Three Polyhydroxyl-Bridged Defective Dicubane Tetranuclear MnIII Complexes: Synthesis, Crystal Structures, and Spectroscopic Properties
Three polyhydroxyl-bridged tetranuclear MnIII complexes [Mn4(L1a)2(μ3-OMe)2(μ2-OMe)2(MeOH)2] (1), [Mn4(L2a)2(μ3-OMe)2(μ2-OMe)2(H2O)2] (2), and [Mn4(L3a)2(μ3-OMe)2(μ2-OMe)2(H2O)2] (3) derived from Mnn+-promoted reactivity of Schiff base ligands (HL1 = 1-(4-{[...
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MDPI AG
2018-06-01
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| author | Hao-Ran Jia Jian Chang Hong-Jia Zhang Jing Li Yin-Xia Sun |
| author_facet | Hao-Ran Jia Jian Chang Hong-Jia Zhang Jing Li Yin-Xia Sun |
| author_sort | Hao-Ran Jia |
| collection | DOAJ |
| description | Three polyhydroxyl-bridged tetranuclear MnIII complexes [Mn4(L1a)2(μ3-OMe)2(μ2-OMe)2(MeOH)2] (1), [Mn4(L2a)2(μ3-OMe)2(μ2-OMe)2(H2O)2] (2), and [Mn4(L3a)2(μ3-OMe)2(μ2-OMe)2(H2O)2] (3) derived from Mnn+-promoted reactivity of Schiff base ligands (HL1 = 1-(4-{[(E)-3,5-dichlorine-2-hydroxybenzylidene]amino}phenyl)ethanone O-benzyloxime, HL2 = 1-(4-{[(E)-3-bromine-5-chloro-2-hydroxybenzylidene]amino}phenyl) ethanone O-benzyloxime, and HL3 = 1-(4-{[(E)-3,5-dibromine-2-hydroxybenzylidene]amino}phenyl)ethanone O-benzyloxime) have been synthesized and characterized. In the MnIII complexes 1, 2, and 3, the newly formed ligands (L1a)4−, (L2a)4−, and (L3a)4− are derived from the chemoselective cleavage of the C=N bond in the original Schiff base ligands HL1, HL2, and HL3 to form corresponding halogenated salicylaldehyde, 3,5-dichlorosalicylaldehyde, 3-bromine-5-chlorosalicylaldehyde, and 3,5-dibrominesalicylaldehyde, respectively. Then, the further addition of acetone to two halogenated salicylaldehyde molecules in situ α,α double aldol reaction promoted by Mnn+ ions in the presence of base to give the new ligands ((Lna)4−. X-ray crystallographic analyses of the MnIII complexes 1, 2, and 3 show that the three complexes are all tetranuclear structure and crystallizes in the triclinic system, space group P-1. The four MnIII ions and bridging alkoxido groups are arranged in a face-shared dicubane-like core with two missing vertices. In the three MnIII complexes, the asymmetric unit contains two kinds of different MnIII ions (Mn1 and Mn2), where the MnIII ions are all hexacoordinated with slightly distorted octahedral geometries. Simultaneously in the synthesis of multinuclear Mnn+ complexes above, we explored the crystal structure, spatial configuration, and spectroscopic properties of the multinuclear MnIII complexes with different halogen substituents. |
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| spelling | doaj.art-9faeda104954482bb73e1d6464999f9c2022-12-22T03:59:10ZengMDPI AGCrystals2073-43522018-06-018727210.3390/cryst8070272cryst8070272Three Polyhydroxyl-Bridged Defective Dicubane Tetranuclear MnIII Complexes: Synthesis, Crystal Structures, and Spectroscopic PropertiesHao-Ran Jia0Jian Chang1Hong-Jia Zhang2Jing Li3Yin-Xia Sun4School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, ChinaSchool of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, ChinaSchool of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, ChinaSchool of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, ChinaSchool of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, ChinaThree polyhydroxyl-bridged tetranuclear MnIII complexes [Mn4(L1a)2(μ3-OMe)2(μ2-OMe)2(MeOH)2] (1), [Mn4(L2a)2(μ3-OMe)2(μ2-OMe)2(H2O)2] (2), and [Mn4(L3a)2(μ3-OMe)2(μ2-OMe)2(H2O)2] (3) derived from Mnn+-promoted reactivity of Schiff base ligands (HL1 = 1-(4-{[(E)-3,5-dichlorine-2-hydroxybenzylidene]amino}phenyl)ethanone O-benzyloxime, HL2 = 1-(4-{[(E)-3-bromine-5-chloro-2-hydroxybenzylidene]amino}phenyl) ethanone O-benzyloxime, and HL3 = 1-(4-{[(E)-3,5-dibromine-2-hydroxybenzylidene]amino}phenyl)ethanone O-benzyloxime) have been synthesized and characterized. In the MnIII complexes 1, 2, and 3, the newly formed ligands (L1a)4−, (L2a)4−, and (L3a)4− are derived from the chemoselective cleavage of the C=N bond in the original Schiff base ligands HL1, HL2, and HL3 to form corresponding halogenated salicylaldehyde, 3,5-dichlorosalicylaldehyde, 3-bromine-5-chlorosalicylaldehyde, and 3,5-dibrominesalicylaldehyde, respectively. Then, the further addition of acetone to two halogenated salicylaldehyde molecules in situ α,α double aldol reaction promoted by Mnn+ ions in the presence of base to give the new ligands ((Lna)4−. X-ray crystallographic analyses of the MnIII complexes 1, 2, and 3 show that the three complexes are all tetranuclear structure and crystallizes in the triclinic system, space group P-1. The four MnIII ions and bridging alkoxido groups are arranged in a face-shared dicubane-like core with two missing vertices. In the three MnIII complexes, the asymmetric unit contains two kinds of different MnIII ions (Mn1 and Mn2), where the MnIII ions are all hexacoordinated with slightly distorted octahedral geometries. Simultaneously in the synthesis of multinuclear Mnn+ complexes above, we explored the crystal structure, spatial configuration, and spectroscopic properties of the multinuclear MnIII complexes with different halogen substituents.http://www.mdpi.com/2073-4352/8/7/272defective dicubane tetranuclear MnIII complexSchiff base ligandmanganese-promoteddouble aldol additioncrystal structurespectroscopic property |
| spellingShingle | Hao-Ran Jia Jian Chang Hong-Jia Zhang Jing Li Yin-Xia Sun Three Polyhydroxyl-Bridged Defective Dicubane Tetranuclear MnIII Complexes: Synthesis, Crystal Structures, and Spectroscopic Properties Crystals defective dicubane tetranuclear MnIII complex Schiff base ligand manganese-promoted double aldol addition crystal structure spectroscopic property |
| title | Three Polyhydroxyl-Bridged Defective Dicubane Tetranuclear MnIII Complexes: Synthesis, Crystal Structures, and Spectroscopic Properties |
| title_full | Three Polyhydroxyl-Bridged Defective Dicubane Tetranuclear MnIII Complexes: Synthesis, Crystal Structures, and Spectroscopic Properties |
| title_fullStr | Three Polyhydroxyl-Bridged Defective Dicubane Tetranuclear MnIII Complexes: Synthesis, Crystal Structures, and Spectroscopic Properties |
| title_full_unstemmed | Three Polyhydroxyl-Bridged Defective Dicubane Tetranuclear MnIII Complexes: Synthesis, Crystal Structures, and Spectroscopic Properties |
| title_short | Three Polyhydroxyl-Bridged Defective Dicubane Tetranuclear MnIII Complexes: Synthesis, Crystal Structures, and Spectroscopic Properties |
| title_sort | three polyhydroxyl bridged defective dicubane tetranuclear mniii complexes synthesis crystal structures and spectroscopic properties |
| topic | defective dicubane tetranuclear MnIII complex Schiff base ligand manganese-promoted double aldol addition crystal structure spectroscopic property |
| url | http://www.mdpi.com/2073-4352/8/7/272 |
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