A Theoretical Investigation of Gas Phase OH-Initiated Acenaphthylene Degradation Reaction

The mechanisms for OH-initiated acenaphthylene degradation reactions are investigated theoretically by using the density function theory method at M06-2X/aug-cc-pVTZ level in the present paper. There are two possible reaction pathways for the degradation processes have been predicted: the hydrogen abstraction pathway and the hydroxyl addition elimination pathway. Additionally, the formation mechanism for a series of the products such as epoxide, naphthalene-1,8-dicarbaldehyde, dialdehydes, 1-acenaphthenone and nitroacenaphthylene are discussed in detail as well. From the analyses of the decomposition of OH-acenaphthylene adducts, it is found that the favorable reaction with O2/NO is to form the acenaphthenone rather than epoxide, and the most stable isomer is acenaphthenone react from the C1-site reaction. The advantage reaction pathway with NO2 is to form nitroacenaphthylene and nitroacenaphthylenol from C1-site, too.

Theoretical Studies on the Molecular Structures and Thermodynamic Properties of Polychlorinated Acenaphthylenes

Geometric structures of 135 polychlorinated acenaphthylene （PCAC） molecules were optimized using density functional theory （DFT） at the B3LYP/6-311G^＊＊ level and some thermodynamic properties of them in the ideal gas state were calculated. The relations of these thermodynamic properties with the number and position of chlorine atoms were also explored, from which the relative stability of PCAC congeners was theoretically proposed according to the magnitude of the relative standard Gibbs free energy of formation （△r,fGθ）. The results show that all PCAC isomers have planar geometric configuration. There exists intramolecular Cl···Cl weak interaction in some PCAC molecules. The change of △fHθ and fGθ of most stable PCAC isomers with increasing the number of chlorine atoms is different from that in the least stable PCAC congeners. The values of fHθ and fGθ for PCAC isomers with the same number of chlorine atoms show a strong dependence on the position of chlorine atoms and the relative stability of PCAC congeners has close relation with the intramolecular Cl···Cl nuclear repulsive interaction.

Copper-promoted domino cyanation/Ullmann coupling toward difunctionalized acenaphthylenes with various optoelectronic properties

Tremendous progress has been made on aromatic fusion of acenaphthylene towards organic semiconductors.However,scarce studies focus on the functionalization of acenaphthylene without resort to aromatic extension,although vinylene double bond is highly reactive ascribed to the ring strain of the fused cyclopentene.Herein,for the first time we employ copper-promoted domino cyanation/Ullmann coupling to achieve a series of difunctionalized acenaphthylene imides(ANIs)with varied optoelectronic properties.Both Ullmann homocoupling and crosscoupling can be combined with cyanation for difunctionalization of ANIs.The introduction of cyano groups influences oppositely not only the energy levels but also the antiaromaticity of the fivemembered rings in ANIs relative to the dimethylamino substituent due to the electron donating or withdrawing effects.By altering the functional units,the optical and electrical characteristics have been tailored rationally;thus p,n or ambipolar semiconducting properties can be achieved for the ANI derivatives.This article opens up possibilities to the development of organic semiconducting materials based on ANIs without aromatic extension,which is promising for applications in organic electronics.

基于苊烯酰二亚胺小分子/二氧化钛双分子电子传输层的高效钙钛矿太阳能电池（英文）

设计合成高效n型小分子半导体作为钙钛矿太阳能电池的电子传输层对实现低温、可溶液加工的钙钛矿太阳能电池具有重要意义.本文合成了三个低LUMO能级、基于苊烯酰二亚胺的小分子受体材料AI1, AI2, AI3,系统表征了其光物理性质及电化学、热力学性质,研究了其在钙钛矿太阳能电池器件中的应用.当使用TiO_2/AI1作为电子传输层时,钙钛矿太阳能电池的平均光电转换效率为15%,比单独TiO_2电子传输层11.7%的平均光电转换效率有较大提升,表明基于苊烯酰二亚胺的小分子AI1, AI2, AI3是良好的电子传输层材料,可实现低温、可溶液加工的高效钙钛矿太阳能电池.