聚硅氧烷负载富勒烯铂配合物的合成及其催化性能

对 C60 及其衍生物的金属化合物催化性能的研究表明 ,以富勒烯为基体的催化剂对许多化学反应具有独特的催化活性 ,这方面的研究是富勒烯科学的一个重要发展方向 ,并显示出良好的应用前景 .但在已有的工作中 ,研究的主要是 C60 的小分子金属配合物、有机金属复合物以及纳米级金属吸附在C60 的表面所形成的金属 - C60 混合物等的催化性能 ,而有关高分子负载富勒烯金属配合物在催化方面的应用较少报道 [1～ 5] .富勒烯是一个具有独特球形 π电子体系的弱电子给体 ,且体积庞大 ,它的引入势必会改变高分子负载催化剂金属活性中心的局部电荷密度…     

富勒烯的金属配合物及其催化性能

富勒烯的金属配合物及其催化性能１）刘英陈远荫２）盛蓉生（武汉大学化学系武汉４３００７２）关键词富勒烯金属配合物催化分类号Ｏ６４３．３２碳元素的第三种存在形式富勒烯正以其独特的结构和性能以及诱人的应用前景引起人们日益浓厚的兴趣．其中又以Ｃ６０的研究为主...     

新型富勒烯膦金属配合物的合成

用配体取代法合成了新型富勒烯膦金属配合物——C60.双(二苯基膦)戊烷合钯[C60Pd(dpppe),1],其结构经UV-Vis,IR,XPS及元素分析表征。在1的分子结构中,C60以σ-π配位方式与Pd配位,形成新型的η2-C60双齿膦金属配合物。     

富勒烯配合物η2-C60[Ru(NO)(PPh3)]2的合成与表征

从1985年Kroto等[1]发现富勒烯至今, 其在化学、材料和物理等领域已有较多的研究[2～8]. 目前有关C60取代的金属小分子配合物(如羰基、亚硝酰基等)的研究方兴未艾. 而以NO为配体的亚硝酰基金属富勒烯配合物仅有数例[2,3], Green等[3]在研究以CO和NO为配体的金属富勒烯系列化合物的合成中, 认为C60不能与Ru(NO)2(PPh3)2发生反应. 本文利用Ru(NO)2(PPh3)2与C60反应首次合成出η2-C60[Ru(NO)(PPh3)]2配合物, 并对其进行了表征.     

C60Pt(CO)(Pph3)配合物的合成及氧化还原性能研究

采用配体取代法,即在惰性气氛下以C60取代Pt(CO)2(Pph3)2中的CO及Pph3,合成了C60Pt(CO)(Pph3)富勒烯金属配合物,利用元素分析、红外光谱、紫外可见光谱、光电子能谱等手段对产物进行鉴定和表征,结果表明,C60以σ-π配位方式与Pt形成了稳定的η2型C60配合物.由于该分子存在超共轭作用,分子内电子流动性大,因而该配合物可能具有良好的光电转化性能及催化性能.氧化还原性能研究表明,C60在与金属有机基团Pt(CO)(Pph3)形成配合物后,其还原电位向负方向发生了移动.     

新型内嵌混合金属氮化物原子簇富勒烯的合成、结构与性质*

内嵌混合金属氮化物原子簇富勒烯的发现极大地扩展了内嵌富勒烯家族。内嵌混合金属氮化物原子簇富勒烯是一类新型的内嵌富勒烯,其内嵌物为由2-3种不同的金属组成的氮化物原子簇。本文首先介绍了新型内嵌混合金属氮化物原子簇富勒烯的发现、合成和分离方法,并对目前所分离出来的内嵌混合金属氮化物原子簇富勒烯进行了分类。然后总结了目前所报导的内嵌混合金属氮化物原子簇富勒烯的结构表征手段,对于不同的内嵌混合金属氮化物原子簇富勒烯的分子结构分别进行了阐述。最后着重讨论了内嵌混合金属氮化物原子簇富勒烯的特殊电子性质以及物理和化学性质。本文还对内嵌混合金属氮化物原子簇富勒烯潜在的应用前景作了展望,在内嵌具有不同物理性质的两到三种金属原子的基础上,所形成的内嵌混合金属氮化物原子簇富勒烯有可能兼具不同金属原子各自的性质,从而成为多功能综合的功能材料。     

（C60）2Ru2Cl4[Ph2P（CH2）4PPh2]配合物的合成

在氮气氛中采用配体取代法合成了C60以σ-π配位方式与Ru形成的稳定η2型富勒烯双核钌金属配合物(C60)2Ru2Cl4[Ph2P(CH2)4PPh2],其结构经UV,IR,XPS,XRD和元素分析表征.     

