Publication detail

Solvent-induced structural transformation from heptanuclear to decanuclear [Co-Ln] coordination clusters: trapping of unique counteranion and understanding of aggregation pathways

BASAK, D. MARTI, E.R. MURRIE, M. NEMEC, I. RAY, D.

Original Title

Solvent-induced structural transformation from heptanuclear to decanuclear [Co-Ln] coordination clusters: trapping of unique counteranion and understanding of aggregation pathways

Type

journal article in Web of Science

Language

English

Original Abstract

Five new cobalt(ii/ili)-lanthanide(m)-based coordination aggregates, [Ln(3)(III)Co(2)(II)Co(2)(III)(L1)(2)(O2CCMe3)(8)(OH)(4) (OMe)(2)(H2O)(4)]center dot Ln(eta(1)-O2CCMe3)(2)(eta(2)-O2CCMe3)(2)(MeOH)(2)center dot 2MeOH center dot 2H(2)O (where Ln = Tb (1), Ho (3), and H(2)L1 = N-(2-hydroxyethyl)-salicylaldimine), (Tb3Co3Co4III)-Co-III-Co-II(L1)(4)(O2CCMe3)(9)(OH)(10)(H2O) (4) and Ln(3)(III)Co(2)(II)CoT (L1)(4)(O2CCMe3)(10)(OH)(10) (Ln = Dy (5), Ho (6)) have been synthesized and characterized, including structural analysis via single-crystal X-ray diffraction. The dysprosium analogue (2) of 1 and 3 was previously reported by us. The heptanuclear monocationic clusters in 1 and 3 were formed by placement of seven metal ions (4 Co and 3 Ln) in a vertex shared dicubane structure from the control of two Schiff base anions and crystallized in the presence of in situ generated and literature unknown counter anions Tb(eta(1)-O2CCMe3)(2)(eta(2)-O2CCMe3)(2)(MeOH)(2)(-) and Ho(eta(1)-O2CCMe3)(2)(eta(2)-O2CCMe3)(2)(MeOH)(2)(-). Interesting solvent-induced cluster structure transformation was observed on dissolving the heptanuclear aggregates in MeCN for the formation of decanuclear clusters 4-6. These high nuclearity clusters consist of a vertex shared heptanuclear dicubane part and a curved trinuclear chain linking the two cubic halves. The dicubane unit differs from that of the heptanuclear precursors in the presence of Co-II/III at the shared vertex as opposed to Ln(III) and the absence of OMe- bridges. HRMS (+ve) analysis shed light on the pathway of formation of these heptanuclear molecules, while at the same time revealing a different aggregation process for the decanuclear clusters.

Keywords

SCHIFF-BASE LIGANDS; X-RAY-STRUCTURE; ASSEMBLIES SYNTHESIS; COMPLEXES SYNTHESIS; CRYSTAL-STRUCTURES; 3D-4F COMPLEXES; NUCLEARITY; ANION; FAMILY; UNITS

Authors

BASAK, D.; MARTI, E.R.; MURRIE, M.; NEMEC, I.; RAY, D.

Released

21. 7. 2021

Publisher

ROYAL SOC CHEMISTRY

Location

CAMBRIDGE

ISBN

1477-9234

Periodical

Dalton Transactions

Year of study

50

Number

27

State

United Kingdom of Great Britain and Northern Ireland

Pages from

9574

Pages to

9588

Pages count

15

URL

https://pubs.rsc.org/en/content/articlelanding/2021/DT/D1DT01278A

BibTex

@article{BUT173165,
  author="BASAK, D. and MARTI, E.R. and MURRIE, M. and NEMEC, I. and RAY, D.",
  title="Solvent-induced structural transformation from heptanuclear to decanuclear [Co-Ln] coordination clusters: trapping of unique counteranion and understanding of aggregation pathways",
  journal="Dalton Transactions",
  year="2021",
  volume="50",
  number="27",
  pages="9574--9588",
  doi="10.1039/d1dt01278a",
  issn="1477-9234",
  url="https://pubs.rsc.org/en/content/articlelanding/2021/DT/D1DT01278A"
}