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Andrea Cornia Antonio Costantino Fabretti Roberta Sessoli Lorenzo Sorace Dante Gatteschi Anne‐Laure Barra Carole Daiguebonne Thierry Roisnel 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(7):m371-m373
The structure of hexadeca‐μ‐acetato‐tetraaquadodeca‐μ3‐oxo‐dodecamanganese bis(acetic acid) tetrahydrate, [Mn12O12(CH3COO)16(H2O)4]·2CH3COOH·4H2O, known as Mn12–acetate, has been determined at 83 (2) K by X‐ray diffraction methods. The fourfold (S4) molecular symmetry is disrupted by a strong hydrogen‐bonding interaction with the disordered acetic acid molecule of solvation, which displaces one of the acetate ligands in the cluster. Up to six Mn12 isomers are potentially present in the crystal lattice, which differ in the number and arrangement of hydrogen‐bonded acetic acid molecules. These results considerably improve the structural information available on this molecular nanomagnet, which was first synthesized and characterized by Lis [Acta Cryst. (1980), B 36 , 2042–2046]. 相似文献
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Summary LetC be the symmetric cusp {(x, y)2:–x
yx
,x0} where >1. In this paper we decide whether or not reflecting Brownian motion inC has a semimartingale representation. Here the reflecting Brownian motion has directions of reflection that make constant angles with the unit inward normals to the boundary. Our results carry through for a wide class of asymmetric cusps too. 相似文献
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Barone V Bencini A Gatteschi D Totti F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(21):5019-5027
Density functional theory (DFT) was applied to describe the magnetic and electron-transfer properties of dinuclear systems containing the [MnO2Mn]n+ core, with n=0,1,2,3,4. The calculation of the potential energy surfaces (PESs) of the mixed-valence species (n=1,3) allowed the classification of these systems according to the extent of valence localization as Class II compounds, in the Robin-Day classification scheme. The fundamental frequencies corresponding to the asymmetric breathing vibration were also computed. 相似文献
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Pacchioni M Cornia A Fabretti AC Zobbi L Bonacchi D Caneschi A Chastanet G Gatteschi D Sessoli R 《Chemical communications (Cambridge, England)》2004,(22):2604-2605
A novel single-molecule magnet of the Mn12 family, [Mn12O12(O2CC6H5)8(L)4(H2O)4].8CH2Cl2, has been synthesised by site-specific ligand exchange using a tailor-made dicarboxylate (L2-), which leads to selective occupation of axial binding sites. 相似文献
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(R)-Phenylglycinol is shown to be an efficient building block for the synthesis of chiral amino diols in pure diastereomeric form by epoxide ring-opening reactions. The reaction with rac-trans-stilbene oxide gives [HOCH(2)-(R)-PhCH]NH[(S)-PhCH-(R)-PhCHOH] [2(R)-3(R)-4(S)-HNO(2)H(2)] in 32% yield, which can be methylated at nitrogen to give enantiomerically pure [HOCH(2)-(R)-PhCH]NCH(3)[(S)-PhCH-(R)-PhCHOH] [2(R)-3(R)-4(S)-MeNO(2)H(2)]. These amino diol ligands have been used to prepare chiral dioxomolybdenyl complexes of the formula N(R)-2(R)-3(R)-4(S)-(HNO(2))MoO(2) (1) and N(R)-2(R)-3(R)-4(S)-(MeNO(2))MoO(2) (2). The absolute configuration at each stereocenter in the Mo(VI) complexes has been established by (1)H NOESY spectroscopy. The configuration determined for 1 has been confirmed by an X-ray analysis. Crystal data: orthorhombic P2(1)2(1)2(1), a =7.620(3), b = 13.589(2), c = 20.339(3) ?, Z = 4, R = 0.0336. The structure consists of a polymeric chain of N(R)-2(R)-3(R)-4(S)-(HNO(2))MoO(2) molecules connected through unsymmetrical Mo=O --> Mo bridges. Each metal center is coordinated in a distorted octahedral geometry by a cis dioxo unit and by two trans alkoxo atoms. The coordination polyhedron is completed by a nitrogen atom and by a bridging oxo oxygen atom from an adjacent molecule. Compound 2 catalyzes the oxidation of PPh(3) to OPPh(3) by DMSO through a mechanism that involves the intermediacy of a Mo(IV) species. 相似文献