C60RuH2(CO)(PPh3)配合物的合成和氧化还原性能研究

自从1985年Kroto等人发现C60等碳原子簇以来,在化学、物理以及材料科学掀起了富勒烯的研究热潮。目前富勒烯配合物的制备及其性质的研究是富勒烯化学最为活跃的研究领域之一,人们正致力于探索富勒烯各类衍生物的结构与性质之间的依赖关系,以期合成出具有特殊性能的富勒烯配合物,为富勒烯的实际开发应用奠定基础。本文合成表征了C60RuH2(OH)(PPh3)配合物,研究了其氧化还原特性。     

内嵌富勒烯的研究进展

内嵌富勒烯由于其结构新颖以及独特而优异的性质在国际上引起持续而广泛的关注,成为近年来的研究热点之一.目前已经研究发现的内嵌富勒烯多达近百种,从惰性气体到碱土金属再到稀土元素都已被成功地嵌入到不同尺寸的碳笼中.其中金属离子或含金属的离子簇内嵌入富勒烯碳笼形成的内嵌金属富勒烯,以其种类丰富、结构多样成为内嵌富勒烯的主要研究对象.本文就近年来研究报道的种类繁多的内嵌富勒烯按其内嵌物类型进行归纳阐述,为今后开发更多新型的内嵌富勒烯提供一定的参考.     

(η2-C60)[Pd(pph3)2]n配合物的合成和光电性能研究

从1985年Kroto等[1]发现C60等富勒烯(球烯)至1996年富勒烯的发现者获诺贝尔化学奖期间,在化学、物理、材料等学科领域逐渐地形成了富勒烯的研究热潮[1,2].现在人们正以较多注意力投向富勒烯的各类衍生物结构与性能之间关系的研究,以期望在开发应用方面迈出更大的步伐.它首次合成出-系列的(η2-C60)[Pd(pph3)2]n(n=1、2、3、4)配合物,并比较这些在结构与组成上有差异配合物的光电转换性能.     

π-Electronic Charge-Transfer Interactions in Inclusion Complexes of Fullerenens with Cyclic Dimers of Metalloporphyrins

Spectroscopic and voltammetric analyses on inclusion complexes of a fullerene such as C₆₀ with a cyclic dimer of a free-base porphyrin (1-M; M = 2H) and its metal complexes (M = Co, Ag, and Zn) showed that a charge-transfer interaction is partly responsible for the complexation.     

Chemically modified fullerene derivatives as photosensitizers in photodynamic therapy: A first‐principles study

The first‐principles density functional theory (DFT) and its time‐dependent approach (TD‐DFT) are used to characterize the electronic structures and optical spectra properties of five chemically modified fullerenes. It is revealed that the metal fullerene derivatives possess not only stronger absorption bands in visible light regions than organically modified fullerene but also the large energy gaps (ΔE_S–T > 0.98 eV) between the singlet ground state and the triplet state, which imply their significant aspect of potential candidates as a photosensitizer. We have found that a new metal‐containing bisfullerene complexes (Pt(C₆₀)₂), with the extended conjugated π‐electrons, much degenerate orbitals and a uniform electrostatic potential surface, behave more pre‐eminent photosensitizing properties than other examined fullerene derivatives. © 2012 Wiley Periodicals, Inc.     

富勒烯(C~6~0, C~7~0)的金属有机化学

综述了1990年以来富勒烯金属有机化学研究的进展,结果表明富勒烯(C~6~0,C~7~0)能与第VIII及IVB、VB、VIB、VIIB族等过渡金属形成各类衍生物,具有潜在的应用前景。     

Complexes of C60 fullerene with simple donor molecules: Theoretical study

The complex formation between fullerene C60 and simple donor molecules such as dimethyl ether, dimethylamine, dimethylsulfide, furan, pyrrole, and thiophene has been studied applying the hybrid MP2/6‐31G(d′):PM3 ONIOM approach for geometry optimization. Local implementation of Møller–Plesset perturbation theory in combination with 6‐31G(d) and 6‐311G(d,p) basis sets was used for binding energies estimation of fullerene complexes. Two factors were found to contribute most to the complex stability: the polarizability and molecular volume of donor molecule. As follows from positive stabilization energies at the Hartree–Fock level, the stabilization of fullerene complexes is entirely due to dispersion interactions in accordance with available experimental data. The calculations show that for donors of similar molecular volume the binding energy of molecular complex increases with polarizability of donor molecules. Similarly, for such complexes the partial charges on molecules increase with decreasing of ionization potentials of donor molecules. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

C60负离子化学的研究进展

中性的C60是很强的缺电子体,主要和亲核试剂进行化学反应.与之不同的是C60经还原生成负离子后,由缺电子变为富含电子,具有很强的亲核性质,可与亲电试剂进行反应.由于这种电子结构的变化,C60负离子进行的反应从机理至产物均有可能与中性富勒烯不同.从而丰富了富勒烯的反应方式和富勒烯产物的类型.结合我们的工作综述了C60负离子化学的研究进展,对丰富富勒烯化学、扩展富勒烯衍生物的种类及制备方法具有一定意义.     

