Three Manganese Complexes of Anionic N4-Donor Schiff-Base Macrocycles: Monomeric MnII and MnIII, and dimeric MnIV

Rajni K. Wilson; Sébastien Dhers; Stephen Sproules; Eric J.L. McInnes; Sally Brooker

doi:10.1071/CH19209

Three Manganese Complexes of Anionic N₄-Donor Schiff-Base Macrocycles: Monomeric Mn^II and Mn^III, and dimeric Mn^IV

Rajni K. Wilson, Sébastien Dhers, Stephen Sproules, Eric J.L. McInnes, Sally Brooker^*

^*Corresponding author for this work

University of Otago

Research output: Contribution to journal › Article › peer-review

Abstract

Three manganese macrocyclic complexes of two anionic N₄-donor [1 + 1] Schiff-base macrocycles that differ in ring size (14 versus 16 membered), HL^Et and HL^Pr (obtained from condensation of diphenylamine-2,2′-dicarboxaldehyde and either diethylenetriamine or dipropylenetriamine), are reported. Specifically, a pair of monomeric complexes Mn^IIL^Et(NCS)(H₂O) and [Mn^IIIL^Pr(NCS)₂]·0.5H₂O, plus a dimeric complex [Mn^IV₂L^Et₂(O)₂](ClO₄)₂·3DMF have been synthesised and characterised. Single crystal structure determinations on [Mn^IIIL^Pr(NCS)₂]·0.5H₂O and [Mn^IV₂L^Et₂(O)₂](ClO₄)₂·3DMF revealed octahedral manganese centres in both cases: N₆-coordinated Jahn-Teller distorted Mn^III in the former and a pair of N₄O₂-coordinated Mn^IV in the latter. UV-Vis, IR, and electron paramagnetic resonance spectroscopy as well as magnetic measurements are reported. These macrocyclic complexes feature a simple and original design, and could find future uses as models for manganese catalase or as building blocks for the assembly of larger supramolecular architectures.

Original language	English
Journal	Australian Journal of Chemistry
Early online date	26 Jul 2019
DOIs	https://doi.org/10.1071/CH19209
Publication status	Published - 2019

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@article{1f1a7bc691ad452aa24ad9572436f8d3,

title = "Three Manganese Complexes of Anionic N4-Donor Schiff-Base Macrocycles: Monomeric MnII and MnIII, and dimeric MnIV",

abstract = "Three manganese macrocyclic complexes of two anionic N4-donor [1 + 1] Schiff-base macrocycles that differ in ring size (14 versus 16 membered), HLEt and HLPr (obtained from condensation of diphenylamine-2,2′-dicarboxaldehyde and either diethylenetriamine or dipropylenetriamine), are reported. Specifically, a pair of monomeric complexes MnIILEt(NCS)(H2O) and [MnIIILPr(NCS)2]·0.5H2O, plus a dimeric complex [MnIV2LEt2(O)2](ClO4)2·3DMF have been synthesised and characterised. Single crystal structure determinations on [MnIIILPr(NCS)2]·0.5H2O and [MnIV2LEt2(O)2](ClO4)2·3DMF revealed octahedral manganese centres in both cases: N6-coordinated Jahn-Teller distorted MnIII in the former and a pair of N4O2-coordinated MnIV in the latter. UV-Vis, IR, and electron paramagnetic resonance spectroscopy as well as magnetic measurements are reported. These macrocyclic complexes feature a simple and original design, and could find future uses as models for manganese catalase or as building blocks for the assembly of larger supramolecular architectures.",

author = "Wilson, \{Rajni K.\} and S{\'e}bastien Dhers and Stephen Sproules and McInnes, \{Eric J.L.\} and Sally Brooker",

year = "2019",

doi = "10.1071/CH19209",

language = "English",

journal = "Australian Journal of Chemistry",

issn = "0004-9425",

publisher = "CSIRO Publishing ",

}

TY - JOUR

T1 - Three Manganese Complexes of Anionic N4-Donor Schiff-Base Macrocycles

T2 - Monomeric MnII and MnIII, and dimeric MnIV

AU - Wilson, Rajni K.

AU - Dhers, Sébastien

AU - Sproules, Stephen

AU - McInnes, Eric J.L.

AU - Brooker, Sally

PY - 2019

Y1 - 2019

N2 - Three manganese macrocyclic complexes of two anionic N4-donor [1 + 1] Schiff-base macrocycles that differ in ring size (14 versus 16 membered), HLEt and HLPr (obtained from condensation of diphenylamine-2,2′-dicarboxaldehyde and either diethylenetriamine or dipropylenetriamine), are reported. Specifically, a pair of monomeric complexes MnIILEt(NCS)(H2O) and [MnIIILPr(NCS)2]·0.5H2O, plus a dimeric complex [MnIV2LEt2(O)2](ClO4)2·3DMF have been synthesised and characterised. Single crystal structure determinations on [MnIIILPr(NCS)2]·0.5H2O and [MnIV2LEt2(O)2](ClO4)2·3DMF revealed octahedral manganese centres in both cases: N6-coordinated Jahn-Teller distorted MnIII in the former and a pair of N4O2-coordinated MnIV in the latter. UV-Vis, IR, and electron paramagnetic resonance spectroscopy as well as magnetic measurements are reported. These macrocyclic complexes feature a simple and original design, and could find future uses as models for manganese catalase or as building blocks for the assembly of larger supramolecular architectures.

AB - Three manganese macrocyclic complexes of two anionic N4-donor [1 + 1] Schiff-base macrocycles that differ in ring size (14 versus 16 membered), HLEt and HLPr (obtained from condensation of diphenylamine-2,2′-dicarboxaldehyde and either diethylenetriamine or dipropylenetriamine), are reported. Specifically, a pair of monomeric complexes MnIILEt(NCS)(H2O) and [MnIIILPr(NCS)2]·0.5H2O, plus a dimeric complex [MnIV2LEt2(O)2](ClO4)2·3DMF have been synthesised and characterised. Single crystal structure determinations on [MnIIILPr(NCS)2]·0.5H2O and [MnIV2LEt2(O)2](ClO4)2·3DMF revealed octahedral manganese centres in both cases: N6-coordinated Jahn-Teller distorted MnIII in the former and a pair of N4O2-coordinated MnIV in the latter. UV-Vis, IR, and electron paramagnetic resonance spectroscopy as well as magnetic measurements are reported. These macrocyclic complexes feature a simple and original design, and could find future uses as models for manganese catalase or as building blocks for the assembly of larger supramolecular architectures.

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U2 - 10.1071/CH19209

DO - 10.1071/CH19209

M3 - Article

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SN - 0004-9425

JO - Australian Journal of Chemistry

JF - Australian Journal of Chemistry

ER -

Three Manganese Complexes of Anionic N₄-Donor Schiff-Base Macrocycles: Monomeric Mn^II and Mn^III, and dimeric Mn^IV

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Three Manganese Complexes of Anionic N4-Donor Schiff-Base Macrocycles: Monomeric MnII and MnIII, and dimeric MnIV

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Three Manganese Complexes of Anionic N₄-Donor Schiff-Base Macrocycles: Monomeric Mn^II and Mn^III, and dimeric Mn^IV