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A series of rigid hexadentate salen-type (H2L) ytterbium complexes, namely, [Yb2L3(CH3OH)]·3CH3CN (1), [Yb2LL'L″(CH3OH)(H2O)2](ClO4)2·CH3OH·H2O (2), [Yb2L(OAc)4(CH3OH)2]·2CH3OH (3), and {[Yb2L(OAc)4]·3H2O}n (4) (H2L = N,N'-bis(2-oxy-3-methoxybenzylidene)-1,2-phenylenediamine, HL' = 2-(2'-hydroxy-3'-methyloxy-phenyl)benzimidazole and HL" = 3-methoxysalicylaldehyde) have been synthesized by reactions of H2L with multifarious Yb(3+) salts. X-ray crystallographic analyses demonstrate that complex 1 is of a triple-decker sandwich-type Yb2L3 structure with a ratio of H2L/Yb = 3:2, 2 and 3 possess the unique Yb2 core with a ratio of H2L/Yb = 2:2 and 1:2, respectively, 4 exhibits one dimensional coordination polymers in which the polymeric structures are formed by acetate (OAc(-)) groups. All complexes 1-4 exhibit near-IR luminescence, which can be rationalized on the basis of the disparate structural effects. The magnetic analysis unveils that all complexes 1-4 are of field-induced single-molecule magnet behavior with the energy barriers (Ueff/kB) of 14.5, 2.0, 9.5, and 2.4 K at 3 kOe direct current fields, respectively.

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The cyclization mechanism of (E)-2,6-dimethyl-6-hydroxyocta-2,7-dienoic acid to wine lactone under acidic aqueous conditions was investigated using the two stereoselectively deuterium-labeled precursors (2E,6R,7Z)-[8-2H]-2,6-dimethyl-6-hydroxyocta-2,7-dienoic acid and (2E,7E)-(+/-)-[8-2H]-2,6-dimethyl-6-hydroxyocta-2,7-dienoic acid. A detailed analysis of the generated wine lactone isomers by enantioselective multidimensional gas chromatography (MDGC)/ion trap tandem mass spectrometry demonstrates that the formation of wine lactone proceeds via a nonenzymatic stereoselective cationic cyclization cascade that includes a 1,3-hydride shift. Usually, such mechanisms are features of cyclization reactions that are catalyzed by terpene cyclases. This nonenzymatic conversion of an acyclic precursor to a bicyclic monoterpene under relevant cationic cyclization conditions has rarely been observed and confirms recent suggestions that the precursor itself can provide the chemical functionality required for specific steps in the cyclization cascade.

A series of three β-diketone mononuclear dysprosium complexes, namely, Dy(TFI)3(H2O)2 (1), Dy(TFI)3(bpy) (2), and [Dy(TFI)3(Phen)]·0.02CHCl3 (3) (TFI = 2-(2,2,2-trifluoroethyl)-1-indone, bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline) have been designed and synthesized. Crystal structure analysis reveals that complexes 1-3 have haveisomorphic structures in which the central Dy(III) ion is eight-coordinated by six oxygen atoms from three TFI ligands and two O/N atoms from auxiliary ligands, forming a distorted bicapped trigonal prismatic geometry for 1, a distorted dodecahedral geometry for 2, and a distorted square antiprismatic geometry for 3, respectively. Magnetic studies indicate that complex 2 with D(2d) symmetry and 3 with D(4d) symmetry exhibit slow magnetic relaxation with barrier heights (U(eff)/k(B)) of 48.8 K for 2 and 57.9 K for 3. Strikingly, the relaxation time (τ) of 0.0258 s for 3 is about 20 times that for 2, which is presumably associated with larger rotation of the SAP surroundings for 3. Further, complexes 2 and 3 exhibit essential magnetic hysteresis loops at 1.8 K. These extend the recent reports of the single-ion magnets (SIMs) of β-diketone mononuclear dysprosium complexes.

The enantiomeric ratios of various free and glycosidically bound monoterpene polyols in musts of the aromatic grapes Vitis vinifera L. cvs. Morio Muscat and Muscat Ottonel were determined by means of enantioselective multidimensional gas chromatography-mass spectrometry. Reference compounds of defined stereochemistry were synthesized and permitted the unequivocal determination of the elution order of the target compounds on chiral columns with modified cyclodextrins as stationary phases. It could be shown for the first time that the linalool-derived polyol 3,7-dimethylocta-1,7-dien-3,6-diol occurs predominately as the (3S,6S)-configured stereoisomer, providing evidence that this compound is generated by an enzymatic process in grape berries. The involvement of a cytochrome P450 monooxygenase in the oxidative metabolism of monoterpenes in grapes is dicussed.