The Correlation between the Zeroth-Order General Randic Indices and the π-Electronic Energies of Hexagonal Systems

A formula was proved for computing the zeroth-order general Randic index of a hexagonal system to explore the correlation between the zeroth-order general Randic index and the π-electronic energy of a hexagonal system.As a consequence,the extremal hexagonal systems with minimum or maximum zeroth-order general Randic index were completely characterized.Moreover,by using the least-square fit method and regression analysis,a new and close relation was found between the zeroth-order general Randic index and the π-electronic energy of a hexagonal system.So the zeroth-order general Randic index is a good measure of the π-electronic energies for benzenoid hydrocarbons.

有机/聚合物π半导体的四元设计原理

从物质结构的角度来看,有机/聚合物半导体是以组合π-轨道为主要电荷载流子输运通道的分子凝聚态固体.其化学本质是π系统,可以通过π-轨道的分子工程技术来巧妙地合成.本文以自己课题组的工作为主线,从物理有机化学的角度,阐述了有机/聚合物半导体设计的基本四要素,即电子结构、空间位阻、构象与拓扑以及超分子弱作用.同时,总结了四个单元要素在有机/聚合物半导体设计方面的研究进展,并展望了四元设计正成为科学家的一种重要思维模式.

π-σ-π型单分子电子器件:分子内电子转移及其外电场效应

将由联苯阴离子和中性萘之间通过刚性环己烷所连接的经典的电子转移体系作一构象修正,得到一个π σ π型分子。UHF/6 31G 研究表明,此体系具有更高的能垒和小得多的电子转移耦合,而且其耦合几乎完全通过环己烷桥上的化学键实现。外电场效应的研究进一步发现,该体系在无外场条件下几乎没有电子转移反应发生,但当外电场增至0 001463au时,反应的能垒消失,其电子转移速率达到105s-1数量级。所有特征均显示,该体系具有作为单分子电子器件的分子原型的巨大潜力。

共轭体系同系物平均π-电子能的递变函数

用非线性规划得到 7个烃类同系列平均π -电子能的递变函数 ,对 7个系列部分化合物的平均π -电子能进行了计算 .结果表明 ,计算值与文献值十分吻合 ,残差均方数量级在 1 0 - 3～ 1 0 - 5β之间 ,58个化合物的平均绝对误差仅为 5.3× 1 0 - 5β ,最大绝对误差仅为 0 .0 0 7β.

π-σ-π型双稳态分子器件的分子内电子转移及外电场效应

将由联苯阴离子和中性萘之间通过刚性环己烷所连接的经典的电子转移体系作一构象修正,得到一个新的π-σ-π型分子.UHF/6-31G**研究表明,新体系具有较高的能垒和很小的电子转移耦合,而且其耦合几乎完全通过环己烷桥上的化学键实现.外电场效应的研究进一步发现,该体系的电荷可稳定地定域在联苯片段或萘片段上,仅当出现外部刺激(如电、光等),其电荷定域态才会迅速转变.因此,认为该体系可以作为双稳态分子器件材料的原型分子.

染料发色原理新论(一)

提出了研究染料发色原理的新概念，即“推电子中心”与“吸电子中心”，并用此新概念来解释各类染料的化学结构与其发色关系的规律，进而推测染料的色光。

儿茶酚胺的Hückel分子轨道理论及作用机理的研究

儿茶酚胺是茶汤主要功效成份之一，其功效与它的分子轨道函数相关。通过HMO的计算，π—电子体系中的7，8原子具有很强的电子给予能力。又由于σ—电子体系极性基团的存在，因此为Belleau模型提供了有力的理论依据。

Calculation of Energies of the Ground and Low Excited States of a Confined Helium Atom in a Spherical Parabolic Well

Making use of the adiabatic hyperspherical approach, we report a calculation for the energy spectrum of the ground and low-excited states of the confined helium atom in a spherical parabolic well. We find that the energies of a spherical parabolic well are in good agreement with those of an impenetrable spherical box for the larger confined potential radius. However, the energy values of a spherical parabolic well are much lower than those of an impenetrable spherical box for small values of re. We also find that the confinement may cause accidental degeneracies between levels with different low-excited states and the inversion of the energy values.

