Theoretical Studies on Electronic Structures and Spectra for C80^n （D5d,C2v） Singlet

1INTRODUCTIONC80iscalledthemissingfullereneduetoitsinstabilityinkineticsandlowerLUMO-HOMOenergygap[1],aswellasthelowerabundanceintheexperimentandthedifficultyinsynthesis[1~5].However,thestableexistenceofcomplexLa2@-C80[2]stimulatestheresearchinterestinionsofC80.Zhang[3]performedtheoreticalstudiesonthestabi-lityandNMRspectraforC80isomers.Nakao[4]cal-culatedtheLUMO-HOMOenergygapofC80byusingabinitiomolecularorbital.Hennrich[5]syn-thesizedC80(D5)fromfullerenesootextractionbydHPLC.…     

Synthesis and Characterization of （CH3CH2CH2CH2NH3）2SnBr6

1 INTRODUCTION Recently, the researches on inorganic-organic hy-brid compounds represent an advanced field in mate-rial science[1]. At the molecular level, the combina-tion of two extremely different components providesan avenue to design new hybrid materials as well asthe ability to modulate properties of one or more ofthe components[2～6]. Some attractive properties, suchas efficient luminescence[2～4], ideal thermal and me-chanical stability, interesting magnetic[5], non-linearoptical[…     

Synthesis and Characterization of [NH3（CH2）2NH2（CH2）2NH3]BiCl6

1 INTRODUCTION During the past decade, a series of organic-inor- ganic hybrid compounds based on metal halide units have been prepared and studied[1]. The combination of organic and inorganic components at the mole- cular level affords us the opportunity to design new hybrid materials and modulate the properties of components[2]. As a result, some interesting proper- ties, such as non-linear optical[3], interesting magne- tic[4], efficient luminescence[2], ideal thermal and mechanical sta…     

Preparation and Crystal Structure of Hetero—metal Clusters[η^5—C5H4C（O）CH2CH2C（O）OCH3]FeCoM（μ3—S）（CO）8（M=Mo or W）

1 INTRODUCTIONTransition metal clusters have been attracting intensive attention largely because they are suggested as active catalysts in a variety of homogeneous catalyzed reactions. However, no unequivocal proof exists that metal clusters themselves serve as the true catalysts among the catalytic process. In many cases it is known that fragments of the original clusters are the actual catalytic species. The unambiguous proof would be the use of a rigid chiral cluster to catalyze an asy…     

Semi-Empirical and DFT Studies on Structures and Spectra for C78（CH2）2

Eighteen possible isomers of C78（CH2）2 weTe investigated by the INDO method. It was indicated that the most stable isomer was 42,43,62,63-C78（CH2）2, where the -CH2 groups were added to the 6/6 bonds located at the same hexagon passed by the longest axis of C78 （C2v）, to form cyclopropane structures. Based on the most stable four geometries of C78（CH2）2 optimized at B3LYP/3-21G level, the first absorptions in the electronic spectra calculated with the INDO/CIS method and the IR frequencies of the C-C bonds on the carbon cage computed using the AM1 method were blue-shifted compared with those of C78 （C2v） because of the bigger LUMO-HOMO energy gap and the less conjugated carbon cage after the addition. The chemical shifts of ^13C NMR for the carbon atoms on the added bonds calculated at B3LYP/3-21G level were moved upfield thanks to the conversion from sp^2-C to sp^3-C.     

[（n-C4H9）3SnO2C（CH2）2CO2Sn（C4H9-n）3]：A Novel Three-dimensional Framework Structure of Organotin Complex

The bis(tributyltin) ester of succinic acid was synthesized by the reaction of disodium salt of succinic acid with tributyltin chloride in a molar ratio of 1:2. The crystal structure was determined by X-ray single-crystal diffraction. It belongs to orthorhombic with space group Pccn, a = 20.949(3), b = 17.470(3), c = 20.345(3)A, V= 7446(2)A^3, Z= 8, Dc = 1.242 g/cm^3, μ=1.365 mm^-1, F(000) = 2864, R = 0.0544 and wR = 0.1417. The tin atom is of five-coordination in a trigonal bipyramidal structure by bridging two carboxylate groups in different directions and the resulting structure which contains straight twist large ring channels along the axes of a, b and c is a three-dimensional framework polymer containing two different tin atoms.     

Changing Rules of Bonding Electron Pair Correlation Energies of CH3X （X = F, OH, NH2） Systems

1 INTRODUCTION It has been known that the electron correlation energy of molecular systems was, and still is, one of the most serious bottleneck problems to the chemis- try accuracy of computational quantum chemistry. Since L鰓din[1] gave the definition …     

Synthesis, Crystal Structure, UV-vis and EPR Studies of（ NH3CH2CH2NH2 ） 2.5 [ Mo0.5^（V）W0.5^（VI）O2 （ OC6H4O ） 2]

Cis-dioxo-metal complex ( NH3CH2CH2NH2 ) 2.5 [ Mo0.5^(V)W0.5^(VI)O2 ( OC6H4O ) 2] 1 was obtained by the reaction of tetra-butyl ammonium hexamolybdotungstate with 1, 2-dihydroxybenzene in the mixed solvent of CH3OH, CH3CN and ethylenediamine,and characterized by X-ray diffraction, UV-vis and EPR analysis. Compared with its analogous complexes (NH3CH2CH2NH2)3[Mo^(V)O2(OC6H40)2] 2 and (NH3CH2CH2NH2)2[W^(VI)O2(OC6H4O)2] 3, the results show that tungsten(VI) is less active in redox than molybdenum (VI) and that the change of the valence induced by substitution of W(VI) for Mo(V) in EMO2(OC6H40)2]n- does not influence the coordination geometry of the complex anion in which the metal center exhibits distorted octahedral coordination with cis-dioxo catechol. The responses to EPR of complexes 1 and 2 are active but complex 3 is silent,and the UV-vis spectra exhibited by the three complexes are obvious different because of the different electronic configuration between the central Mo(V) and W(VI) ions in the complexes.It is noteworthy that complexes 1 and 2 have the similar EPR signal to flavoenzyme, suggesting that the three complexes have the same coordination geometry feature with the co-factor of flavoenzyme.     

