Publication detail

From tetranuclear to pentanuclear [Co-Ln] (Ln = Gd, Tb, Dy, Ho) complexes across the lanthanide series: effect of varying sequence of ligand addition

BASAK, D. SMYTHE, L. HERCHEL, R. MURRIE, M. NEMEC, I. RAY, D.

Original Title

From tetranuclear to pentanuclear [Co-Ln] (Ln = Gd, Tb, Dy, Ho) complexes across the lanthanide series: effect of varying sequence of ligand addition

Type

journal article in Web of Science

Language

English

Original Abstract

Two new families of cobalt(II/III)-lanthanide(III) coordination aggregates have been reported: tetranuclear [Ln(2)(III)Co(2)(III)L(2)(N-BuDEA)(2)(O2CCMe3)(4)(H2O)(2)]center dot(MeOH)(n)center dot(H2O)(m) (Ln = Gd, 1; Tb, 2; Dy, 3; n=2, m=10 for 1 and 2; n=6, m=2 for 3) and pentanuclear Ln(2)(III)Co(II)Co(2)(III)L(2)(N-BuDEA)(2)(O2CCMe3)(6)(MeOH)(2) (Ln = Dy, 4; Ho, 5) formed from the reaction of two aggregation assisting ligands H2L (o-vanillin oxime) and N-BuDEAH(2) (N-butyldiethanolamine). A change in preference from a lower to higher nuclearity structure was observed on going across the lanthanide series brought about by the variation in the size of the Ln(III) ions. An interesting observation was made for the varying sequence of addition of the ligands into the reaction medium paving the way to access both structural types for Ln = Dy. HRMS (+ve) of solutions gave further insight into the formation of the aggregates via different pathways. The tetranuclear complexes adopt a modified butterfly structure with a more complex bridging network while trapping of an extra Co-II ion in the pentanuclear complexes destroys this arrangement putting the Co-Co-Co axis above the Ln-Ln axis. Direct current (dc) magnetic susceptibility measurements reveal weak antiferromagnetic coupling in 1. Complexes 2 and 5 display no slow magnetic relaxation, whereas complexes 3 and 4 display out-of-phase signals at low temperature in ac susceptibility measurements. All compounds were analyzed with DFT and CASSCF calculations and informations about the single-ion anisotropies and mutual 4f-4f/4f-3d magnetic interactions were derived.

Keywords

SINGLE-MOLECULE MAGNET; COORDINATION CLUSTERS; BASIS-SETS; MAGNETIZATION RELAXATION; FAMILY; REPLACEMENT; NUCLEARITY; PARAMETERS ;DYNAMICS; CRYSTAL

Authors

BASAK, D.; SMYTHE, L.; HERCHEL, R.; MURRIE, M.; NEMEC, I.; RAY, D.

Released

14. 9. 2021

Publisher

ROYAL SOC CHEMISTRY

Location

CAMBRIDGE

ISBN

1477-9234

Periodical

Dalton Transactions

Year of study

50

Number

34

State

United Kingdom of Great Britain and Northern Ireland

Pages from

11861

Pages to

11877

Pages count

17

URL

https://pubs.rsc.org/en/content/articlelanding/2021/DT/D1DT02038B

BibTex

@article{BUT173070,
  author="Dipmalya {Basak} and Lucy {Smythe} and Radovan {Herchel} and Mark {Murrie} and Ivan {Nemec} and Debashis {Ray}",
  title="From tetranuclear to pentanuclear [Co-Ln] (Ln = Gd, Tb, Dy, Ho) complexes across the lanthanide series: effect of varying sequence of ligand addition",
  journal="Dalton Transactions",
  year="2021",
  volume="50",
  number="34",
  pages="11861--11877",
  doi="10.1039/d1dt02038b",
  issn="1477-9234",
  url="https://pubs.rsc.org/en/content/articlelanding/2021/DT/D1DT02038B"
}