Synthesis,Characterization and Photoelectric Property of Bidentate-diphosphine Fullerene Metal Complexes

通过低价态过渡金属有机基团的配位对C60进行化学修饰，可调整C60的电子结构，使其具有光电、催化等方面的特殊性能，因此，这方面的研究为富勒烯及其金属配合物的应用开发有着比较重要的意义。对于Ⅷ族金属而言，富勒烯单齿膦金属配合物的研究已较为深入，如不同合成方法、晶体结构的表征、催化与光电转换等性能的研究，而对富勒烯双齿膦金属配合物的研究却开展较少。在本课题组以往三苯基膦系列富勒烯金属配合物研究的基础上，论文选择双齿膦dppm、dppe为配体，Pd、Ni、Ru等Ⅷ族金属为中心金属，合成出一系列富勒烯双齿膦金属配合物。按文献方法合成的双齿膦dppm、dppe配体，与Pd、Ni、Ru等化合物反应合成相应...In the structure of C60 molecule, there are two distinct types of C-C bonds in which the bonds at 6:6 ring junctions are shorter and behave as olefin unit. So the metal ions can easily coordinate to them in a η2-fashion. Hyperconjugation effect maybe lies in the fullerene metal complex, which makes the electrons flow easier in the large scope. Therefore, the complexes show promising properties in ...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：20012500

Synthesis,Characterization and Photoelectric Property of Bidentate-diphosphine Fullerene Metal Complexes

通过低价态过渡金属有机基团的配位对C60进行化学修饰，可调整C60的电子结构，使其具有光电、催化等方面的特殊性能，因此，这方面的研究为富勒烯及其金属配合物的应用开发有着比较重要的意义。对于Ⅷ族金属而言，富勒烯单齿膦金属配合物的研究已较为深入，如不同合成方法、晶体结构的表征、催化与光电转换等性能的研究，而对富勒烯双齿膦金属配合物的研究却开展较少。在本课题组以往三苯基膦系列富勒烯金属配合物研究的基础上，论文选择双齿膦dppm、dppe为配体，Pd、Ni、Ru等Ⅷ族金属为中心金属，合成出一系列富勒烯双齿膦金属配合物。按文献方法合成的双齿膦dppm、dppe配体，与Pd、Ni、Ru等化合物反应合成相应...In the structure of C60 molecule, there are two distinct types of C-C bonds in which the bonds at 6:6 ring junctions are shorter and behave as olefin unit. So the metal ions can easily coordinate to them in a η2-fashion. Hyperconjugation effect maybe lies in the fullerene metal complex, which makes the electrons flow easier in the large scope. Therefore, the complexes show promising properties in ...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：20012500

Synthesis and Photovoltaic Effect Study for Fullerene Complexe C_(60)Pd(Ph_2PCH_2PPh_2)

在氮气氛下 ,采用配体取代法 ,即以C60 取代Pd(Ph2 PCH2 PPh2 ) 2 中一个Ph2 PCH2 PPh2 合成出富勒烯金属配合物C60 Pd(Ph2 PCH2 PPh2 ) ,采用元素分析、红外光谱、紫外可见光谱、光电子能谱以及X射线粉末衍射等手段对产物进行表征 .同时研究了产物的光电性能、氧化还原性能及热稳定性能 .光伏效应研究结果表明 ,产物具有优良的光电转化性能 ,尤其是在BQ/H2 Q介质电对中 ,光生电压最大达到 174mV ;当C60 Pd(Ph2 PCH2 PPh2 )薄膜厚度为 1μm时 ,光伏效应值最大 .Fulerene complexe C_ 60Pd(Ph_2PCH_2PPh_2) was perpared by the method of ligand substitution via the reaction of C_ 60 with Pd(Ph_2PCH_2PPh_2)_2 under condition of a nitrogen atmosphere and refluxing, and the title compound was appraised and characterized by methods of elemental analysis, FT-IR, UV-vis, XPS and XRD.The results showed that the structure of purposeful product was that the Ph_2PCH_2PPh_2 took up two coordination sites of the central metal, and C_ 60 took up another two sites in σ-π feeback pattern. The porperties on photoelectricity, redox and thermostability of the title complexe were studied. The results of studying on photoelectricity showed that the photovoltaic effect of (n+n) heterojunction electrode formed by C_ 60Pd(Ph_2PCH_2PPh_2)/GaAs was supper, especially in the BQ/H_2Q redox couple, and the greatest value of photovoltaic potential was up to 174 mV. The photovoltaic performance of C_ 60Pd(Ph_2PCH_2PPh_2)/GaAs electrode at 1 μm for thickness of C_ 60Pd(Ph_2PCH_2PPh_2) film was the best.ProjectsupportedbytheNaturalScienceFoundationofFujianprovince (E0 4 10 0 0 1,E0 110 0 0 1,F0 2 10 0 10 ) ,DoctorProgramofHighterEductionofChina (980 384 10 )andSelf selectProgramofXiamenUniversity

