Lowest electronic states of neutral and ionic LiN

We have investigated the potential energy curves (PECs) of the LiN heteronuclear diatomic molecule, including its ionic species LiN⁺ and LiN⁻, using explicitly correlated multi-reference configuration interaction (MRCI-F12) calculations in conjunction with the correlation consistent quintuple-𝜁 basis set. The effect of core–valence correlation, scalar relativistic effects, and the size of the basis sets has been investigated. A comprehensive set of spectroscopic constants determined based on the above-mentioned calculations are also reported for the lowest electronic states and all systems, including dissociation energies, harmonic and anharmonic vibrational frequencies, and rotational constants. Additional parameters, such as the dipole moments, equilibrium spin-orbit constants, excitation energies, and rovibrational energy levels, are also documented. We found that the three triplet states of LiN, namely, X ³∑⁻, A ³Π, and 2 ³∑⁻, exhibit substantial potential wells in the PEC diagrams, while the quintet states are repulsive in nature. The ground state of the anion also shows a deep potential well in the vicinity of its equilibrium geometry. In contrast, the ground and excited states of the cation are very loosely bound. Charge transfer properties of each of these states are also analyzed to obtain an in-depth understanding of the interatomic interactions. We found that the core–valence correlation has a substantial effect on the calculated spectroscopic constants.     

Spectrophotometric Determination of Oxygen as Its Charge-Transfer Complex with N,N-Dimethylaniline

Abstract

Oxygen (5–100%) in gas mixtures is determined by measuring the absorbance of its charge-transfer complex with dimethylaniline at 347 nm. The method is essentially specific, and merely requires bubbling the gas through the reagent, stabilized with EDTA. Oxygen is simply removed from the reagent by purging with nitrogen or carbon dioxide.     

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.     

Transformations of 4,4′-dimethoxystilbene in early stages of oxidation

4,4-Dimethoxystilbene forms a dimer as a result of one-electron anodic oxidation and undergoescis/trans-isomerization when bound in a charge-transfer complex (chloranil as acceptor).A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1219–1221, May, 1992.     

一种有机-无机电荷转移配合物的合成、结构及性能研究

A charge-transfer complex, [(C₂H₄OH)₃NH]₂·[HPMo₁₂O₄₀]·3H₂O, has been synthesized and characterized.The crystal structure of the complex was determined by X-ray diffraction. It belongs to orthorhombic, space grounp Pnna, with a=1.541 30(5) nm, b=1.884 23 (7) nm, c=2.049 06(7) nm, α=β=γ=90.00°, V=5.950 8(4) nm³, Z=4, D_c=2.427 Mg·m^-3 , F(000)=4 132, μ(Mo Kα)=2.568 mm^-1. The structure was refined to R₁=0.043 5 and wR₂=0.122 4 by full-matrix least-squares method. The O atoms of the polyoxometalate, the C atoms of the organic substrates and the O atoms of water molecules are involved in hydrogen bonding. Spectral data support the presence of an electronic interaction between the organic substrate and the inorganic anion in the solid state. It is strongly photochromic under ultraviolet light resulting from charge-transfer. The electrochemical behavior of the compound shows that the redox peak currents are proportional to the scan rate in pH=4.0 NaAc-HAc buffer solution, which indicates that the electrode reaction are surface controlled processes.     

具有纳米尺寸的四聚四硫富瓦烯大环冠醚的合成

以二(碘乙基)醚和2,3-二氰乙硫基四硫富瓦烯衍生物作为起始原料, 采用腈乙基保护与脱保护技术, 通过多步反应以较好的收率合成了两个纳米结构的大环四硫富瓦烯冠醚5a～5b. 通过循环伏安法(CV)研究了化合物4b和5b的电化学性质, 并用¹H NMR谱研究了5b与[60]富勒烯之间的相互作用. 结果表明: 5b存在环结构效应, 与[60]富勒烯有一定程度的电荷转移相互作用.     

Complementary,Cooperative Ditopic Halogen Bonding and Electron Donor-Acceptor π-π Complexation in the Formation of Cocrystals

This study expands and combines concepts from two of our earlier studies. One study reported the complementary halogen bonding and π-π charge transfer complexation observed between isomeric electron rich 4-N,N-dimethylaminophenylethynylpyridines and the electron poor halogen bond donor, 1-(3,5-dinitrophenylethynyl)-2,3,5,6-tetrafluoro-4-iodobenzene while the second study elaborated the ditopic halogen bonding of activated pyrimidines. Leveraging our understanding on the combination of these non-covalent interactions, we describe cocrystallization featuring ditopic halogen bonding and π-stacking. Specifically, red cocrystals are formed between the ditopic electron poor halogen bond donor 1-(3,5-dinitrophenylethynyl)-2,4,6-triflouro-3,5-diiodobenzene and each of electron rich pyrimidines 2- and 5-(4-N,N-dimethyl-aminophenylethynyl)pyrimidine. The X-ray single crystal structures of these cocrystals are described in terms of halogen bonding and electron donor-acceptor π-complexation. Computations confirm that the donor-acceptor π-stacking interactions are consistently stronger than the halogen bonding interactions and that there is cooperativity between π-stacking and halogen bonding in the crystals.     

Reactivity Ratios for Microemulsion Copolymerization of N-butyl Maleimide and Styrene

The oil-in-water microemulsion containing N-butyl maleimide(NBMI, M1) and styrene(St, M2) was prepared. The complexation properties of NBMI and St in microemulsion were investigated by means of 1H-NMR. With the participation of charge-transfer complex(CTC), four reactivity ratios and the relative reactivity of free monomers and CTC were obtained. The result was compared with that measured by Mayo-Lewis method.     

Estimation of Photoelectrocatalytic Activity of Titanium Oxide Film Electrodes by Ac Impedance

Over the last few decades, there has been a growing interest in the application of photocatalysis towards the treatment of polluted water1-4. It was well demonstrated that the anodic bias potential exerted on photoanode could prevent significantly the recombination rate of photogenerated carriers, consequently, it can improve the efficiency of photocatalytic degradation of organics2-4. For this, the study of photoelectrocatalytic degradation of pollutants has been of particular interest to r…     

电荷转移盐[C5H10NO]3[PW12O40]·C5H9NO·3H2O的合成和晶体结构

由N-甲基吡咯烷酮和H3PW12O40·nH2O反应得到了标题化合物,并以元素分析,红外光谱,质谱和X射线单晶衍射对其结构进行了表征．结构解析表明,该化合物属于三斜晶系,Pi空间群,晶胞参数为：α=1．335（2）nm,b=1．374（2）nm,c=1．826（2）nm,α=98．92（2）°,β=107．7（2）°,γ=109．9（2）°,V=2．873（1）nm^3,Z=2,Dc=3．840Mg/m^3,μ=24．05mm^-1,F（000）=2926,R1=0．0632,wR2=0．1403．在该化合物中,杂多阴离子仍保持其Keggin结构,通过静电引力与阳离子作用．