Dangling and hydrolyzed ligand arms in [Mn3] and [Mn6] coordination assemblies: synthesis, characterization, and functional activity

Krishna Chattopadhyay, Gavin A. Craig, María José Heras Ojea, Moumita Pait, Animesh Kundu, Junseong Lee, Mark Murrie, Antonio Frontera, Debashis Ray

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Two flexible, branched, and sterically constrained di- and tripodal side arms around a phenol backbone were utilized in ligands H3L1 and H5L2 to isolate {Mn6} and {Mn3} coordination aggregates. 2,6-Bis{(1-hydroxy-2-methylpropan-2-ylimino)methyl}-4-methylphenol (H3L1) gave trinuclear complex [Mn3(μ-H2L1)2(μ1,3-O2CCH3)4(CH3OH)2](ClO4)2·4CH3OH (1), whereas 2,6-bis[{1-hydroxy-2-(hydroxymethyl)butan-2-ylimino}methyl]-4-methylphenol (H5L2) provided hexanuclear complex [Mn6(μ4-H2L2)2(μ-HL3)2(μ3-OH)2(μ1,3-O2CC2H5)4](ClO4)2·2H2O (2). Binding of acetates and coordination of {H2L1}− provided a linear MnIIIMnIIMnIII arrangement in 1. A MnIII6 fused diadamantane-type assembly was obtained in 2 from propionate bridges, coordination of {H2L2}3–, and in situ generated {HL3}2–. The magnetic characterization of 1 and 2 revealed the properties dominated by intramolecular anti-ferromagnetic exchange interactions, and this was confirmed using density functional theory calculations. Complex 1 exhibited field-induced slow magnetic relaxation at 2 K due to the axial anisotropy of MnIII centers. Both the complexes show effective solvent-dependent catechol oxidation toward 3,5-di-tert-butylcatechol in air. The catechol oxidation abilities are comparable from two complexes of different nuclearity and structure.
LanguageEnglish
Pages2639-2652
Number of pages14
JournalInorganic Chemistry
Volume56
Issue number5
Early online date15 Feb 2017
DOIs
Publication statusPublished - 6 Mar 2017

Fingerprint

assemblies
Ligands
Magnetic relaxation
Oxidation
ligands
Exchange interactions
Propionates
synthesis
Phenol
Density functional theory
oxidation
Acetates
Anisotropy
magnetic relaxation
phenols
acetates
assembly
Air
density functional theory
anisotropy

Keywords

  • coordination assembly
  • 2-amino-2-ethyl-propane-1,3-diol
  • 2-amino-2- methylpropan-1-ol
  • imine hydrolysis

Cite this

Chattopadhyay, Krishna ; Craig, Gavin A. ; Heras Ojea, María José ; Pait, Moumita ; Kundu, Animesh ; Lee, Junseong ; Murrie, Mark ; Frontera, Antonio ; Ray, Debashis. / Dangling and hydrolyzed ligand arms in [Mn3] and [Mn6] coordination assemblies : synthesis, characterization, and functional activity. In: Inorganic Chemistry. 2017 ; Vol. 56, No. 5. pp. 2639-2652.
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abstract = "Two flexible, branched, and sterically constrained di- and tripodal side arms around a phenol backbone were utilized in ligands H3L1 and H5L2 to isolate {Mn6} and {Mn3} coordination aggregates. 2,6-Bis{(1-hydroxy-2-methylpropan-2-ylimino)methyl}-4-methylphenol (H3L1) gave trinuclear complex [Mn3(μ-H2L1)2(μ1,3-O2CCH3)4(CH3OH)2](ClO4)2·4CH3OH (1), whereas 2,6-bis[{1-hydroxy-2-(hydroxymethyl)butan-2-ylimino}methyl]-4-methylphenol (H5L2) provided hexanuclear complex [Mn6(μ4-H2L2)2(μ-HL3)2(μ3-OH)2(μ1,3-O2CC2H5)4](ClO4)2·2H2O (2). Binding of acetates and coordination of {H2L1}− provided a linear MnIIIMnIIMnIII arrangement in 1. A MnIII6 fused diadamantane-type assembly was obtained in 2 from propionate bridges, coordination of {H2L2}3–, and in situ generated {HL3}2–. The magnetic characterization of 1 and 2 revealed the properties dominated by intramolecular anti-ferromagnetic exchange interactions, and this was confirmed using density functional theory calculations. Complex 1 exhibited field-induced slow magnetic relaxation at 2 K due to the axial anisotropy of MnIII centers. Both the complexes show effective solvent-dependent catechol oxidation toward 3,5-di-tert-butylcatechol in air. The catechol oxidation abilities are comparable from two complexes of different nuclearity and structure.",
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Dangling and hydrolyzed ligand arms in [Mn3] and [Mn6] coordination assemblies : synthesis, characterization, and functional activity. / Chattopadhyay, Krishna; Craig, Gavin A.; Heras Ojea, María José; Pait, Moumita; Kundu, Animesh; Lee, Junseong; Murrie, Mark; Frontera, Antonio; Ray, Debashis.

