异质富勒烯C58P2的理论研究

用ＭＮＤＯ半径能方法研究了异质富勒烯Ｃ５８Ｐ２各异构体的结构和相对稳定性。结果表明,１,４－位取代的异构体最稳定,异构体的稳定性随杂原子同距离的增加而降低。Ｃ５５８Ｐ２分子和稳定性比全碳富勒烯Ｃ６０低,但仍具有相当的稳定性,是潜在的合成目标。杂原子磷的掺杂改善了富勒烯的氧化还原性能。考察了各异构体的整体硬度和绝对电负性,产根据绝对电负性的差异预测了富勒烯和异质富勒烯间形成聚合物时的电子转移。     

C60亮氨酸衍生物的合成及其理论研究

用１，３－偶极环加成方法合成了含吡咯环Ｃ６０衍生物Ｃ６６ＮＨ１３，并以ＦＴＩＲ，ＵＶ－Ｖｉｓ，＾１Ｈ ＮＭＲ和ＬＤ－ＴＯＦＭＳ进行表征，用ＡＭ１方法对两种可能的加成产物－「６，６」和「６，５」异构体进行几何构型优化。结果表明，「６，６」异构体更稳定，以优化构型为基础，用ＩＮＤＯ／ＣＩ方法计算两种加成产物的ＵＶ谱，结果表明，「６，６」异构体的特征吸收与实验值一致。     

C60哌嗪加成物的结构及光谱研究

用ＩＮＤＯ系列方法研究了Ｃ６０的哌嗪衍生物Ｃ６０Ｎ２（Ｃ２Ｈ４）２的结构。结果表明［６，６］，异构体具有Ｃ２ｖ对称性［６，５］，异构体具有Ｃｓ对称性，前者能量较低。以优化构型为基础，计算两种加成产物的ＵＶ谱，结果表明，［６，６］异构体的特征吸收与实验值相符，同时对［６，５］异构体的ＵＶ谱进行理论预测，对电子跃迁进行了理论指认，并分析了光谱红移的原因。     

STUDY ON THE SYNTHESIS OF N~6 AROMATIC HETEROCYCLIC METHYL SUBS

ＳＴＵＤＹ　ＯＮ　ＴＨＥ　ＳＹＮＴＨＥＳＩＳ　ＯＦ　Ｎ~６　ＡＲＯＭＡＴＩＣ　ＨＥＴＥＲＯＣＹＣＬＩＣ　ＭＥＴＨＹＬ　ＳＵＢＳＴＩＴＵＴＥＤ　ＡＤＥＮＯＳＩＮＥ　ＡＮＤ　ＡＤＥＮＩＮＥＢＹ　ＤＩＭＲＯＴＨ　ＲＥＡＲＲＡＮＧＥＭＥＮＴ　ＲＥＡＣＴＩＯＮ?..     

REACTION OF C_60 AND 2-AMINO-ETHYLHYDROGENSULFATE

ＲＥＡＣＴＩＯＮ ＯＦ Ｃ_６０ ＡＮＤ ２－ＡＭＩＮＯ－ＥＴＨＹＬＨＹＤＲＯＧＥＮＳＵＬＦＡＴＥ￥ＬｉａｎｇＢｉｎｇＧＡＮ；ＤｅＪｉａｎＺＨＯＵ；ＣｈｕＰｉｎｇＬＵＯ；ＣｈｕｎＨｕｉＨＵＡＮＧ；ＪｉｎＱｉＰＡＮ；ＭｕＪｉａｎＬＵ（Ｄｅｐａｒｔｍｅｎ?..     

C70O2可能异构体的结构和电子光谱的理论研究

用ＡＭ１、ＰＭ３及ＩＮＤＤ系列方法研究了Ｃ７０Ｏ２可能异构体的结构和稳定性,在Ｃ７０Ｏ稳定型的基础上,考察了Ｃ７０Ｏ２的４５种异构体,结果表明,两个Ｏ原子加在碳球极端处同一个六元环内不等价的６／６键上形成环氧结构的构型最稳定,在优化构型的基础上,进行电子光谱计算,并与Ｃ７０和Ｃ７０Ｏ进行了比较。     

MOLECULAR MECHANICAL AND QUANTUM CHEMICAL CALCULATION ON ACYLATION REACTIVITY FOR 1－（NITRO SUBSTITUTED ANILINO）－4－SUBSTITUTED－2，6－PIPERAZINEDIONES

ＭＯＬＥＣＵＬＡＲＭＥＣＨＡＮＩＣＡＬＡＮＤＱＵＡＮＴＵＭＣＨＥＭＩＣＡＬＣＡＬＣＵＬＡＴＩＯＮＯＮＡＣＹＬＡＴＩＯＮＲＥＡＣＴＩＶＩＴＹＦＯＲ１－（ＮＩＴＲＯＳＵＢＳＴＩＴＵＴＥＤＡＮＩＬＩＮＯ）－４－ＳＵＢＳＴＩＴＵＴＥＤ－２，６－ＰＩＰＥＲＡＺ...     

