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41.
IntroductionIn the past decades, chemists have exp1Ored the relatively weak noncovalent interactionsthat could exist between molecules, and also developed the means to design and fabricate.nanostructures serving as candidate for new matefials[1--4]. When these interactions act in acooperative and convergent way, organized assemblies can be constructed by molecular recog-nition directed self-assembly. Many successful nanostructures have been fabricated via suchmethods[5--9]. However, for the a… 相似文献
42.
The reaction of CuCl2 · 2 H2O, 1,10‐phenanthroline (phen), suberic acid and Na2CO3 in a CH3CN–H2O solution yielded blue needle‐like crystals of [Cu2(phen)2(C8H12O4)2] · 3 H2O. The crystal structure (monoclinic, P21/n, a = 10.756(2) Å, b = 9.790(2) Å, c = 18.593(4) Å, β = 91.15(3)°, Z = 2, R = 0.043, wR2 = 0.1238) consists of suberato‐bridged [Cu2(phen)2(C8H12O4)4/2] layers and hydrogen bonded H2O molecules. The Cu atoms are coordinated by two N atoms from one bidentate chelating phen ligand and three carboxyl O atoms from different suberato ligands to form distorted [CuN2O3] square‐pyramids with one carboxyl O atom at the apical position (d(Cu–N) = 2.017(2), 2.043(3) Å, basal d(Cu–O) = 1.936(2), 1.951(2) Å and axial d(Cu–O) = 2.389(2) Å). Two [CuN2O3] square‐pyramids are condensed via a common O–O edge to a centrosymmetric [Cu2N4O4] dimer with the Cu…Cu distance of 3.406(1) Å indicating no interaction between Cu atoms. The resultant [Cu2N4O4] dimers are interlinked by the tridentate suberato ligands to form [Cu2(phen)2(C8H12O4)4/2] layers parallel to (101). These are assembled via π‐π stacking interactions into 3D network with H2O molecules in the tunnels extending in the [010] direction. 相似文献
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A new mono-nuclear Mn(Ⅱ) complex [Mn(MPT)2(NCS)(HOCH3)]ClO4(MPT = 2-methoxyl-1,10-phenanthroline) has been synthesized with 2-methoxyl-1,10-phenanthroline and thiocyanate anion as ligands,and its crystal structure was determined by X-ray crystallography.The crystal data:monoclinic system,space group P21/c with a = 12.8849(17),b = 15.684(2),c = 14.2703(19) ,β = 92.126(2)°,V = 2881.9(7) 3,Z = 4,C28H24ClMnN5O7S,Mr = 664.97,Dc = 1.533 g/cm3,F(000) = 1364 and μ = 0.679 mm-1.In the crystal,MPT functions as a bidentate ligand and Mn(Ⅱ) ion assumes a distorted octahedral geometry.In the crystal there are two types of π-π stacking interactions among the adjacent complexes,which involves 1,10-phenanthroline rings.The theoretical calculations reveal that the two types of π-π stacking resulted in a weak anti-ferromagnetic coupling with 2J =-14.68 cm-1 and a weak ferromagnetic coupling with 2J = 0.70 cm-1,respectively.The theoretical calculations also reveal that there are both spin polarization and spin delocalization in the two π-π stacking systems,and the magnetic coupling signs are unable to explain with McConnell I spin-polarization mechanism. 相似文献
45.
An analytical procedure enabling routine analysis of human plasma for total homocysteine has been developed and validated.
The method includes reduction of homocysteine disulfides to thiol with tris 2-carboxyethylphosphine, derivatization of the
thiol with 2-chloro-1-methylquinolinium tetrafluoroborate, separation of homocysteine 2-S-quinolinium derivative from those of plasma endogenous and exogenous thiol derivatives by capillary zone electrophoresis,
and quantitation with the use of ultraviolet detection based on acetonitrile stacking. Method performance characteristics,
for example recovery, calibration, precision, limit of detection, and limit of quantitation, are presented. The procedure
was applied to analysis of plasma samples donated by apparently healthy volunteers. 相似文献
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Xavier Solans‐Monfort Dr. Roser Pleixats Prof. Mariona Sodupe Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(24):7331-7343
The catalytic activity and catalyst recovery of two heterogenized ruthenium‐based precatalysts ( H and NO2(4) ) in diene ring‐closing metathesis have been studied by means of density functional calculations at the B3LYP level of theory. For comparison and rationalization of the key factors that lead to higher activities and higher catalyst recoveries, four other Grubbs–Hoveyda complexes have also been investigated. The full catalytic cycle (catalyst formation, propagation, and precatalyst regeneration) has been considered. DFT calculations suggest that either for the homogeneous and heterogenized systems the activity of the catalysts mainly depends on the ability of the precursor to generate the propagating carbene. This ability does not correlate with the traditionally identified key factor, the Ru???O interaction strength. In contrast, precatalysts with lower alkoxy‐dissociation energy barriers and lower stabilities compared with the propagating carbene also present larger C1? C2 bond length (i.e., lower π character of the C? C bond that exists between the metal–carbene (Ru?C) and the phenyl ring of the Hoveyda ligand). Catalyst recovery, regardless of whether a release–return mechanism occurs or not, is also mainly determined by the π delocalization. Therefore, future Grubbs–Hoveyda‐type catalyst development should be based on fine‐tuning the π‐electron density of the phenyl moiety, with the subsequent effect on the metalloaromaticity of the ruthenafurane ring, rather than considering the modification of the Ru???O interaction. 相似文献
48.
Herein, we present three imidazo[1,2‐a]pyridin‐2(3 H)‐one derivatives that are diamagnetic in solution, but paramagnetic in the solid state, possibly owing to a stacking‐induced formation of phenoxide‐type radicals. Notably, a larger bathochromic shift of the absorption (even up to the near‐ infrared region) of these three compounds was observed in the solid state than in solution, which was attributable to the ordered columnar stacking arrangements or their single‐electron character as radicals in the solid state. Interestingly, compared to that in solution, (E)‐3‐(pyridin‐4′‐ylmethylene)imidazo[1,2‐a]pyridine 2(3 H)‐one displayed a largely red‐shifted emission (centered at 660 nm, with tailing above 800 nm) in the solid state. A larger bathochromic shift (260 nm) of the emission is an indication of better order and tight stacking in the solid state, which is brought about by the rigid and polar acceptor. These three compounds also reveal different magnetic susceptibilities at 300 K, thus implying that they possess various columnar stacking structures. Most interestingly, these three radicals exhibit unusual ferromagnetic‐to‐antiferromagnetic phase transitions, which can be attributed to anisotropic contraction and non‐uniform slippage of the columnar stacking chains. 相似文献
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