In: Inorganic Chemistry, Vol. 56, No. 5, 06.03.2017, p. 2639-2652.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Dangling and hydrolyzed ligand arms in [Mn3] and [Mn6] coordination assemblies

T2 - Inorganic Chemistry

AU - Chattopadhyay, Krishna

AU - Craig, Gavin A.

AU - Heras Ojea, María José

AU - Pait, Moumita

AU - Kundu, Animesh

AU - Lee, Junseong

AU - Murrie, Mark

AU - Frontera, Antonio

AU - Ray, Debashis

PY - 2017/3/6

Y1 - 2017/3/6

N2 - Two flexible, branched, and sterically constrained di- and tripodal side arms around a phenol backbone were utilized in ligands H3L1 and H5L2 to isolate {Mn6} and {Mn3} coordination aggregates. 2,6-Bis{(1-hydroxy-2-methylpropan-2-ylimino)methyl}-4-methylphenol (H3L1) gave trinuclear complex [Mn3(μ-H2L1)2(μ1,3-O2CCH3)4(CH3OH)2](ClO4)2·4CH3OH (1), whereas 2,6-bis[{1-hydroxy-2-(hydroxymethyl)butan-2-ylimino}methyl]-4-methylphenol (H5L2) provided hexanuclear complex [Mn6(μ4-H2L2)2(μ-HL3)2(μ3-OH)2(μ1,3-O2CC2H5)4](ClO4)2·2H2O (2). Binding of acetates and coordination of {H2L1}− provided a linear MnIIIMnIIMnIII arrangement in 1. A MnIII6 fused diadamantane-type assembly was obtained in 2 from propionate bridges, coordination of {H2L2}3–, and in situ generated {HL3}2–. The magnetic characterization of 1 and 2 revealed the properties dominated by intramolecular anti-ferromagnetic exchange interactions, and this was confirmed using density functional theory calculations. Complex 1 exhibited field-induced slow magnetic relaxation at 2 K due to the axial anisotropy of MnIII centers. Both the complexes show effective solvent-dependent catechol oxidation toward 3,5-di-tert-butylcatechol in air. The catechol oxidation abilities are comparable from two complexes of different nuclearity and structure.

AB - Two flexible, branched, and sterically constrained di- and tripodal side arms around a phenol backbone were utilized in ligands H3L1 and H5L2 to isolate {Mn6} and {Mn3} coordination aggregates. 2,6-Bis{(1-hydroxy-2-methylpropan-2-ylimino)methyl}-4-methylphenol (H3L1) gave trinuclear complex [Mn3(μ-H2L1)2(μ1,3-O2CCH3)4(CH3OH)2](ClO4)2·4CH3OH (1), whereas 2,6-bis[{1-hydroxy-2-(hydroxymethyl)butan-2-ylimino}methyl]-4-methylphenol (H5L2) provided hexanuclear complex [Mn6(μ4-H2L2)2(μ-HL3)2(μ3-OH)2(μ1,3-O2CC2H5)4](ClO4)2·2H2O (2). Binding of acetates and coordination of {H2L1}− provided a linear MnIIIMnIIMnIII arrangement in 1. A MnIII6 fused diadamantane-type assembly was obtained in 2 from propionate bridges, coordination of {H2L2}3–, and in situ generated {HL3}2–. The magnetic characterization of 1 and 2 revealed the properties dominated by intramolecular anti-ferromagnetic exchange interactions, and this was confirmed using density functional theory calculations. Complex 1 exhibited field-induced slow magnetic relaxation at 2 K due to the axial anisotropy of MnIII centers. Both the complexes show effective solvent-dependent catechol oxidation toward 3,5-di-tert-butylcatechol in air. The catechol oxidation abilities are comparable from two complexes of different nuclearity and structure.

KW - coordination assembly

KW - 2-amino-2-ethyl-propane-1,3-diol

KW - 2-amino-2- methylpropan-1-ol

KW - imine hydrolysis

UR - http://eprints.gla.ac.uk/137697/

U2 - 10.1021/acs.inorgchem.6b02813

DO - 10.1021/acs.inorgchem.6b02813

M3 - Article

VL - 56

SP - 2639

EP - 2652

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 5

ER -