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Aggregate manganese Schiff base moieties by terephthalate or acetate: Dinuclear manganese and trinuclear mixed metal Mn-2/Na complexes
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2003 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 42, no 11, 3540-3548 p.Article in journal (Refereed) Published
Abstract [en]

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.

Place, publisher, year, edition, pages
2003. Vol. 42, no 11, 3540-3548 p.
Keyword [en]
dual-mode epr, photosystem-ii, magnetic-properties, crystal-structure, bond formation, mn cluster, photosynthesis, oxygen, water, compound
URN: urn:nbn:se:kth:diva-22534ISI: 000183222100024OAI: diva2:341232
QC 20100525Available from: 2010-08-10 Created: 2010-08-10Bibliographically approved

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