4，6－DIMETHYL－2－MERCAPTOPYRIMIDINE AS NEW PROMOTER FOR THE VOLTAMMETRIC RESPONSE OF HORSE HEART CYTOCHROME CAT A MICROBAND GOLD ELECTRODE

４，６－ＤＩＭＥＴＨＹＬ－２－ＭＥＲＣＡＰＴＯＰＹＲＩＭＩＤＩＮＥＡＳＮＥＷＰＲＯＭＯＴＥＲＦＯＲＴＨＥＶＯＬＴＡＭＭＥＴＲＩＣＲＥＳＰＯＮＳＥＯＦＨＯＲＳＥ　ＨＥＡＲＴＣＹＴＯＣＨＲＯＭＥＣＡＴＡ　ＭＩＣＲＯＢＡＮＤＧＯＬＤ　ＥＬＥＣＴＲＯＤＥＨｏ...     

6－0－DEMETHYL－（19S）－DIHYDROETORPHINE， A NEW SYNTHETIC COMPOUND， ISOLATED FROM CRUDE DIHYDROETORPHINE AS A MINOR BY－PRODUCT

６－０－ＤＥＭＥＴＨＹＬ－（１９Ｓ）－ＤＩＨＹＤＲＯＥＴＯＲＰＨＩＮＥ，　Ａ　ＮＥＷ　ＳＹＮＴＨＥＴＩＣ　ＣＯＭＰＯＵＮＤ，　ＩＳＯＬＡＴＥＤ　ＦＲＯＭ　ＣＲＵＤＥ　ＤＩＨＹＤＲＯＥＴＯＲＰＨＩＮＥ　ＡＳ　Ａ　ＭＩＮＯＲ　ＢＹ－ＰＲＯＤＵＣＴ６－０－...     

杂富勒烯的电子结构与性质关系的研究：Ⅱ.C57X3,C56X4（X=B,N,P）的位 …

用ＣＮＤＯ／２方法在５８６微机上计算了Ｃ５７Ｘ３，Ｃ５６Ｘ４的２３４个位置异构体的电子结构。在Ｃ５７Ｘ３位置异构体中，Ｃ５７Ｘ３分别是最稳定的。对于Ｃ５６Ｘ４位置异构体，Ｃ５６Ｂ４，Ｃ５６Ｎ４和Ｃ５６Ｐ４分别是最稳定的，但稳定性都比Ｃ６０差。其氧化或还原性都比Ｃ６０好，将它们和Ｃ６０比较，与Ｘ相距一个或两个健的Ｃ原子电荷密度增加或减少较多，其亲电或亲核反应性增加；     

用原子转移自由基聚合法合成末端含碳笼烯-60的窄分子量分布聚苯乙烯

Ｃ６０是碳笼烯一族的代表,其独特的球笼形空间结构和电子结构决定了其有许多奇异的性质［１］．关于Ｃ６０的化学反应性的研究方兴未艾［２］,其中Ｃ６０的高分子衍生物的合成也是关注所在．迄今关于含Ｃ６０的高聚物的合成已有许多报道［３,４］,而关于窄分布的含Ｃ６０高聚物的合成的研究尚少．Ｆｒｅｙ等［５］将阴离子聚合所得的聚苯乙烯链的末端转变为氨基,再与过量的Ｃ６０发生单电子转移加成反应制得窄分布的以Ｃ６０封端的聚苯乙烯．Ａｓｔｒｕｓ等［６］将活性阳离子聚合所得的六臂星形聚苯乙烯的末端转化为氨基,得到Ｃ６０…     

Structure and stability of the defect fullerene clusters of C60: C59, C58, and C57

We have performed density functional calculations for the structures and stabilities of various isomers of the defect fullerene clusters of C(60): C(59), C(58), and C(57). The C(59_)5-8, C(58_)5-5-7, and C(57_)4-5-9 clusters were calculated to be the most stable isomers of the C(59), C(58), and C(57) clusters, respectively. There are obvious relationships between structure and stability of the defect fullerene clusters. First, an unsaturated carbon atom favors being located at a 6-membered ring rather than a 5-membered ring. Second, the most stable isomers prefer to have newly formed 5-membered rings, rather than newly formed 4-membered rings.     

Theoretical studies on the BN substituted fullerenes C70−2x(BN)x (x=1–3)—isoelectronic equivalents of C70

The equilibrium structures and relative stabilities of BN-doped fullerenes C_70−2x(BN)_x (x=1–3) have been studied at the AM1 and MNDO level. The most stable isomers of C_70−2x(BN)_x have been found out and their electronic properties have been predicted. The calculation results show that the BN substituted fullerenes C_70−2x(BN)_x have considerable stabilities, though they are less stable than their all carbon analog. For C₆₈BN, the isomers whose BN is located in the most chemically active bonds of C₇₀ (namely B and A) are among the most stable species, of which B is predicted to be the ground state. The stabilities of C₆₈BN decrease and the dipole moments increase with increasing the distance between the heteroatoms. For C₆₆(BN)₂, the lowest energy species is the isomer in which the B–N–B–N bond is formed; For C₆₄(BN)₃, the most stable species should have three BN units located in the same hexagon to form B–N–B–N–B–N ring. The ionization potentials and the affinity energies of the most stable species of BN-doped C₇₀ are almost the same as those of C₇₀ because of the isoelectronic relationship. The ionization potentials and affinity energies depend on the relative position of the heteroatoms in C₆₈BN, the chemical reactivities of the isomers whose heteroatoms are well separated should differ significantly from their all carbon analog.     

