Diferrocenophosphaborin: A Planar‐Chiral,Redox‐Active and Anion‐Responsive Ambiphilic Ligand

A new class of Janus‐like ambiphilic ligands is introduced. The rigid diferrocene backbone in heterocycles 4‐SnP and 4‐BP creates an unprecedented chiral environment as demonstrated by multinuclear NMR and single‐crystal X‐ray studies. In addition, the ligands are redox‐responsive and the Lewis acidic borane moiety in 4‐BP can be exploited to further tune the properties: a clear decrease in the CO stretching frequency of a Vaska‐type Rh^I complex 5‐BP is observed upon addition of fluoride ions. Thus, the Lewis acid and Lewis base sites influence each other and their strength can be modulated by redox chemistry and anion binding.     

古斯—汉欣位移的发现与发展

目前古斯-汉欣位移泛指有限束宽光束在界面处反射或透射时,在入射平面内会出现偏离几何光学预言的一小段横向移动量。古斯—汉欣位移的研究可追溯至牛顿时代,但直到1947年才在实验上发现了该位移,此后人们开始对其逐步深入研究。作为一种基本的物理现象,它已延伸到声学、量子力学和物质波等领域。文章作者结合自身研究经历与认识,从古斯—汉欣位移的发现、理论解释及最新的研究进展等方面对其进行介绍。     

Diferrocenylmercury‐Bridged Diphosphine: A Chiral,Ambiphilic, and Redox‐Active Bidentate Ligand

A diphosphine chelate ligand with a wide and flexible bite angle, a unique stereochemical environment, and redox‐active and ambiphilic character is reported. Initially generated as its HgCl₂ complex by reaction of 1,2‐fc(PPh₂)(SnMe₃) (fc=ferrocenediyl) with HgCl₂ in acetone, treatment with [n‐Bu₄N]CN readily liberates the free chiral bidentate ligand. An intermolecular ClHg−Cl→Hgfc₂ (2.9929(13) Å) interaction that is unprecedented in ambiphilic ligand chemistry is seen in the solid structure of Hg(fcPPh₂)₂⋅HgCl₂ where the bridging mercury atom acts as a σ‐acceptor. Furthermore, a bis‐[Rh(COD)Cl] complex is introduced, which displays relatively short Rh⋅⋅⋅Hg contacts of 3.4765(5) and 3.4013(1) Å. Wiberg indices of 0.12 are determined for these Rh⋅⋅⋅Hg interactions and an AIM analysis reveals bond paths with an electron density ρ(r) of 1.2×10⁻² and 1.4×10⁻² e/a₀³ at the bond critical points.     

黑体辐射公式的多种推导及其在近代物理构建中的意义(Ⅰ)

黑体辐射是近代物理史上一只会下金蛋的鹅,是近代物理的摇篮。黑体辐射研究的意义还在于这是唯一一个涉及c,k,h三个普适常数的物理情景。黑体辐射谱抗测量误差的特性带来了辐射标准和绝对温度参照,谱分布公式对模型的不敏感则使得黑体辐射成为独特的物理研究母题。黑体辐射谱分布公式,普朗克多角度推导过,德拜推导过,艾伦菲斯特推导过,劳厄推导过,洛伦兹和庞加莱深入讨论过,泡利推导过,玻色推导过,爱因斯坦在20多年的时间里多角度推导过且产出最为丰硕,近代还有从相对论角度的推导,每一个角度的推导都带来了物理学的新内容,这包括量子力学、固体量子论、受激辐射、量子统计、相对论统计,等等。认真回顾黑体辐射研究的历史细节,考察其中的思想概念演化,不啻于体验一次教科书式的学(做)物理之旅,比如也可以尝试给出能量局域分立化的简单新证明。