Synthesis and photovoltaic effect study for fullerene complexe C60Pd(Ph2PCH2PPh2)

Fulerene complexe C-60 Pd (Ph2PCH2PPh2) was perpared by the method of ligand substitution via the reaction of C-60 with Pd(Ph2PCH2PPh2)(2) under condition of a nitrogen atmosphere and refluxing, and the title compound was appraised and characterized by methods of elemental analysis, FT-IR, UV-vis, XPS and XRD. The results showed that the structure of purposeful product was that the Ph2PCH2PPh2 took up two coordination sites of the central metal, and C-60 took up another two sites in sigma-pi feeback pattern. The porperties on photoelectricity, redox and thermostability of the tide complexe were studied. The results of studying on photoclectricity showed that the photovoltaic effect of (n + n) heterojunction electrode formed by C60Pd(Ph2PCH2PPh2)/GaAs was supper, especially in the BQ/H(2)Q redox couple, and the greatest value of photovoltaic potential was up to 174 mV. The photovoltaic performance of C60Pd (Ph2PCH2PPh2)/GaAs electrode at 1 mum for thickness of C60Pd(Ph2PCH2PPh2) film was the best

Synthesis and Redox Property of Complex η~2-C_(60)Ru(dppe)

采用还原取代法合成了配合物C60Ru(dppe),通过元素分析、红外光谱、紫外-可见光谱、X射线光电子能谱和X射线多晶粉末衍射等多种手段对配合物进行表征,并研究了配合物的氧化还原性能.结果表明,C60以碳碳6 6双键与Ru配位形成稳定的2η型配合物;氧化还原性能研究表明,C60与金属有机基团形成配合物后,其还原电位向负方向发生了移动.In the structure of C_(60) molecule,there are two distinct types of C-C bonds in which the bond at 66 ring junctions are shorter and behave as olefin unit.So the metal ion can easily coordinate to them in a η~2-fashion.Hyperconjugation effect lies in fullerene metal complexes,which makes the electrons flow easier in the large scope.Therefore,the complex shows promising properties in photoelectric and catalysis aspects.In the present work,we chose Ru as the central metal of complex.The fullerene complex C_(60)Ru(dppe) was prepared by the method of reduction and substitution via the reaction of C_(60) with the reductive product of Ru(dppe)_2Cl_2,with NaBH_4 as reducing agent under the conditions of a nitrogen atmosphere and refluxing.The synthesized complex was characterized by methods of elemental analysis,infrared spectra,UV-vis electronic spectra,X-ray photoelectron spectra,X-ray diffraction spectra,etc.In addition,the oxidation and reduction properties of the complex was studied by cyclic voltammetry.The result of the redox study indicates that the reduction potential of the complex is more negative than that of pure C_(60).福建省自然科学基金(F0210010、E0410001)资

Synthesis and Characterization of Pd(dppm)_2 and Its Catalytic Properties

合成了以双齿膦dppm为配体的金属配合物Pd(dppm)2,通过元素分析、红外光谱、热分析、光电子能谱、多晶粉末衍射等技术对该配合物的结构进行表征;用该配合物制备负载型Pd催化剂,并对其催化性能进行了研究,表明该催化剂对CO催化氧化成CO2的反应具有较好的催化效果.The title complex,Pd(dppm)_2 was prepared by treatment of a solution of PdCl_2 with bis(diphenylphosphino)methane (dppm) and NH_2NH_2·H_2O in nitrogen atmosphere,with yield at 81.2 percent.As a new palladium complex with ligand of phosphine,Pd(dppm)_2 was characterized by elementary analysis,IR spectra,XPS spectra,X-ray powder analysis,as well as thermal analysis.A plane square structure of the complex was supposed.The IR and XPS measurements showed that the state of Pd in the complex of Pd(dppm)_2 was in between zero- and +2 state,and Ph-P-Pd-P-Ph hyperconjugation was found in the complex.Pd(dppm)_2/γ-Al_2O_3 catalyst was prepared by solvated metal atom impregnation (SMAI) method.The result of activity assay indicated that the catalyst of Pd(dppm)_2 supported onγ-Al_2O_3 with high dispersion showed high catalytic activity for the oxidation of carbonmonoxide,with CO conversion reaching 100% at 75℃ and GHSV=30 000 mL(STP)·h~(-1)·g~(-1),with good stability during 19 h of reaction operation.The Ph-P-Pd-P-Ph hyperconjugation enlarge the dislocalization scope of the electron cloud,which may be an important reason that Pd(dppm)_2/γ-Al_2O_3 catalyst exhibited higher activity for CO oxidation at low temperature than that of PdCl_2/γ-Al_2O_3 catalyst at the same experimental condition.福建省自然科学基金(F0210010);; 厦门大学校级自选课题基金资