Supramolecular Dimeric MnIII Complexes: Synthesis, Structure, Magnetic Properties, and Catalytic Oxidation Studies

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abstract

In this study, a tetradentate Schiff-base ligand (H2L), synthesized by the condensation of ethylenediamine with 2-hydroxy-3-methoxy-5-methylbenzaldehyde, was reacted with either manganese salts or manganese salts in the presence of various pseudohalides in methanol. This reaction resulted in the formation of five mononuclear MnIII complexes: [Mn(L)(H2O)2](NO3)1/2H2O1/2CH3OH (1), [Mn(L)(H2O)2](ClO4)H2O (2), [Mn(L)(N3)(H2O)]1/3H2O (3), [Mn(L)(NCS)(H2O)] (4), and [Mn(L)(H2O)2](dca) (5) (where dca is dicyanamide ion). X-ray crystallography revealed that the MnIII centers adopt a hexa-coordinate pseudo-octahedral geometry, where the equatorial plane is constructed with phenoxo oxygen and imine nitrogen atoms from the Schiff base ligand, while the axial positions are occupied by water molecules or a combination of water and pseudohalides. Supramolecular interactions, primarily pi-pi stacking and hydrogen bonding, contribute to the formation of pseudodimeric structures in the solid state. Magnetic susceptibility measurements indicated antiferromagnetic coupling within quasi-dimers, primarily through hydrogen bonds. Catalytic studies showed that the complexes effectively catalyze the aerobic oxidation of substrates such as 2-aminophenol and 3,5-di-tert-butylcatechol to yield 2-aminophenoxazin-3-one and 3,5-di-tert-butylquinone, respectively. They also catalyze the oxidation of styrene to its corresponding oxirane, demonstrating their versatile catalytic proficiency. Mechanistic insights, supported by ESI mass spectrometry and EPR studies, suggest that catalysis involves the formation of a complex-substrate aggregate, followed by an intramolecular electron transfer.

keywords

SINGLE-MOLECULE MAGNETS; PHENOXAZINONE SYNTHASE; COORDINATION CHEMISTRY; NANOSIZED CLUSTER; CATECHOL OXIDASE; SALEN COMPLEXES; MANGANESE(III); LIGAND; SUBSTITUTION; EPOXIDATION

subject category

Chemistry

authors

Jana, NC; Jaglicic, Z; Brandao, P; Panja, A

our authors

foto Paula Cristina Ferreira da Silva Brandão

Paula Cristina Ferreira da Silva Brandão

Assistant Researcher

Groups

G1 - Porous Materials and Nanosystems

Projects

CICECO - Aveiro Institute of Materials (UIDB/50011/2020)

CICECO - Aveiro Institute of Materials (UIDP/50011/2020)

Associated Laboratory CICECO-Aveiro Institute of Materials (LA/P/0006/2020)

acknowledgements

A.P. gratefully acknowledges the financial support for this work from the Council of Scientific and Industrial Research (CSIR), New Delhi, India (Sanction no. 01/3118/23/EMR-II dated 08.07.23). Z.J. acknowledges the financial support from the Slovenian Research Agency (Grant No. P2-0348). P.B. is grateful for the financial support from the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020, UIDP/50011/2020, and LA/P/0006/2020, financed by National Funds through Fundacao para a Ciencia e a Tecnologia (FCT), MCTES (PIDDAC).

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Publication Details

type
Journal Article
year
2024
journal
ACS OMEGA
volume
9
publisher
AMER CHEMICAL SOC
issn
2470-1343
issue
50
digital object identifier
10.1021/acsomega.4c09254
web of science article identifier
WOS:001370936000001

Journal Metrics (JCR 2019)

Journal Impact Factor
2.87
Journal Impact Factor (5 yrs)
2.905
category normalized journal percentile
54.52

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