C60衍生物与C60混合物中富勒烯的生长研究

富勒烯分子生长方面的研究，对于富勒烯的基础研究以及潜在应用有着重要的意义，因此引起了科学界的广泛兴趣和研究，Yeretzian[1]、Campbell[2],Rao[3]等人相继用不同的实验方法对C60的融合作了详细研究，但C60的生长动力学过程依然是个悬而未决的问题．我们实验室已对C60的正负离子解离以及C60加成衍生物中C60的解离和生长作了较深入的研究：发现C60正负离子解离时电荷具有不同的转移通道，即C朋解离时电荷留在碳笼上，而C60解离时电荷易转移到小碳簇上，且C60解离以较缓慢的笼子收缩过程进行间．衍生物基团（如节基、薛基）对C。。…     

Photophysical and electronic properties of five PCBM-like C60 derivatives: spectral and quantum chemical view

By means of transient UV-visible absorption spectra/fluorescence spectra, combined with electronic structure calculations, the present work focuses on characterizing the photophysical and electronic properties of five PCBM-like C(60) derivatives (F1, F2, F3, F4, and F5) and understanding how these properties are expected to affect the photovoltaic performance of polymer solar cells (PSCs) with those molecules as acceptors. Spectral data reveal that the fluorescence quantum yields (Φ(F)) are enhanced and the triplet quantum yields (Φ(T)) are lowered for the five PCBM-like C(60) derivatives as compared to those of the pristine C(60), suggesting that functionalization of a C═C double bond perturbs the fullerene's π-system and breaks the I(h) symmetry of pristine C(60), which results in modifications of photophysical properties of the fullerene derivatives. PBEPBE/6-311G(d,p)//PBEPBE/6-31G(d) level of electronic structure calculations yields the HOMO-LUMO gaps and LUMO energies, showing that the electron-withdrawing effect induced by the side chain functional groups perturbs LUMO energies, from which different open circuit voltages V(oc) are resulted. The predicted V(oc) from our calculation agrees with previous experiment results. Basically, we found that functionalization of a C═C double bond sustains the fullerene structure and its electron affinitive properties. Adducted side chains contribute to adjust the HOMO-LUMO gap and LUMO levels of the acceptors to improve open circuit voltage. The results could provide fundamental insights for understanding how structural modifications influence the photovoltaic performance, which paves a way for guiding the synthesis of new fullerene derivatives with improved performance in polymer solar cells.     

C60的六加成反应

以六加成反应为代表的C60的多加成反应已经成为富勒烯化学的一个重要组成 部分。综述了C60的六加成反应，包括具有不同对称性的各种C 60六加成产物的合 成和表征，以及六加成产物的基本性质和应用。     

侧基上带有C60基团的聚苯乙烯的表征

用UV、FTIk、DSC、TG和DTA及GPC等方法证明了通过三步反应(氯甲基化,叠氮化,环加成反应)确实将C₆₀引入到聚苯乙烯的侧基上,C₆₀基本上以单取代的方式存在,并通过TG和DTA方法估算了C₆₀在聚苯乙烯C₆₀衍生物中的含量。     

B2C3簇的结构和振动光谱的理论研究

用量子化学从头计算方法研究了Ｂ２Ｃ３簇各种可能的空间结构，计算了相应的振动光谱和结合能。对Ｂ２Ｃ３最稳定构型的电子结构进行了深入的分析和讨论。     

Quantum chemical study of the reactivity of C60HR and C60(CHR) derivatives

In the present work a quantum chemical study of a series of substituted hydrofullerenes, C(60)HR, and a series of methanofullerenes, C(60)(CHR), is presented. Their reactivity and geometrical, energetic, electronic, and magnetic properties, as well as the influence of the substituent, are discussed. As a probe of the reactivity, the acidic properties of these fullerene derivatives were predicted, based on the calculated deprotonation energies, with a previously set up scheme. The electronic delocalization upon deprotonation was described, and the global (magnetizabilities) and local aromaticity (nucleus-independent chemical shifts) was analyzed and compared with respect to the group properties for the series of functional groups. The geometries of both acidic and basic forms were fully optimized at the AM1 level, and all property calculations were performed at the HF/3-21G and the B3LYP/6-31G* level of theory.     