Thermal Decomposition of Fullerene Derivatives A Synthesis Method of New Fullerene Based Molecules

The thermal decomposition of methano-fullerene derivatives such as ethoxycarbonyl methano[60] fullerene and various isomers of bis-(ethoxycarbonyl methano)[60] fullerene leads to new fullerene derivatives, which have been preliminary characterized. The analysis of separated species was performed by UV-VIS, IR, H- and C-NMR, STM, FAB, LDI and MALDI-TOF MS spectroscopy. One of the isolated phases is a C₁₂₂ molecule with a dumbbell-like structure. This revised version was published online in July 2006 with corrections to the Cover Date.     

60]Fullerene metal complexes with large effective two-photon absorption cross-section

Fourteen novel complexes of fullerene C(60) with metal dialkyldithiophosphate, {[(RO)(2)PS(2)](2)M}·2C(60) (R = Me and Et; M = Mn, Fe, Co, Ni, Cu, Zn and Pd), can be obtained in high yield by the reaction of metal(II) dialkyldithiophosphate complexes with C(60) fullerene. Their structures are determined by (1)H, (13)C, and (31)P NMR spectroscopy, elemental analysis, FT-IR and UV-vis, and are supplied by single crystal X-ray data. The compound {[(EtO)(2)PS(2)](2)Pd}·2C(60) was also studied by the HRTEM image and SAED patterns. Studies of the optical properties of the complexes of fullerene C(60) with metal dialkyldithiophosphate show that these compounds all have very strong nonlinear optical absorption effects. The nonlinear absorption of fourteen complexes of fullerene C(60) with metal dialkyldithiophosphate (in o-dichlorobenzene and in the solid state) was measured by the open-aperture Z-scan technique at a wavelength of 532 nm. DFT calculations are also used to discuss the stability of these complexes and to confirm the structural assignments.     

Interactions of metal‐encapsulated fullerenes with solvents

The present investigation reports on the interaction of M@C₆₀(M = Be, Mg, Ca) with solvents (H₂O, CH₃OH, HF, NH₃) using Density Functional Theory calculations. Our computations reveal that the interaction of the fullerene species increases when endohedral metal atoms are inserted into its cavity. The most profound interaction of the fullerene systems is with water and hydrogen fluoride. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Transition Metal Complexes of a Salen–Fullerene Diad: Redox and Catalytically Active Nanostructures for Delivery of Metals in Nanotubes

A covalently‐linked salen–C₆₀ (H₂L) assembly binds a range of transition metal cations in close proximity to the fullerene cage to give complexes [M(L)] (M=Mn, Co, Ni, Cu, Zn, Pd), [MCl(L)] (M=Cr, Fe) and [V(O)L]. Attaching salen covalently to the C₆₀ cage only marginally slows down metal binding at the salen functionality compared to metal binding to free salen. Coordination of metal cations to salen–C₆₀ introduces to these fullerene derivatives strong absorption bands across the visible spectrum from 400 to 630 nm, the optical features of which are controlled by the nature of the transition metal. The redox properties of the metal–salen–C₆₀ complexes are determined both by the fullerene and by the nature of the transition metal, enabling the generation of a wide range of fullerene‐containing charged species, some of which possess two or more unpaired electrons. The presence of the fullerene cage enhances the affinity of these complexes for carbon nanostructures, such as single‐, double‐ and multiwalled carbon nanotubes and graphitised carbon nanofibres, without detrimental effects on the catalytic activity of the metal centre, as demonstrated in styrene oxidation catalysed by [Cu(L)]. This approach shows promise for applications of salen–C₆₀ complexes in heterogeneous catalysis.     

Products of reaction of fullerene C60 with fuming sulfuric acid studied by IR and ESR spectroscopy

The products of reaction of fullerene C₆₀ with fuming sulfuric acid were precipitated from a solution with water and triethylamine and studied by IR and ESR spectroscopies. A comparison of the obtained data with the spectra of fullerene, dimers C₁₂₀ and C₁₂₀O, and fullerene polymers produced by photopolymerization allowed the conclusion that fullerene polymers were formed by fullerene oxidation with fuming sulfuric acid.