| 1. |
- Chen, C. N., et al.
(författare)
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Aggregate manganese Schiff base moieties by terephthalate or acetate : Dinuclear manganese and trinuclear mixed metal Mn-2/Na complexes
- 2003
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 42:11, s. 3540-3548
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Tidskriftsartikel (refereegranskat)abstract
- A reaction system consisting of terephthalic acid, NaOH, inorganic Mn(II) or Mn(III) salt, and salicylidene alkylimine resulted in dinuclear manganese complexes (salpn)(2)Mn-2(mu-phth)(CH3OH)(2) (1, salpn = N,N'-1,3-propylene-bis(salicylideneiminato); phth = terephthalate dianion), (salen)(2)Mn-2(mu-phth)(CH3OH)(2) (2, salen = N,N'-ethylene-bis(salicylideneiminato)), (salen)(2)Mn-2(mu-phth)(CH3OH)(H2O) (3), and (salen)(2)Mn-2(mu-phth) (4), while the absence of NaOH in the reaction led to a mononuclear Mn complex (salph)Mn(CH3OH)(NO3) (5, salph = N,N'-1,2-phenylene-bis(salicylideneiminato)). In addition, a trinuclear mixed metal complex H{Mn2Na(salpn)(2)(mu-OAc)(2)(H2O)(2)}(OAc)(2) (6) was obtained from the reaction system by using maleic acid instead of terephthalic acid. Five-coordinate Mn ions were found in 4 giving rise to an intermolecular interaction and constructing a one-dimensional linear structure. Antiferromagnetic exchange interactions were observed for 1-3, and a total ferromagnetic exchange of 4 was considered to stem from intermolecular magnetic coupling. H-1 NMR signals of phenolate ring and alkylene (or phenylene) backbone of the diamine are similar to those reported in the literature, and the phth protons are at -2.3 to -10.1 ppm. Studies on structure, bond valence sum analysis, and magnetic properties indicate the oxidation states of the Mn ions in 6 to be +3, which are also indicated by ESR spectra in dual mode. Ferromagnetic exchange interaction between the Mn(III) sites was observed with J = 1.74 cm(-1). A quasireversible redox pair at -0.29V/0.12V has been assigned to the redox of Mn-2(III)/Mn(III)Mn(II), implying the intactness of the complex backbone in solution.
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| 2. |
- Huang, D. G., et al.
(författare)
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Synthesis, structural characterizations and magnetic properties of a series of mono-, di- and polynuclear manganese pyridinecarboxylate compounds
- 2004
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Ingår i: European Journal of Inorganic Chemistry. - : Wiley. - 1434-1948 .- 1099-1948 .- 1099-0682. ; :7, s. 1454-1464
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Tidskriftsartikel (refereegranskat)abstract
- Seven new manganese(II, III, IV) pyridinecarboxylate compounds (Et4N)[MnCl2(pic)(2)] (1, Hpic = picolinic acid) [MnCl(Pic)(2)(H2O)].H2O (2), [MnCl(pic)(H2O)2](n) (3), [Mn(Pic)(2)](n) (4), [MnCl(pic)](n) (5), [MnCl2(4-C5H4NHCOO)](n) (6) and [Mn2O2(pic)(4)] (7) were synthesized and structurally characterized. The picolinate ligand coordinates to the Mn ion forming a chelating five-membered ring which constructs diverse architectures by various bridging modes, such as mu-Cl, mu(1,1)(-) and mu(1,3)-carboxylate bridges (syn-syn and syn-anti modes). The interaction between the pyridyl rings is discussed, displaying a face-to-face pi-pi stacking for complex 6 and a T-shaped C-H...pi attraction for complex 4. Complex 3 has an infinite zigzag chain structure in which two neighboring Mn ions are linked by a carboxylate bridge in a syn-anti mode. In complex 4, the Mn(pic)(2) fragments are joined to each other by double mu(1,1)-carboxylate bridges, forming a 2D layer structure. Complex 5 contains Mn4O4 square subunits which are connected by double mu-Cl bridges to form a grid-like 2D structure. The isonicotinate complex 6 has a zigzag chain structure containing mixed double mu-Cl and mu(1,3)-carboxylate bridges in a syn-syn mode. Protonation at the pyridyl-N position was found and identified by the IR and magnetic properties of 6. The participation of an oxidizing agent like MnO4- leads to complexes containing higher valent manganese (1, 2 and 7). The IR spectra of these complexes are discussed and found to be consistent with the structural features. The magnetic properties of complexes 4, 5 and 6 have been investigated. Antiferromagnetic coupling interactions were observed and satisfactory fitting results were obtained with J values ranging from -0.63 cm(-1) to -2.35 cm(-1). The magnetic parameters of these complexes, together with the parameters of other Mn complexes with comparable structures, are compared and discussed based on the bridging modes. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).