C_(60)环酮衍生物C_(66)H_8O与C_(67)H_(10)O顺反异构体的结构及光谱研究

用AM1，INDO/CI方法研究了C60与2-环己烯-1-酮和2-环庚烯-1-酮[2+2]环加成所得衍生物C_(66)H8O和C67H1O的结构。结果表明，两种衍生物的顺反异构体都只具有C1对称，C66H8O的顺式异构具有较低的能量和较小的偶极矩，C67H10的顺式并构体能量较低，但偶极矩较大，以优化构型为基础，计算加成产物的UV谱，对电子跃迁进行了理论指认，并分析了光谱移动的原因。     

中间体C60(CH3)-和产物C60(CH3)2的结构及产物

用INDO系列方法对C₆₀^2-与CH₃反应的中间体C₆₀(CH₃)^-进行理论研究,得到具有Cs对称性的构型。结果表明,CH₃加成到C₁₅上,将使与其相邻的双键碳(C₃₀)的电荷密度和自旋密度达极大值,故加成反应部位在C₃₀处;另外,C₁₅的对位C₁₂(或C₂₇)也较其它部位易于反应,且有两个反应场所,因而产物C₆₀(CH₃)₂可能为六元环上的1,2-加成和1,4-加成两种异构体的混合物。同时对两种加成产物的结构和电子光谱进行了理论研究,指认其电子跃迁,并讨论了其光谱红移的原因。     

Synthesis of C_(60) Nitroxide Derivatives

MagginiIfirstreportedthesynthesisoffulleropyrrolidinederivativesbyl,3dipolarcycloaddition,whichprovedtobeoneofthemosteffectivemethodtoobtainfullerenemonoadductderivatives.In1995,Corvaja'reportedthesynthesisofC,,derivativecovalentlylinkedwitha11itroxideradical2,2,6,6-tetramethylpiperidine-l-oxylbyl,3dipolarcycloadditionusingC,,,TOACandparaformaldehydeasthereactants.ThiscompoundisuniqueinthestudyoftheintramolecularinteractionofaradicalspecieswiththeC,.>core.Herewereportanothermethodtosynthes…     

含氮Ylide对C_(60)的1,3-偶极环加成反应法合成含吡咯环C_(60)衍生物

利用肌氨酸与对位含不同取代基的苯甲醛、共轭烯烃醛类及酮类反应生成的含氮Ylide对C60的加成反应，合成并分离、纯化制得了一系列含不同取代基的C60吡咯环纯衍生物，并用1HNMR、13CNMR、FDMS、FT－IR、UV－Vis等光谱手段确定了它们的分子结构．     

C2H5C60H的加成产物的结构和光谱性质的量子化学研究

用INDO系列方法对C₂H₅C₆₀H的1,2-加成和1,4-加成两种产物异构体的结构进行了理论研究,结果表明1,2-C₂H₅C₆₀H具有Cs对称性,1,4-C₂H₅C₆₀H没有任何对称性,1,2-C₂H₅C₆₀H的总能量比1,4-C₂H₅C₆₀H的低。以此优化构型为基础,计算了两种产物异构体的电子吸收光谱,讨论了其光谱红移的原因,同时对产物的NMR谱进行了探讨。     

外电场对N@C60, P@C60, As@C60分子结构和性质的影响

用量子力学方法研究了N@C60, P@C60, As@C60分子的几何和电子特征. 计算结果表明, 形成富勒烯包合物后, 碳笼只有微小的变形, 3种内包原子在笼中处于不同的位置, 碳笼与内包原子之间有明显的电荷转移和自旋轨道相互作用, 生成能分别为6.32, 70.88, -53.05 kJ/mol. 内包原子的3个单占据分子轨道(SOMO)能量变化很大, 并由于和碳笼作用而发生劈裂. 在外电场作用下, 分子的电子密度沿电场方向发生转移.分子的能量随外加电场的增强而降低. 分子轨道能级、能隙及SOMO轨道的能量和能级劈裂也发生了变化.     