共轭体系特征指数简易计算法

以直链共轭烃的π电子能级和π分子轨道表达式为基础，从分子各特征量的定义出发，推导出能直接用于计算分子特征量为表达式。因此简化了运算过程，为建立分子图和对共轭烃的讨论带来了方便。

周环反应的理论基础及应用

周环反应已经广泛地运用于有机合成的各个领域,在合成环烯反应中起着重要作用。π电子体系的判断依据及相应顺旋/对旋的规律是周环反应的重点和难点,通过举例讨论4n和4n+2π电子体系的判断准则及在周环反应中关环/开环的规律和应用。针对立体思维较薄弱的初学者,在遵循该法则的基础上,引导学生探索规律,帮助学生系统掌握相关知识体系。

显色理论与染料的颜色综述

有机染料的颜色非常丰富。本文通过实例,从物质结构的内在因素——电子跃迁的诸种形式进行综合分析,揭示有机染料的生色原理。

Increasingπ-electron availability in benzene ring incorporated graphitic carbon nitride for increased photocatalytic hydrogen generation

Increasing the availability ofπ-electron in graphitic carbon nitride(g-C_(3)N_(4))can reduce the band gap and thus enhance the photocatalytic hydrogen(H_(2))generation activity upon exposure to visible light,However,such strategy has not yet been largely applied to increase the H_(2)generation of g-C_(3)N_(4).Herein,we succes s fully increased the amount ofπ-electron in g-C_(3)N_(4)by incorporatingπ-electron-rich benzene rings through copolymerization of melamine and trimesic acid in air.The incorporation of benzene rings not only extends the light absorption of g-C_(3)N_(4)to 650 nm,but also improves the electrical conductivity due to delocalization ofπelectrons in benzene rings.As a result,a 3.4 times enhancement of photocatalytic H_(2)generation was achieved from the g-C_(3)N_(4)with benzene ring incorporation in comparing with that of pristine g-C_(3)N_(4).More interestingly,H_(2)generation still occurs under irradiation of the light ofλ≥490 nm,above the absorption edge of pristine g-C_(3)N_(4)(~460 nm),illustrating the positive effectiveness of incorporated benzene rings on enhancing the H_(2)generation capacity of g-C_(3)N_(4).The present work manifests the advantages of increasingπ-conjugated electrons on designing highly active g-C_(3)N_(4)photocatalysts.

Aromatic alcohols oxidation and hydrogen evolution over π-electron conjugated porous carbon nitride rods

Photocatalysis using polymeric carbon nitride(CN)materials is a constantly evolving field,where the variation of synthetic procedures allows the constant improvement of activity by tackling the intrinsic limitations of these materials(optical absorbance,specific surface area,charge migration,etc.).Amongst the possible photocatalytic reactions,the most popular application of CNs is the hydrogen evolution reaction(HER)from water.In this work,we design precisely-controlled carbon-doped porous CN rods with extended π-electron conjugation from supramolecular assemblies of melem and co-monomers,which partially substitute nitrogen for carbon atoms at the pyrimidine ring of the melem.Dense hydrogen bonds and good thermal stability of the melem-based supramolecular framework allow synthesizing a more ordered structure for improved charge migration;the control from the molecular level over the position of carbon-substituted nitrogen positions tailors the band alignment and photogenerated charge separation.The optimal photocatalyst shows an excellent HER rate(up to 10.16 mmol·h-1·g-1 under 100 W white light-emitting diode(LED)irradiation,with an apparent quantum efficiency of 20.0%at 405 nm,which is 23.2 times higher compared to a reference bulk CN).To fully harness the benefits of the developed metal-free CNs,selective oxidation reaction of aromatic alcohols is demonstrated with high conversion and selectivity.

AN IMPLICIT ANALYTIC ENERGY FUNCTION FOR 1-ELECTRON SYSTEM

In this work, an implicit analytic energy function for an electron in a many-center system is derived. The formalism is based on the concept of LCAO in the direct space and the representation of wave functions in the momentum space. In principle, any order of accuracy can be accomplished by iteration. The implicit analytic energy function is discussed thoroughly with a presentation concerning its potential application to molecular problems which are related to the variation of bond angles and lengths.

