Abstract

Abstract

The syntheses of three anilido–imine ligands of the general formula ortho-C₆H₄(NHAr′)(CH=NAr″ [Ar′ = 7-(2,4-Me₂)C₉H₄N, Ar″ = 2,6-Me₂C₆H₃ (2a); Ar′ = 7-(2,4-Me₂)C₉H₄N, Ar″= 2,6-Et₂C₆H₃ (2b); Ar′ = 7-(2,4-Me₂)C₉H₄N, Ar″= 2,6-iPr₂C₆H₃ (2c)] and four zinc(II) complexes of the general formula [ortho-C₆H₄(NHAr′)(CH=NAr″)]ZnEt [Ar′ = 7-(2,4-Me₂)C₉H₄N, Ar″= 2,6-Me₂C₆H₃ (3a); Ar′ = 7-(2,4-Me₂)C₉H₄N, Ar″= 2,6-Et₂C₆H₃ (3b); Ar′ = 7-(2,4-Me₂)C₉H₄N, Ar″ = 2,6-iPr₂C₆H₃ (3c); Ar″ = 2,6-Me₂C₆H₃, Ar″ = 2,6-iPr₂C₆H₃ (3d)] are described. The complexes were synthesized from the reaction of ZnEt₂ with corresponding ligands 2 by alkane elimination. All compounds were characterized by elemental analysis and ¹H and ¹³C NMR spectroscopy. The molecular structures of compounds 2a, 2b, 3b, and 3c were determined by single-crystal X-ray crystallography. The X-ray analysis reveals that complexes 3b and 3c exist in the dimeric form with the N atom in the quinolyl ring coordinating to the other Zn atom to make the Zn atoms four coordinate. Luminescent properties of ligands 2a–2d and complexes 3a–3d in both solution and the solid state were studied. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Three new boron complexes with anilido-imine ligands, ortho-C₆H₄(NAr¹)(CH=NAr²)BF₂ [Ar¹ = 2,6-Et₂C₆H₃, Ar² = p-MeC₆H₄ (3a); Ar¹ = 2,6-iPr₂C₆H₃, Ar² = p-MeC₆H₄ (3b); Ar¹ = 2,6-iPr₂C₆H₃, Ar² = 2,6-Me₂C₆H₃ (3c)] were synthesized by the reaction of BF₃(OEt₂) with the lithium salt of the corresponding ligands. All complexes were characterized by ¹H, ¹¹B, ¹³C and ¹⁹F NMR spectroscopy, elemental analyses and mass spectrometry. The molecular structures of complexes 3a–3c were determined by X-ray crystallography. DSC analysis of 3a–3c demonstrates their good thermal stability. Luminescent properties of the ligands and the complexes 3a–3c in solution and the solid state were studied. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Four d¹⁰ group 12 metal complexes, 6-(2-methoxyphenyl)-2,2′-bipyridinezinc dichloride (2a), -mercury dichloride (2b), 6-[2-(dimethylamino)phenyl]-2,2′-bipyridinezinc dichloride (2c), and -mercury dichloride (2d), were synthesized and the structures determined by single-crystal X-ray crystallography. Complexes 2a and 2b are four-coordinate and adopt a distorted tetrahedral geometry, while complexes 2c and 2d are five-coordinate with a distorted trigonal bipyramidal geometry for the metal center. Luminescent properties of complexes 2a–2d in both solution and the solid state were studied. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

The syntheses of a number of four-coordinate aluminum complexes, ortho-C₆H₄(NAr′)(CH=NAr′′)AlCl₂ [Ar′ = Ar′′ = 2,6-iPr₂C₆H₃ (2a); Ar′ = 2,6-iPr₂C₆H₃, Ar′′ = 2,6-Me₂C₆H₃ (2b); Ar′ = Ar′′ = 2,6-Me₂C₆H₃ (2c); Ar′ = p-MeC₆H₄, Ar′′ = 2,6-iPr₂C₆H₃ (2d)], are described. Complexes 2a–2d were synthesized from the reaction of AlCl₃ with lithium salt of the corresponding ligand at room temperature. All complexes were characterized by ¹H and ¹³C NMR spectroscopy and molecular structures of complexes 2a, 2b, and 2d were determined by X-ray crystallography. Luminescent properties of complexes 2a–2d in both solution and the solid state were studied. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Four new Cd^II complexes of 2,6-bis[1-(phenylimino)ethyl]pyridine (L¹), 2,6-bis[1-(2,6-diisopropylphenylimino)ethyl]pyridine (L²), 2,6-bis[1-(2,6-dimethylphenylimino)ethyl]pyridine (L³), 2,6-bis[1-(2-methylphenylimino)ethyl]pyridine (L⁴) have been synthesized. These complexes have the formulas [Cd(L¹)Cl₂]·1.5CH₃CN (1), [Cd(L²)Cl₂] (2), [Cd(L³)Cl₂]·CH₃CN (3), and [Cd(L⁴)Cl₂]·CH₃CN (4). The molecular structures of complexes 1−4 were determined by single-crystal X-ray diffraction. Crystallographic studies of 1−4 reveal all four complexes to be five-coordinate with geometries that can be best described as distorted trigonal-bipyramidal. All eight compounds (L¹−L⁴ and 1−4) are luminescent at room temperature in solution and the solid state. At 298 K in dichloromethane solution, all compounds have fluorescent emissions at about 368−409 nm. The fluorescent emission of these compounds originates from ligand-centered π*−π transitions. The Cd^II centers play a key role in enhancing the fluorescent emission of the ligands. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)