Manganese(II) complexes derived from acyclic ligands having flexible alcohol arms: structural chracterization and SOD and catalase mimetic studies

In this work, a series of seven MnII complexes of noncyclic flexible ligands derived from 2,6-diformylpyridine and ethanolamine or alkyl-substituted ethanolamines were prepared and characterized, six structurally by single-crystal X-ray diffraction studies. The complexes are dichlorido{2,2′-[(pyridine-2,6-diyl)bis(nitrilomethanylylidene)]diethanol}manganese(II), [MnCl2(C11H15N3O2)] or [MnCl2(L1)], (2), bis{μ-2,2′-[(pyridine-2,6-diyl)bis(nitrilomethanylylidene)]diethanol}bis[dithiocyanatomanganese(II)], [Mn2(NCS)4(C11H15N3O2)2] or [Mn2(NCS)4(L1)2], (3), chlorido{1,1′-[(pyridine-2,6-diyl)bis(nitrilomethanylylidene)]bis(propan-2-ol)}manganese(II) chloride monohydrate, [MnCl(C13H19N3O2)(H2O)]Cl·H2O or [MnCl(L2)(H2O)]Cl·H2O, (4), {1,1′-[(pyridine-2,6-diyl)bis(nitrilomethanylylidene)]bis(propan-2-ol)}dithiocyanatomanganese(II), [Mn(NCS)2(C13H19N3O2)] or [Mn(NCS)2(L2)], (5), aquadichlorido{2,2′-dimethyl-2,2′-[(pyridine-2,6-diyl)bis(nitrilomethanylylidene)]bis(propan-1-ol)}manganese(II) 0.3-hydrate, [MnCl2(C15H23N3O2)(H2O)]·0.3H2O or [MnCl2(L3)(H2O)]·0.3H2O, (6), (dimethylformamide){2,2′-dimethyl-2,2′-[(pyridine-2,6-diyl)bis(nitrilomethanylylidene)]bis(propan-1-ol)}dithiocyanatomanganese(II), [Mn(NCS)2(C15H23N3O2)(C3H7NO)] or [Mn(NCS)2(L3)(DMF)], (7), and (dimethylformamide){2,2′-[(pyridine-2,6-diyl)bis(nitrilomethanylylidene)]bis(butan-1-ol)}dithiocyanatomanganese(II) dimethylformamide monosolvate, [Mn(NCS)2(C15H23N3O2)(C3H7NO)]·C3H7NO or [Mn(NCS)2(L4)(DMF)]·DMF, (8). The crystal structure of ligand L1 is also reported, but that of (5) is not. All four ligands (L1–L4) have five potential donor atoms in an N3O2 donor set, i.e. three N (pyridine/diimine donors) and two alcohol O atoms, to coordinate the MnII centre. The N3O2 donor set coordinates to the metal centre in a pentagonal planar arrangement; seven-coordinated MnII complexes were obtained via coordination of two auxiliary ligands (anions or water molecules) at the axial positions. However, in some cases, the alcohol O-atom donors remain uncoordinated, resulting in five- or six-coordinated MnII complexes. The structurally characterized complexes were tested for their catalytic scavenging of superoxide and peroxide. The results indicated that the complexes with coordinated exogenous water or chloride ligands showed higher SOD activity than those with exogenous thiocyanate ligands.

Zinc/itaconate coordination polymers as first examples with long-lasting phosphorescence based on acyclic ligands

CPs based on zinc(ii) and the acyclic dicarboxylate itaconate linker show blue fluorescence that turns into green long lasting phosphorescence.

A new route for the synthesis of phosphate esters: 2,2′-[benzene-1,2-diylbis(oxy)]bis(5,5-dimethyl-1,3,2-dioxaphosphinane) 2,2′-dioxide

Podand-type ligands are an interesting class of acyclic ligands which can form host–guest complexes with many transition metals and can undergo conformational changes. Organic phosphates are components of many biological molecules. A new route for the synthesis of phosphate esters with a retained six-membered ring has been used to prepare 2,2′-[benzene-1,2-diylbis(oxy)]bis(5,5-dimethyl-1,3,2-dioxaphosphinane) 2,2′-dioxide, C6H4{O[cyclo-P(O)OCH2CMe2CH2O]}2or C16H24O8P2, (1), 2-[(2′-hydroxybiphenyl-2-yl)oxy]-5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxide, [cyclo-P(O)OCH2CMe2CH2O](2,2′-OC6H4–C6H4OH), (2), and oxybis(5,5-dimethyl-1,3,2-dioxaphosphinane) 2,2′-dioxide, O[cyclo-P(O)OCH2CMe2CH2O]2, (3). Compound (1) is novel, whereas the results for compounds (2) and (3) have been reported previously, but we record here our results for compound (3), which we find are more precise and accurate than those currently reported in the literature. In (1), twocyclo-P(O)OCH2CMe2CH2O groups are linked through a catechol group. The conformations about the two catechol O atoms are quite different,viz.one C—C—O—P torsion angle is −169.11 (11)° and indicates atransarrangement, whereas the other C—C—O—P torsion angle is 92.48 (16)°, showing agaucheconformation. Both six-membered POCCCO rings have good chair-shape conformations. In both thetransandgaucheconformations, the catechol O atoms are in the axial sites and the short P=O bonds are equatorially bound.

High-denticity ligands based on picolinic acid for 111In radiochemistry

Four new acyclic ligands, Bn-H3nonapa (3), H3nonapa (4), p-NO2-Bn-H3nonapa (10), and Bn-H3trenpa (7), were synthesized and studied with nonradioactive In3+ and with radioactive 111In3+. The coordination of these ligands to In3+ was confirmed by high-resolution mass spectrometry and nuclear magnetic resonance spectroscopy. Radiolabeling experiments were performed with 111In3+; these demonstrated H3nonapa (4) to be the best indium ligand of those studied herein, achieving radiochemical yields of ∼97% in 10 min at ambient temperature, and stability to transchelation in mouse serum of 44.5% ± 25.9% after 24 h. Although the radiolabeling kinetics of H3nonapa (4) were excellent, serum stability results were inferior to the previously studied ligands DOTA, DTPA, and H4octapa, suggesting that the presented ligands may find their optimum radiopharmaceutical applications with isotopes other than 111In. Owing to the high denticity of these ligands (9–10 coordinate), they may realize their potential with large ion isotopes such as 177Lu, 86/90Y, and 225Ac.