C_(78)~n(C_(2v))的电子结构和UV谱

用INDO (Intermediateneglectdifferentialoverlap)系列方法对Cn78进行系统研究 .结果表明 ,C78(C2v)比C78(C2v′)稳定 ;Cn78(C2v)和Cn78(C2v′)未发生Jahn Teller畸变 ;Cn78随n绝对值增大 ,体系能量升高 .以优化构型为基础 ,首次计算Cn78电子光谱 ,对电子跃迁进行理论指认 ,讨论Cn78光谱特征吸收与C78相比发生红移的原因 .     

Cn78(C2v)的电子结构和UV谱

用INDO(Intermediate neglect differential overlap)系列方法对Cn78进行系统研究.结果表明,Cn78(G2v)比Cn78(C2v')稳定;Cn78(C2v)和Cn78(C2v')未发生Jahn-Teller畸变;Cn78随n绝对值增大,体系能量升高.以优化构型为基础,首次计算Cn78电子光谱,对电子跃迁进行理论指认,讨论Cn78光谱特征吸收与C78相比发生红移的原因.     

C60O2可能异构体的结构,电子光谱和NMR谱的理论研究

用ＩＮＤＯ系列方法研究Ｃ６０Ｏ２可能异构体的结构，两个氧原子分别加在两个六元环相邻边或五六元环相邻边形成环氧结构，为Ｃｓ对称性，得６种可能构型，计算表明，两个氧原子加在同个六元环的六六元环相邻边所形成环氧结构Ｃｓ构型最稳定，环氧处Ｃ－Ｃ键不断开，与实验结果一致，其电子光谱计算结果亦与实验值相吻合，这种Ｃｓ构环氧结构所在六元环上的另一个Ｃ－Ｃ键有大的键序，为高活性位置，因此Ｃ６０Ｏ２可能有较好的化学     

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。     

H_3PMo_(12-n)WnO_(40)·xH_2O的电子光谱与电化学性质研究

系统地考察了H3PMo12 -nWnO4 0 ·xH2 O系列酸在不同溶剂中的电子光谱行为 ,结果表明 ,Mo Ob ,c Mo键在稀水溶液中断裂 ,而在乙醇溶液中能够稳定存在 ;W Ob ,c W键在极稀的水溶液中也能够稳定存在 ;在有机溶剂中所有酸的特征吸收峰均发生红移。电化学性质的研究表明 ,随着分子中钨原子取代数的增多 ,酸的氧化性降低 ,最高还原峰电位和分子中钨原子取代数之间存在一近似线性关系。     

C74(BN)2的UV和IR 光谱研究

Equilibrium geometries of 16 possible isomers for C74（BN）2 were studied by INDO series of methods, to indicate that the most stable three geometries are those where boron and nitrogen atoms substitute carbon atoms located at the same hexagon near the longest axis of C78 （C2v） to form B-N-B-N unit. Electronic spectra of C74（BN）2 were investigated with INDO/CIS method. The reason for the red shift of UV absorptions for C74（BN）2 compared with those of C78 （C2v） was discussed. IR spectra for 9,8,28,29-C74（BN）2 and 28,29,30,31-C74（BN）2 were calculated on the basis of AM1 geometries.     

簇合物[Fe2(CO)8]2-和[Fe3S(CO)9]2-成簇类型的光谱探讨及电子光谱和电子结构研究

在Fe(CO)₅+[Et₄N]₂MoS₄相同体系中,改变原料配比及碱度,可得到3种簇合物:(Ⅰ)[Et₄N]₂[Fe₂(CO)₈]、(Ⅱ)[Et₄N]₂[Fe₃S(CO)₉]、(Ⅲ)[Et₄N]₃[FeMo₂S₈O₂]。本文用电子光谱法考察了各簇合物的生成条件。根据X光结构分析,用群分解的EHMO程序,计算了(Ⅰ)、(Ⅱ)簇合物阴离子骨架能级,并研究了它们的电子光谱及电子结构。     

自由基C69N及双体(C69N)2结构和电子光谱的理论研究

用INDO系列方法对自由基C₆₉N(Cs)及双体(C₆₉N)₂(C₂h)进行了理论研究,结果表明:笼骨架上N的掺入使C₇₀笼发生畸变,N向笼外突出,与氮相连的碳(6-6环上的C)自旋密度较大,2个C₆₉N自由基在这个碳上以C-C单键连接,形成双体为C₂h对称性,N与附近的3个碳均以单键连接,并不断开。理论计算的电子光谱与实验吻合较好,(C₆₉N)₂易分解为单体C₆₉N.     

C_(70)R_2(R=OH,CH_3)的结构和电子光谱

INDO方法研究了C70R2（R＝OH，CH3）4种异构体的结构和稳定性，表明1，9－C70（OH）2比7，8－C70（OH）2稳定，两者能量差为38．5kJ／mol，而7，8－C70（CH3）2比1，9－C70（CH3）2能量低23．0kJ／mol．以优化构型为基础，对C70R2（R＝OH，CH3）的电子光谱进行了理论预测．