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| 3. |
- Huang, D. U., et al.
(författare)
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Synthesis, structural characterization and magnetic properties of 2-pyrazinecarboxylate manganese compounds Mn(pyz)(2)(H2O)(4) and MnCl(pyz)(H2O) (n) (pyz=2-pyrazinecarboxylate)
- 2003
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Ingår i: Inorganica Chimica Acta. - 0020-1693 .- 1873-3255. ; 353, s. 284-291
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Tidskriftsartikel (refereegranskat)abstract
- Two pyz complexes [Mn(pyz)(2)(H2O)(4)] (1) and [MnCl(pyz)(H2O)] (2) have been synthesized and structurally characterized. Complex 1 contains an eight-coordinate Mn(II) ion with square anti-prismatic geometry. The extensive intermolecular hydrogen-bonding interactions of O-carboxyl...H-O-aqua correlate the complex molecules, forming 2D polymeric layer structure. The structure of complex 2 contains 1D Mn/pyz chains, which link to each other by double mu(2)-Cl bridges to form 2D layer with Mn...Mn distance of 3.664 Angstrom. Hydrogen-bonding interactions of O-carboxyl...H-O-aqua are found between the layers to correlate the 2D layers to form a 3D framework. In addition, the variable temperature magnetic susceptibilities of complex 2 were measured and weak ferromagnetic exchange interactions between the neighboring magnetic species were found with J = 0.42 cm(-1).
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| 4. |
- Ma, C. B., et al.
(författare)
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Great framework variation of polymers in the manganese(II) maleate/alpha,alpha' - Diimine system : Syntheses, structures, and magneto-structural correlation
- 2003
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Ingår i: European Journal of Inorganic Chemistry. - : Wiley. - 1434-1948 .- 1099-1948 .- 1099-0682. ; :15, s. 2872-2879
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Tidskriftsartikel (refereegranskat)abstract
- Three novel manganese(II) coordination polymers, [Mn (maleate)(phen)](n) (1; phen = 1,10-phenanthroline), [Mn-(maleate)(phen)](n).nH(2)O (2), and [Mn(maleate)(bpy)](n) (3; bpy = 2,2'-bipyridine), have been synthesized by treatment of Mn2+ with maleic acid with participation of chelate diimine ligands, and have been identified by single-crystal, X-ray diffraction to have either one-dimensional (1D) zigzag chain structures (1 and 2) or a two-dimensional (2D) sinuous layer structure (3). Each maleate dianion coordinates to three Mn centers, in different bridging modes (syn-anti in 1 and 2, syn-syn and anti-anti in 3). These compounds represent an interesting example of structural topology variation from 1D to 2D mediated by chemically similar auxiliary chelate ligands. Variable-temperature magnetic susceptibility measurements show weak anti-ferromagnetic exchange interactions between the adjacent Mn-II ions, with J = -0.06 cm(-1) (2) and J = -1.3 cm(-1), zJ' = -0.27 cm(-1) (3). The differences in the magnitudes of these coupling interactions agree well with the nature of the carb oxylate-bridging coordination of maleate.
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| 5. |
- Mason, M.G., et al.
(författare)
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Interfacial chemistry of Alq3 and LiF with reactive metals
- 2001
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Ingår i: Journal of Applied Physics. - : AIP Publishing. - 0021-8979 .- 1089-7550. ; 89:5, s. 2756-2765
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Tidskriftsartikel (refereegranskat)abstract
- The electronic structure and chemistry of interfaces between tris-(8-hydroxyquinoline) aluminum (Alq3) and representative group IA and IIA metals, Al, and Al/LiF have been studied by x-ray and ultraviolet photoelectron spectroscopies. Quantum-chemical calculations at the density functional theory level predict that the Alq3 radical anion is formed upon reaction with the alkali metals. In this case, up to three metal atoms can react with a given Alq3 molecule to form the trivalent anion. The anion formation results in a splitting of the N 1 s core level and formation of a new feature in the previously forbidden energy gap. Virtually identical spectra are observed in the Al/LiF/Alq3 system, leading to the conclusion that the radical anion is also formed when all three of these constituents are present. This is support by a simple thermodynamic model based on bulk heats of formation. In the absence of LiF or similar material, the reaction of Al with Alq3 appears to be destructive, with the deposited Al reacting directly with the quinolate oxygen. We proposed that in those circumstances where the radical anion is formed, it and not the cathode metal are responsible for the electron injection properties. This is borne out by producing excellent injecting contacts when Ag and Au are used as the metallic component of the cathode structure. © 2001 American Institute of Physics.
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