One-Pot Self-Assembly of Dinuclear, Tetranuclear, and H-Bonding-Directed Polynuclear Cobalt(II), Cobalt(III), and Mixed-Valence Co(II)/Co(III) Complexes of Schiff Base Ligands with Incomplete Double Cubane Core
| Autor: | Esther C. Wang, Rachel Thompson, Laurence K. Thompson, Neil Patel, Santokh S. Tandon, Scott D. Bunge |
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| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
Coordination number
tetranuclear chemistry.chemical_element polynuclear Co(II) Co(III) 010402 general chemistry 01 natural sciences lcsh:Technology Article self-assembly of Co(II) Co(III) chemistry.chemical_compound Deprotonation H-bonding-directed formation of cobalt supramolecular architectures with1D-single chains and 2D-sheet structures Moiety General Materials Science Hydroxymethyl dinuclear lcsh:Microscopy lcsh:QC120-168.85 Schiff base lcsh:QH201-278.5 010405 organic chemistry Hydrogen bond lcsh:T Cobalt(II)/Cobalt(III) complexes of Schiff base ligands with incomplete double cubane core mixed-valence Co(II)/Co(III) complexes 0104 chemical sciences Crystallography chemistry mixed-valence Co(II)/Co(III) complexes of Schiff base ligands Cubane lcsh:TA1-2040 Co(II)/Co(III) complexes lcsh:Descriptive and experimental mechanics lcsh:Electrical engineering. Electronics. Nuclear engineering lcsh:Engineering (General). Civil engineering (General) Cobalt lcsh:TK1-9971 |
| Zdroj: | Materials, Vol 13, Iss 5425, p 5425 (2020) Materials Volume 13 Issue 23 |
| ISSN: | 1996-1944 |
| Popis: | The reaction of 2,6-diformyl-4-methylphenol (DFMF) with 1-amino-2-propanol (AP) and tris(hydroxymethyl)aminomethane (THMAM) was investigated in the presence of Cobalt(II) salts, (X = ClO4&minus CH3CO2&minus Cl&minus NO3&minus ), sodium azide (NaN3), and triethylamine (TEA). In one pot, the variation in Cobalt(II) salt results in the self-assembly of dinuclear, tetranuclear, and H-bonding-directed polynuclear coordination complexes of Cobalt(III), Cobalt(II), and mixed-valence CoIICoIII: [Co2III(H2L&minus 1)2(AP&minus 1)(N3)](ClO4)2 (1), [Co4(H2L&minus 1)2(µ 3-1,1,1-N3)2(µ 1,1-N3)2Cl2(CH3OH)2]·4CH3OH (2), [Co2IICo2III(HL&minus 2)2(µ CH3CO2)2(µ 3-OH)2](NO3)2·2CH3CH2OH (3), and [Co2IICo2III (H2L12&minus )2(THMAM&minus 1)2](NO3)4 (4). In 1, two cobalt(III) ions are connected via three single atom bridges two from deprotonated ethanolic oxygen atoms in the side arms of the ligands and one from the1-amino-2-propanol moiety forming a dinuclear unit with a very short (2.5430(11) Å ) Co-Co intermetallic separation with a coordination number of 7, a rare feature for cobalt(III). In 2, two cobalt(II) ions in a dinuclear unit are bridged through phenoxide O and &mu 3-1,1,1-N3 azido bridges, and the two dinuclear units are interconnected by two &mu 1,1-N3 and two &mu 3-1,1,1-N3 azido bridges generating tetranuclear cationic [Co4(H2L&minus 1,1-N3)2Cl2(CH3OH)2]2+ units with an incomplete double cubane core, which grow into polynuclear 1D-single chains along the a-axis through H-bonding. In 3, HL2&minus holds mixed-valent Co(II)/Co(III) ions in a dinuclear unit bridged via phenoxide O, &mu 1,3-CH3CO2&minus and &mu 3-OH&minus bridges, and the dinuclear units are interconnected through two deprotonated ethanolic O in the side arms of the ligands and two &mu bridges generating cationic tetranuclear [Co2IICo2III(HL&minus 3-OH)2]2+ units with an incomplete double cubane core. In 4, H2L1&minus 2 holds mixed-valent Co(II)/Co(III) ions in dinuclear units which dimerize through two ethanolic O (&mu RO&minus ) in the side arms of the ligands and two ethanolic O (&mu 3-RO&minus ) of THMAM bridges producing centrosymmetric cationic tetranuclear [Co2IICo2III (H2L1&minus 2)2(THMAM-1)2]4+ units which grow into 2D-sheets along the bc-axis through a network of H-bonding. Bulk magnetization measurements on 2 demonstrate that the magnetic interactions are completely dominated by an overall ferromagnetic coupling occurring between Co(II) ions. |
| Databáze: | OpenAIRE |
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