Magnetic circular dichroism spectra of some 3-arylfervenulins and 3-aryltoxoflavins

The magnetic circular dichroism (MCU) spectra of some 3-arylfervenulins and 3-aryltoxo-flavins were measured. From the dependence of the Faraday B values of 3-arylfervenulins and 3-aryltoxoflavins on the Hammet σpara values, it is concluded that the substituent effects on the Faraday B values of 3-aryltoxoflavins are reverse to the substituent effects on the Faraday B values of 3-arylfervenulins and the reverse property of 3-aryltoxoflavins concerning the substituent effects rises from the contribution of the 1,5-dipolar structure of 3-aryltoxoflavins.     

Magnetic circular dichroism spectra of triphenylene and coronene

The absorption spectra of triphenylene (I) and coronene (II) are assigned by using the MCD spectra and the results of the SCF screened potential π-MO CI calculations. The calculated Faraday A/D values for the ¹E and ¹E_1u excited states of I and II are in excellent agreement with the experimental values, in contrast to the calculated Faraday B value for the ¹E_1u state of II.     

A dinuclear MnIII-CuII single-molecule magnet

The reaction of 1/3 equivalent of CuCl2.2H2O with MnCl2.4H2O and 5-bromo-2-salicylideneamino-1-propanol (H(2)5-Br-sap) in methanol gave dark brown crystals of [MnIIICuIICl(5-Br-sap)2(MeOH)] (1). Complex 1 has an alkoxo-bridged dinuclear core of MnIII and CuII ions, which have elongated octahedral and square-planar coordination geometries, respectively. In dc magnetic susceptibility measurements, chi(m)T values increased as the temperature was lowered, followed by a sudden decrease below 20 K. This behavior is indicative of the occurrence of intramolecular ferromagnetic interactions, and fitting gave an S=5/2 spin ground state with an exchange coupling constant J(MnCu) of +78 cm(-1). Magnetization data collected as a function of temperature and applied magnetic field were analyzed by using a spin Hamiltonian with isotropic Zeeman and axial zero-field splitting (ZFS) terms, and a negative D(5/2) value (-1.86 cm(-1)) was obtained. A high-field EPR (HFEPR) spectrum (342.0 GHz) at 4.2 K was composed of four peaks, and two additional peaks at higher magnetic field appeared as the temperature was increased. The temperature dependences in the HFEPR spectra are indicative of a negative D(5/2) value, and fitting of the data gave D(5/2)=-1.81 cm(-1). In the ac magnetic susceptibility measurements, frequency dependent in-phase (chi(m)') and out-of-phase (chi(m)') signals with peak maxima at 0.7-1.5 K were observed and small peaks below 0.7 K appeared. The ac susceptibility data supports that 1 is a single-molecule magnet (SMM). Arrhenius plots for the chi(m)' peaks from 0.7-1.5 K gave the re-orientation energy barrier (DeltaE) of 10.5 K with a pre-exponential factor of 8.2x10(-8) s.     

Photochromism of diarylethene derivatives bearing a benzo[b]silole unit

Photochromic benzo[b]silole derivatives, 1-(1,1-dimethyl-2-phenylbenzo[b]silol-3-yl)-2-(2-phenylbenzo[b]thien-3-yl)perfluorocyclopentene and 1-(1,1-dimethyl-2-phenylbenzo[b]silol-3-yl)-2-(2-phenyl-1-benzofuran-3-yl)perfluorocyclopentene, were synthesized and their photochromic performance was examined in solution.     

Screened potential in π-electron systems and its application to the estimation of excitation energies

A diagrammatic technique was developed for the estimation of the screened potential of -electron systems. The screened potential was expanded in terms of the polarization propagators which were constructed from either the singlet, , or triplet vertex part, . These vertex parts correspond to the singlet or triplet excitations, respectively, in the Random Phase Approximation (RPA) containing exchange diagrams. The excitation energies were calculated by using the screened potential in the framework of RPA with exchange. The excitation energies of several conjugated molecules with or without a hetero atom are in agreement with the experimental data.     

Figure-eight thermal hysteresis of aminomethylenehelicene oligomers with terminal C16 alkyl groups during hetero-double-helix formation

1 : 1 mixtures of aminomethylenehelicene (P)-tetramer and (M)-pentamer with terminal C₁₆ alkyl groups in fluorobenzene showed structural changes between hetero-double-helices B and C and random-coils 2A. Figure-eight thermal hysteresis appeared when the solution was cooled and heated at a constant rate and involved the crossing of cooling and heating curves in Δε/temperature profiles. This unusual thermal hysteresis emerged in the intermediate state between counterclockwise and clockwise thermal hystereses. This phenomenon arose from the competition between self-catalytic reactions to form B and C from 2A. Significant effects of terminal C₁₆ alkyl groups on the thermodynamic and kinetic phenomena are also described.

1 : 1 mixtures of aminomethylenehelicene (P)-tetramer and (M)-pentamer with terminal C₁₆ alkyl groups in fluorobenzene showed structural changes between hetero-double-helices B and C and random-coils 2A.     

Geometry optimizations of the dioxetane,perepoxide and 1,4-diradicals for the ethylene plus molecular oxygen system: mechanism of photooxygenation of olefins

Geometry optimization of perepoxide, 1,4-diradicals and dioxetane for the ethylene plus molecular oxygen system is performed using the energy gradients of the HF 4-31G and STO-3G solutions. Perepoxide is less stable than the singlet (σπ) diradical by ≈24 k cal/mole at the 4-31G level, incompatible with the GVB CI plus thermochemical estimations. The rotational barrier of the terminal methylene group around the C-C bond is small.     

Local plasmon sensor with gold colloid monolayers deposited upon glass substrates

A new optical sensor that uses local plasmon resonance is proposed. A peak that is due to the local plasmon resonance appears in the absorption spectrum of a gold colloid suspension in the visible region, and its height and wavelength depend on the refractive index of the suspension. These properties are used for optical sensors. We used gold colloid monolayers in which colloidal gold particles a few tens of nanometers in diameter were immobilized upon a glass slide by a functional organic coupling agent. We measured the absorption spectra of the the gold colloid monolayers, which were immersed in liquid samples or coated with thin films. We observed increases of both the resonance wavelength and the absorbance as the refractive indices of the sample liquids or the thickness of the coated films increased. The proportional constants of the resonance wavelength to the film thickness were 3.6 and 5.7 for a 13.9- and a 20.2-nm gold colloid monolayer, respectively.     

6He中t+t结构的实验研究

在25MeV/u ⁶He轰击⁹Be靶的反应中,用探测器望远镜测得氚碎片,得到了5个角度的能谱,经过仔细的分析取得了高能直接破碎成分的角分布.利用Serber模型进行了破碎反应的理论计算,证实了实验中高能成分的t来自于⁶He的直接破碎反应.利用Fermi破碎模型计算了⁶He中各破碎反应道基于相空间的百分比产额,进而估算出⁶He初态中t+t结构的概率约占1/3, 而⁴He核心加价中子的组态约占2/3.