Electrochemically induced electron transfer through molecular bridges

In this Opinion, we address some of the most important results obtained electrochemically in the area of intramolecular electron transfer (ET). The focus is on freely diffusing molecular systems in which a donor D and an acceptor A are separated by a well-defined bridge B (D-B-A systems). B can be a saturated spacer, a delocalized bridge, or the more complex peptide backbones. As to the acceptors, the selected examples encompass species that can be charged reversibly but a special emphasis is on ETs associated with the concerted cleavage of a sigma bond (dissociative ETs). Our goal is to showcase the essential background, the most appropriate electrochemical tools and methodologies, and a series of selected examples where molecular electrochemistry has provided invaluable information on the mechanisms of intramolecular ET and electronic communication through bridges.     

The importance of a hot-sequential mechanism in triplet-state formation by charge recombination in reaction centers of bacterial photosynthesis

In photosynthesis, pigment-excitation energies in the antenna system produced by light harvesting are transferred among antenna pigments toward the core antenna, where they are captured by the reaction center and initially fixed in the form of a charge separation. Primary charge separation between an oxidized special pair (P⁺) and a reduced bacteriopheohytin (H⁻) is occasionally intervened by recombination, and a spin-triplet state (³P*) is formed on P in the bacterial reaction center. The ³P* state is harmful to bio-organisms, inducing the formation of the highly damaging singlet oxygen species. Therefore, understanding the ³P*-formation mechanism is important. The ³P* formation is mediated by a state |m〉 of intermediate charge separation between P and the accessory chlorophyll, which is located between P and H. It will be shown theoretically in the present work that at room temperature, not only the mechanism of superexchange by quantum-mechanical virtual mediation at |m〉, but also a hot-sequential mechanism contributes to the mediation. In the latter, although |m〉 is produced as a real state, the final state ³P* is quickly formed during thermalization of phonons in the protein matrix in |m〉. In the former, the final state is formed more quickly before dephasing-thermalization of phonons in |m〉. ³P* is unistep formed from the charge-separated state in the both mechanisms.     

The effect of La-substitution on magnetic properties of nanosized Sr1−xLaxTi0.05Zn0.2(Fe)11.75−δ(Fe)δO19 powders

A series of La-substituted M-type Sr hexaferrite powders Sr_1−xLa_xTi_0.05Zn_0.2Fe³⁺_11.75O₁₉, wherein x ranges from 0.1 to 0.5 with a step of 0.1, have been prepared by the conventional ceramic method and were then milled in a high energy mill to prepare nanosized powders. XRD investigation of the calcined and the milled powders shows that single phase hexaferrite structure has been formed after calcining and has not changed after milling. The lattice parameters and the mean crystallite sizes of the samples have been determined from the XRD data and Scherrer's formula. The results show that the lattice parameters (“а” and “c”) decrease with increase in La-substitution and the mean crystallite size of the milled powders is about 17 nm. Coercivities and magnetizations of the samples in a magnetic field of 16 kOe have been determined from the room temperature hysteresis loops. It was found that both parameters increase with La substitutions up to 0.3 and then decrease for higher substitutions. These variations were attributed to the enhancement of hyperfine field and spin-canting magnetic structure when La content increases. In addition, the magnetizations were smaller for the nanosized samples in comparison with those of bulk ones, which were discussed according to the core-shell model. Also the results show that annealing of the nanosized samples up to 500 °C can enhance coercivity and magnetization of the samples, which is discussed based on crystallite size growth.     

双链DNA分子内电荷转移超交换机理

设计并合成了一系列寡聚核苷酸组成的双链DNA分子,通过检测样品中二氨基嘌呤(Ap)荧光峰强度和相对荧光量子产率来研究DNA分子内电荷转移.实验中直接分辨和观测到双链DNA分子内电荷转移超交换机理,超交换机理在近距离起作用；而电荷转移跳跃机理,可能是通过极子运动形式体现.     

A Triphenylamine Derivative with Three p-(N-tert-Butyl-N-oxylamino)phenyl Radical Units and Yet a Doublet Ground State

A superexchange interaction through the lone pair of electrons on the central nitrogen atom in 1 is invoked to explain the existence of a doublet ground state; two spins on the aminoxyl radical centers couple antiferromagnetically, and one spin remains intact. This proposal is supported by EPR spectroscopic and magnetic measurements.     

Efficient Photoinduced Electron Transfer in a Rigid U-Shaped Tetrad Bearing Terminal Porphyrin and Viologen Units

Apparently solvent-mediated and not through-bond photoinduced electron transfer (ET) takes place from the porphyrin (P) unit to the methylviologen (MV²⁺) unit in the rigid U-shaped molecules 1 (i.e., k_TS^ET>k_TB^ET; TS=through-solvent, TB=through-bond). The ratio of the rates of charge separation to charge recombination is greater than 1400:1.     

Magnetic Orbitals and Mechanisms of Exchange II. Superexchange

Summary. In a first step, we examine the concept of magnetic orbital which is very useful to treat the mechanism of superexchange. After that, we recall the general broad lines of the first historical model proposed by Anderson. In a second step, we develop a new general treatment for superexchange, in the case of the centrosymmetrical model AXB, where A and B are metal cations and X a common bridging ligand (with here, for simplification, A = B, without transfer between cations). It allows one to retrieve the expression of exchange energy J vs. key molecular integrals, as respectively proposed by several authors such as Anderson on the one hand, Hay, Thibeault, and Hoffmann on the other one, and, finally, Kahn and Briat. This model may be easily generalized to the case where a transfer does exist between both cations, with A = B or A ≠ B. An erratum to this article is available at .     

Mössbauer study of chromium-substituted nickel ferrites

The structural and magnetic properties of the Cr substituted NiCr_xFe_1−xO₄ (0x1.4) spinel ferrites have been investigated by means of X-ray diffraction and Mössbauer spectroscopy techniques. Their crystal structures are found to be pure cubic phases. The Mössbauer spectra at 295 and 78 K of all samples showed two well-resolved magnetic patterns corresponding to the tetrahedral A-sites and octahedral B-sites. The cation distributions driven from the area under resonance curve of each site revealed that the compounds are gradually transferred from perfect inverse spinel to partially normal spinel structure. The behavior of the magnetic properties as a function of Cr³⁺ concentration has been explained on the basis of the driven cation distribution and it showed that the chrome-rich compositions can be explained in terms of the non-collinear spin model.     

HoIG中Ho3+离子低温下磁性各向异性现象的理论研究

基于量子理论计算了不同方向上HoIG中不同晶位上Ho3 离子的磁矩,继而求平均分别得到了[111],[110],[100]三个方向上在T=150～4.2K温度范围内HoIG中Ho3 离子的自发磁矩.计算结果显示Ho3 离子自发磁矩在低温下(T＜100K)明显出现了各向异性,并且随着温度的降低各向异性现象越来越明显,与实验结果符合较好,在理论上对HoIG中Ho3 离子自发磁矩在低温下出现各向异性现象做出了解释.