C60加成反应的理论研究

用ＡＭ１方法研究了Ｃ６０与醌并二烯加成反应的机理,并对反应的过渡态及加成产物的构型进行了优化。研究发现,醌并二烯与Ｃ６０的加成是协同进行的,反应的活化能较低;     

N@C60的结构和振动光谱的理论研究

用ａｂｉｎｉｔｉｏ分子轨道ＵｎｒｅｓｔｒｉｃｔｅｄＨａｒｔｒｅｅ－Ｆｏｃｋ（ＵＨＦ）方法,对Ｎ＠Ｃ６０的几何构型进行了全优化。计算结果表明,Ｎ基本上以原子的形成存在于笼中,但原子与碳笼之间存在一定的相互作用,这与实验结果相符。进一步计算了Ｎ＠Ｃ６０的振动光谱,并与Ｃ６０进行了比较分析。     

DFT study on the stabilities of the heterofullerenes Sc3N@C67B, Sc3N@C67N, and Sc3N@C66BN

On the basis of calculations using density functional theory, we investigated the relative stabilities of all isomers of Sc3N@C67B and Sc3N@C67N as well as those of stable isomers of Sc3N@C66BN. As a result, we predict that Sc3N@C68 can be doped substitutionally with a boron atom much better than C60. This effect can be ascribed to the favorable electrostatic attraction between the encased Sc3N cluster and the polar C-B bonds of the fullerene cage, which show the important role played by the encapsulated atoms in stabilizing the fullerene. A difference in the interaction also determines the regiospecificity of Sc3N@C67B. On the contrary, N-doping of the fullerenes forming Sc3N@C67N is much less favorable than that in C60 or C70. A judicious choice of stable isomers of Sc3N@C66BN among a vast number of possible isomers indicates that Sc3N@C68 can also be doped with a pair of B and N atoms better than C60 under the simultaneous existence of B and N sources. Relative stabilities of various isomers of the BN-substituted fullerenes can be understood in terms of the combined electrostatic effects in the B- and N-substitutions of Sc3N@C68 complemented by a specific local preference in the N-substitution and the formation of a B-N bond.     

DFT Study on the Structural, Electronic, and Spectroscopic Properties of the Highest Epoxygenated Fullerene C36O18

Theoretical investigation on the highest epoxygenated fullerene C36O18 formed from the initial C36 fullerene with D6h symmetry has been performed at the B3LYP/6-31G(d) level. Their equilibrium structures, thermal stabilities, electronic structures, vertical ionization potentials, vertical electron affinities, vibrational frequencies and 13C NMR chemical shifts have been studied. The calculation results showed that C36O18 isomers have higher LUMO-HOMO energy gaps than the fullerene C36 and should be more stable. Compared with C36 , it is less possible for C36O18 to accept or donate electrons from reduced VEAs and enhanced VIPs. It has been found that C36O18 isomers are not aromatic at all or antiaromatic on analyzing the NICS values. The present study will encourage further theoretical and experimental analyses of this system in future.     

Theoretical Studies on Stabilities of C26BN Isomers

The possible stable stractures of substituted fullerene C26BN formed on the initial C28 cage with Td symmetry have been systematically studied on UHF/3-21g level with constrained syrnmetry(Cs or C1, the charge and multiplicity of all the isomers are zero and five, respectively.The geometry optimization and the vibrational frequencies analysis were performed on the same level with constrained symmetry(Cs or C1. The results show that the most stable isomer of C26BN is formed by boron and nitrogen atoms doping at 5,2-sites.     

C59(CHPh2)N的电子结构、UV-Vis光谱、NMR谱及非线性光学性质的理论研究

用ＩＮＤＯ系列方法对由（Ｃ５９Ｎ）２和ＣＨ２Ｐｈ２合成的第一个Ｃ５９Ｎ衍生物Ｃ５９（ＣＨＰｈ２）Ｎ进行了理论研究,得到了Ｃ５９（ＣＨＰｈ２）Ｎ的稳定分子构型,表明Ｃ５９（ＣＨＰｈ２）Ｎ为Ｃｓ对称性,并在此基础上讨论了Ｃ５９（ＣＨＰｈ２）Ｎ的ＵＶ－Ｖｉｓ光谱、ＮＭＲ谱．计算表明Ｃ５９（ＣＨＰｈ２）Ｎ的二阶非线性光学系数βμ较大