title: Dangling and Hydrolyzed Ligand Arms in [Mn3] and [Mn6] Coordination Assemblies: Synthesis, Characterization, and Functional Activity.
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 MnIIIMnIIMnIIIarrangement in 1. A MnIII6fused 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 MnIIIcenters. 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.
authors.affiliation: Department of Chemistry, Indian Institute of Technology (IIT) , Kharagpur, INDIA.
authors.forename: Krishna
authors.initials: K
authors.lastname: Chattopadhyay
authors.affiliation: School of Chemistry, University of Glasgow , Glasgow G12 8QQ, U.K.
authors.forename: Gavin A
authors.initials: GA
authors.lastname: Craig
authors.affiliation: School of Chemistry, University of Glasgow , Glasgow G12 8QQ, U.K.
authors.forename: María José
authors.initials: MJ
authors.lastname: Heras Ojea
authors.affiliation: Department of Chemistry, Indian Institute of Technology (IIT) , Kharagpur, INDIA.|Chonnam National University , Gwangju 61186, South Korea.
authors.forename: Moumita
authors.initials: M
authors.lastname: Pait
authors.affiliation: Department of Chemistry, Indian Institute of Technology (IIT) , Kharagpur, INDIA.
authors.forename: Animesh
authors.initials: A
authors.lastname: Kundu
authors.affiliation: Chonnam National University , Gwangju 61186, South Korea.
authors.forename: Junseong
authors.identifier: http://orcid.org/0000-0002-5004-7865
authors.initials: J
authors.lastname: Lee
authors.affiliation: School of Chemistry, University of Glasgow , Glasgow G12 8QQ, U.K.
authors.forename: Mark
authors.initials: M
authors.lastname: Murrie
authors.affiliation: Departament de Química, Universitat de les Illes Balears , Crta de Valldemossa km 7.5, 07122 Palma de Mallorca (Baleares), SPAIN.
authors.forename: Antonio
authors.initials: A
authors.lastname: Frontera
authors.affiliation: Department of Chemistry, Indian Institute of Technology (IIT) , Kharagpur, INDIA.
authors.forename: Debashis
authors.identifier: http://orcid.org/0000-0002-4174-6445
authors.initials: D
authors.lastname: Ray