P-glycoprotein(ABCB1)-weak dipolar interactions provide the key to understanding allocrite recognition,binding,and transport

P-glycoprotein(ABCB1)is the first discovered mammalian member of the large family of ATP binding cassette(ABC)transporters.It facilitates the movement of compounds(called allocrites)across membranes,using the energy of ATP binding and hydrolysis.Here,we review the thermodynamics of allocrite binding and the kinetics of ATP hydrolysis by ABCB1.In combination with our previous molecular dynamics simulations,these data lead to a new model for allocrite transport by ABCB1.In contrast to previous models,we take into account that the transporter was evolutionarily optimized to operate within a membrane,which dictates the nature of interactions.Hydrophobic interactions drive lipid-water partitioning of allocrites,the transport process’s first step.Weak dipolar interactions(including hydrogen bonding,π-π stacking,and π-cation interactions)drive allocrite recognition,binding,and transport by ABCB1 within the membrane.Increasing the lateral membrane packing density reduces allocrite partitioning but enhances dipolar interactions between allocrites and ABCB1.Allocrite flopping(or reorientation of the polar part towards the extracellular aqueous phase)occurs after hydrolysis of one ATP molecule and opening of ABCB1 at the extracellular side.Rebinding of ATP re-closes the transporter at the extracellular side and expels the potentially remaining allocrite into the membrane.The high sensitivity of the steady-state ATP hydrolysis rate to the nature and number of dipolar interactions,as well as to the dielectric constant of the membrane,points to a flopping process,which occurs to a large extent at the membrane-transporter interface.The proposed unidirectional ABCB1 transport cycle,driven by weak dipolar interactions,is consistent with membrane biophysics.

Furan-containing Conjugated Polymers for Organic Solar Cells

Development of organic semiconductors is one of the most intriguing and productive topics in material science and engineering. Many efforts have been made on the synthesis of aromatic building blocks such as benzene, thiophene and pyrrole due to the facile preparation accompanied by the intrinsic environmental stability and relatively efficient properties of the resulting polymers. In the past, furan has been less explored in this field because of its high oxidation potential. Recently, furan has attracted obsession due to its weaker aromaticity, the greater solubilities of furan-containing π-conjugated polymers relative to other benzenoid systems and the accessibility of furan-based starting materials from renewable resources. This review elaborates the advancements of organic photovoltaic polymers containing furan building blocks. The uniqueness and advantages of furan-containing building blocks in semiconducting materials are also discussed.

Application of molecular orbital graph theory——A cutting vertex method for evaluating E_π

Just as Tang and Jiang pointed out in ref. [1], the total π-electron energy Eπ of a conjugate molecule is of significance for understanding the stability and aromatic character of molecule or the reaction route. They also proposed the expanded formula for evaluating Eπ by using molecular moment μ1.

Pendant Group Effect of Polymeric Dielectrics on the Performance of Organic Thin Film Transistors

Polymer dielectric is superior to its inorganic counterparts due to not only the low cost and intrinsic flexibility,but also the readily tunable dielectric constant,surface charge trap density,charge ejection and releasing ability and dipole moment,and all these properties play decisive roles in regulating the characteristic and performances of organic thin film transistors(OTFT).However,systematical studies on the relationship between structure and properties of polymeric dielectrics are rare.To this end,a series of polymeric dielectrics with well-defined linkages(ester or amide bonds)and predesigned pendant groups(alkyl-and aromatic-groups)are synthesized in high yields.Detailed studies show that the polyamide dielectrics exhibit higher dielectric constant,surface charge trapping density,and better charge storage capability than corresponding polyester dielectrics.Further,increasing theπelectron delocalization of the pendant groups generally benefits the charge storage property and transistor memory behavior.Theoretical calculation reveals that the hydrogen bonding between the linkage groups and the energy alignment between polymeric dielectric and semiconductor are responsible for the observed performance differences of OTFT with different polymeric dielectrics.These results may shine light on the design of polymeric dielectrics for OTFTs with different applications.

Bowl-shaped conjugated polycycles

The conjugated polycycles show excellent optical and electrical properties that are suitable for application in various organic electronics.While most of attentions have been paid to polycycles having planar π-conjugated system,the curved polycycles seem amazing due to their unique physical and chemical features.The non-planar conjugated polycycles have been created with the geometries of bracelet,saddle,bowl,Mobius band,helicenes,etc.Among them,the bowl-shaped one is of growing interest owing to the multidiscipline applications such as synthetic intermediates for end-cap of carbon nanotube,coordination with metal ions,encapsulation of fullerenes,and fabrication of electronic devices.In this paper,we summarize the recent advances on the chemistry of the bowl-shaped conjugated polycycles,particularly on their synthesis and the further chemical modifications toward organic functional materials.