct a donor-acceptor system with efficient electron transfer, a novel covalently linked fullerene-porphyrin ligand(H_2P-C_-{60-}) was synthesized by 1,3-dipolar cycloaddition reaction of C_-{60-}, sarcosine and H_2P-CHO, and it′s zinc derivative was prepared by metalation of H_2P-C_-{60-} and zinc acetate. The two new fullerene-porphyrin compounds were characterized by means of elemental analysis, IR, electronic spectra, ESI-MS and -{-}~1H NMR.They are also predicted to have good optical and electrical properties.福建省自然科学基金(批准号:E0410001);; 厦门大学自选课题基金(批准号:0040-Y07008)资

Synthesis,Characterization and Photovoltaic Property of Pyrrolidine Ring-fused Metallo-fullerenes

采用肌氨酸甲酯(CH_3NHCH_2COOMe)与C_(60)光化学反应制得富勒烯吡咯衍生物(C_(60)Pyr),产率为67％(基于已反应的C_(60)),并以其为配体,在N_2气气氛下利用配体取代法合成了富勒烯吡咯金属配合物(PyrC_(60))-Pd(dppe),产率为51％(基于C_(60)吡咯衍生物)。采用元素分析、质谱、紫外-可见吸收光谱、红外光谱、X射线光电子能谱和核磁共振(~(31)P NMR)等测试技术对中间物及产物进行了表征,同时在光电化学电池中于GaAs电极上测量了化合物(PyrC_(60))-Pd(dppe)的光伏效应(PVE),研究了介质电对、配合物薄膜厚度对光电性能的影响。研究结果表明,(PyrC_(60))-Pd(dppe)/GaAs电极的值比单纯的GaAs电极的ΔV和ΔI相应值大得多,这种化合物具有优良的光电性能。尤其在O_2/H_2O介质电对中,光生电压值最大可达230 mV,光生电流最大可达8．7μA。镀层厚度在0．5～1μm时,光伏效应值较大。Pyrrolidine ring-fused fullerene derivative(C_(60)Pyr)was prepared by photolysis via the reaction of C_(60) with CH_3NHCH_2COOMe in 67% yield(based on consumed C_(60)).The product(PyrC_(60))-Pd(dppe)was obtained by the method of ligand substitution via the reaction of C_(60)Pyr with Pd(dppe)_2 in nitrogen atmosphere at room temperature in 51% yield(relative to C_(60)Pyr).The products were characterized by means of elemental analysis,IR,UV-Vis,X-ray photoelectron spectroscopy and ~(31)P NMR.The photovohaic effect(PVE)of the compound on GaAs electrode in electrochemical photovohaic cell were measured.Influences of various redox couples and the thickness of the complex film were observed.The results show that the values of△V and△I for (PyrC_(60))-Pd(dppe)-GaAs electrode are much greater than those for pure GaAs electrode.So that the photo- electric properities for the compound are excellent,especially in the O_2/H_2O redox couple,the greatest value of photovoltaic potential was 230 mV,and the greatest value of photovoltaic current was 8.7μA.The results showed that(PyrC_(60))-Pd(dppe)/GaAs electrode at 0.5～1μm for thinckness of(PyrC_(60))-Pd(dppe)film was the best.福建省自然科学基金(F0210010);; 厦门大学校级自选课题基