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1.
2.
Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs.  相似文献   
3.
In this paper, we study the integrals of the Ricci curvature over metric balls in a Finsler manifold,which can be viewed as an L~q-norm of the Ricci curvature. By bounding such integrals from above, we obtain several Myers type theorems.  相似文献   
4.
人造麝香的危害性及其残留检测方法研究进展   总被引:1,自引:0,他引:1  
综述了近年来人造麝香的危害性及其残留检测方法的研究进展。对化妆品、水、大气、土壤和药物中人造麝香的前处理方法和检测方法进行了比较,同时对此领域的发展方向进行了展望(引用文献31篇)。  相似文献   
5.
Construction of receptors with binding sites of specific size, shape, and functional groups is important to both chemistry and biology. Covalent imprinting of a photocleavable template within surface–core doubly cross‐linked micelles yielded carboxylic acid‐containing hydrophobic pockets within the water‐soluble molecularly imprinted nanoparticles. The functionalized binding pockets were characterized by their binding of amine‐ and acid‐functionalized guests under different pH values. The nanoparticles, on average, contained one binding site per particle and displayed highly selective binding among structural analogues. The binding sites could be modified further by covalent chemistry to modulate their binding properties.  相似文献   
6.
It has recently been suggested that the oxidation states of Ir run from the putative ?III in the synthesized solid Na3[Ir(CO)3] to the well‐documented +IX in the species IrO4+. Furthermore, [Ir(CO)3]3? was identified as an 18‐electron species. A closer DFT study now finds support for this picture: The orbitals spanned by the 6s,6p,5d orbitals of the iridium are all occupied. Although some have considerable ligand character, the deviations from 18 e leave the orbital symmetries unchanged. The isoelectronic systems from Os?IV to Au?I behave similarly, suggesting further possible species. To paraphrase Richard P. Feynmann “there is plenty of room at the bottom”.  相似文献   
7.
Ethynylpyridine polymers and oligomers consisting of 4‐substituted pyridine rings linked by acetylene bonds at the 2‐ and 6‐positions have been investigated. Ethynylpyridine oligomers covalently linked with a glycosyl chiral template form chiral helical complexes by intramolecular hydrogen bonding, in which the chirality of the template is translated to the helix. With a view to fixation of the chiral architecture, D /L ‐galactosyl‐ and D /L ‐mannosyl‐linked ethynylpyridine oligomers have been developed with 4‐(3‐butenyloxy)pyridine units having alkene side chains. The helical structures are successfully stapled by alkene metathesis of the side chains. Subsequent removal of the chiral templates by acidolysis produces template‐free stapled oligomers. The chiral, template‐free, stapled oligomers show chiral helicity, which is resistant to polar solvents and heating.  相似文献   
8.
The so‐called magic methyl effect significantly boosts the bioactivities and physical properties of pharmacologically active drugs. Direct introduction of the methyl group by C?H activation was accomplished with a versatile iron catalyst, which enabled the C?H methylation of (hetero)benzamides, anilides, alkenes, and even alkanes by triazole assistance in a chemo‐, site‐ and diastereo‐selective fashion.  相似文献   
9.
This paper deals with a systematic density functional theory (DFT) study aiming to unravel the mechanism of the thyroxine (T4) conversion into 3,3′,5‐triiodothyronine (rT3) by using different bio‐inspired naphthyl‐based models, which are able to reproduce the catalytic functions of the type‐3 deiodinase ID‐3. Such naphthalenes, having two selenols, two thiols, and a selenol–thiol pair in peri positions, which were previously synthesized and tested in their deiodinase activity, are able to remove iodine selectively from the inner ring of T4 to produce rT3. Calculations were performed including also an imidazole ring that, mimicking the role of the His residue, plays an essential role deprotonating the selenol/thiol moiety. For all the used complexes, the calculated potential energy surfaces show that the reaction proceeds via an intermediate, characterized by the presence of a X?I?C (X=Se, S) halogen bond, whose transformation into a subsequent intermediate in which the C?I bond is definitively cleaved and the incipient X?I bond is formed represents the rate‐determining step of the whole process. The calculated trend in the barrier heights of the corresponding transition states allows us to rationalize the experimentally observed superior deiodinase activity of the naphthyl‐based compound with two selenol groups. The role of the peri interactions between chalcogen atoms appears to be less prominent in determining the deiodination activity.  相似文献   
10.
A new non‐innocent ligand redox system, N,N′‐bis(4‐dimethylaminophenyl) substituted acetamidinato/acetamidinyl, has been designed and described by example of structurally and spectroscopically characterized ruthenium complexes. The hitherto unreported ligand is responsible for rather intense and narrow absorptions in the near‐infrared region of the one‐ and two‐electron oxidized forms. The spectroscopic, computational, and first structural characterization of an amidinyl radical complex adds to the list of established N‐based radical ligands.  相似文献   
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