微型氧弹热量计和C60及C70的燃烧焓

富勒烯是新发现的一类碳的稳定单质，其分子骨架中含有多个五员环及非平面球壳状大力键.与全为六员环的平面大r键的石墨结构相比，这些张力提高了分子能量.通过富勒烯的生成焰的测定，对了解这些分子的稳定性和反应性，它们的生成机理，以及研究分子的结构与能量的规律是很有意     

C60O结构和电子光谱的理论研究

用ＩＮＤＯ系列方法研究Ｃ６０Ｏ的两种结构：一是桥氧加在２个六元环之间的键上为Ｃ２ｖ构型；另一个是桥氧加在１个五元环和１个六元环之间的键上为Ｃｓ构型。计算表明，从总能量、ＨＯＭＯ－ＬＵＭＯ能级差和光谱性质看，Ｃ６０Ｏ的稳定构型都应是Ｃ２ｖ构型，该Ｃ２ｖ异构体具有环氧结构（桥Ｃ１５－Ｃ３０键长为０．１５１８ｎｍ，键序为０．８７４４），其电子光谱计算结果与实验值较好地符合。     

Reaction of amino acid derivatives with C_(60)

Ammo acid derivatives react with C60 at 110-120℃to form adduct compounds.The products were isolated by column chromatography and were identified by FD-MS,UV-Vis,FT-IR and 13C NMR spectroscopies.     

C_(60)及其碱金属衍生化合物

本文综述了C_(60)的分子结构,合成,晶体结构和相变,主要物理化学性能,以及碱金属C_(60)化合物M_3C_(60),M_4C_(60)和M_6C_(60)的制备,晶体结构和超导性。     

Energy relationship and the polarization of C_(60) cage in the endohedral complexes (X@C_(60))

In this paper, we carry out the calculation on the system (X@C60)(X=Li, Na, K, Kb, Cs; F, Cl, Br, I), where the position of X changes along 5 typical symmetry directions. For the calculation of quantum chemistry we use EHMO/ASED method, for the calculation of molecular mechanics we use Buckingham potential (exp-6-1) function, and for the calculation of thermo-chemical cycle we use individually isolating the processes such as the structure variation, charge transfer and charge distribution, and their interactions etc. The calculation results show that (1) In the region of radius r≈0.2 nm of the Ceo cage, the potential field is nearly spherical; (2) Except for Li and Na, the systems are the most stable with minimum energies at the center of C60 cage. For Li and Na, the systems are the most stable with minimum energies at r≈0.16 nm and r≈0.13 nm, respectively. In view of the interactive region of chemical bonds, the interactions between X and the C60 cage do not belong to the classical chemical bonds; (     

晶态Ca3C60与Ca5C60的能带结构研究

用三维EHMO晶体轨道程序分别对Ca3C60，Ca5C60进行了能带结构的计算．计算结果表明，Ca3C60没有导电性，能隙约为0．9eV；而在Ca5C60的能带结构中，费米面刚好穿过半满带，表明Ca5C60是导体；同时在费米面附近有较大的态密度值，表明Ca5C60与K3C60等类似，具有较高的超导转变温度．电荷分析表明，在这两种情况下，钙原子的4s电子基本上全转移到C60上，C60分子可形成一个稳定的带6到10个电子的负离子．     

晶态C60,K3C60,K6C60的能带计算

本文用紧束缚法的ＥＨＭＯ三维晶体轨道程序进行计算求得了Ｃ６０，Ｋ３Ｃ６０和Ｋ６Ｃ６０的能带结构，并得到了一系列过去未曾见过报导的原子投影态密度、轨道、原子重叠布据、原子电荷、轨道矢量等数据。从这些能带图中可以充分说明三种物质的区别，并可解释Ｋ３Ｃ６０的超导性和Ｃ６０与Ｋ６Ｃ６０的绝缘性。     

Fullerene(C_(60)) as a Potential Chemical Sensor for Hydrogen Cyanide Detection

To find a novel sensor for the detection and control of toxic hydrogen cyanide(HCN), the geometrical and electronic parameters of HCN adsorption on fullerene C60 were investigated using density functional theory(DFT) calculations by means of B3 LYP functional with 6-31 G* basis set. The calculated density of states(DOSs) shows that the electronic properties of fullerene C60 were very sensitive to the presence of HCN molecule, so that the Eg of C60 was significantly decreased from 2.76 eV in pristine form to 1.81 eV(34.4% change) after the HCN adsorption which would result in electrical conductance increment. The results demonstrated that the C60 may convert the presence of a HCN molecule to an electrical signal for using in HCN-sensor devices through doping, chemical functionalization. Also, based on calculated results, the C60 is expected to be a potential efficient adsorbent as well as a sensor for detecting the presence of toxic HCN.