A family of [Cu2], [Cu4] and [Cu5] aggregates: alteration of reaction conditions, ancillary bridges and capping anions

Manisha Das, Gavin A. Craig, Daniel Escudero, Mark Murrie, Antonio Frontera, Debashis Ray

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

The phenoxido-bridged [Cu2] complex [Cu2(μ-H4L1)(μ-OH)(μ1,3-NO3)(NO3)(OH2)]·H2O (1) and its hierarchical [Cu4] and [Cu5] assemblies [Cu4(μ-H4L1)2(μ-OH)2(μ1,3-ClO4)(OH2)2](ClO4)3·2H2O (2) and [Cu5(μ-H4L1)2(μ3-OH)2(μ1,3-O2CCF3)2(O2CCF3)2](CF3COO)2 (3) were obtained from the reactions of H5L1 (2,6-bis-{(1,3-dihydroxy-2-methylpropan-2-ylimino)methyl}-4-methylphenol) with three copper(ii) salts. The available NO3−, ClO4− and CF3COO− ions have been trapped for ‘spontaneous’ anion-directed ‘self-assembly’ reactions. All the synthesized complexes contain the [Cu2(μ-H4L1)(μ-OH)]2+ fragment, prone to assemble and crystallize [Cu4] and [Cu5] complexes under varying reaction conditions. They were characterized by UV-vis and IR spectroscopy, X-ray diffraction analysis and magnetic studies. A change from NO3− to ClO4− and CF3COO− results in different courses of reactions based on Cu2(μ-H4L1) fragments. Binding of NO3− provided 1 as an isolated [Cu2] complex by trapping the reactive fragment. In 2 a perchlorate ligand, in the μ1,3-binding mode, has been realized as a solitary support for the condensation of two Cu2(μ-H4L1) fragments. The {Cu5(μ3-OH)2(μ1,3-O2CCF3)2}6+ constellation in 3 contains five CuII centers with a unique Z-in distorted octahedral one at the central position. Binding of different anions to the copper(ii) centers controls the nuclearity of the reaction products and tuning of the self-aggregation process within the same ligand environment (μ-H4L1−). The magnetic properties of the compounds have been studied both experimentally and using DFT calculations, revealing moderate to strong antiferromagnetic coupling in all aggregates.
LanguageEnglish
Pages14349-14364
Number of pages16
JournalNew Journal of Chemistry
Volume42
Issue number17
Early online date17 Jul 2018
DOIs
Publication statusPublished - 7 Sep 2018

Fingerprint

Anions
Negative ions
Ligands
Copper
Ultraviolet spectroscopy
Reaction products
Discrete Fourier transforms
Self assembly
X ray diffraction analysis
Condensation
Infrared spectroscopy
Magnetic properties
Agglomeration
Tuning
Salts
Ions
perchlorate

Keywords

  • copper complex
  • copper ion
  • ligand
  • nitrate
  • phenol derivative

Cite this

Das, Manisha ; Craig, Gavin A. ; Escudero, Daniel ; Murrie, Mark ; Frontera, Antonio ; Ray, Debashis. / A family of [Cu2], [Cu4] and [Cu5] aggregates : alteration of reaction conditions, ancillary bridges and capping anions. In: New Journal of Chemistry. 2018 ; Vol. 42, No. 17. pp. 14349-14364.
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abstract = "The phenoxido-bridged [Cu2] complex [Cu2(μ-H4L1)(μ-OH)(μ1,3-NO3)(NO3)(OH2)]·H2O (1) and its hierarchical [Cu4] and [Cu5] assemblies [Cu4(μ-H4L1)2(μ-OH)2(μ1,3-ClO4)(OH2)2](ClO4)3·2H2O (2) and [Cu5(μ-H4L1)2(μ3-OH)2(μ1,3-O2CCF3)2(O2CCF3)2](CF3COO)2 (3) were obtained from the reactions of H5L1 (2,6-bis-{(1,3-dihydroxy-2-methylpropan-2-ylimino)methyl}-4-methylphenol) with three copper(ii) salts. The available NO3−, ClO4− and CF3COO− ions have been trapped for ‘spontaneous’ anion-directed ‘self-assembly’ reactions. All the synthesized complexes contain the [Cu2(μ-H4L1)(μ-OH)]2+ fragment, prone to assemble and crystallize [Cu4] and [Cu5] complexes under varying reaction conditions. They were characterized by UV-vis and IR spectroscopy, X-ray diffraction analysis and magnetic studies. A change from NO3− to ClO4− and CF3COO− results in different courses of reactions based on Cu2(μ-H4L1) fragments. Binding of NO3− provided 1 as an isolated [Cu2] complex by trapping the reactive fragment. In 2 a perchlorate ligand, in the μ1,3-binding mode, has been realized as a solitary support for the condensation of two Cu2(μ-H4L1) fragments. The {Cu5(μ3-OH)2(μ1,3-O2CCF3)2}6+ constellation in 3 contains five CuII centers with a unique Z-in distorted octahedral one at the central position. Binding of different anions to the copper(ii) centers controls the nuclearity of the reaction products and tuning of the self-aggregation process within the same ligand environment (μ-H4L1−). The magnetic properties of the compounds have been studied both experimentally and using DFT calculations, revealing moderate to strong antiferromagnetic coupling in all aggregates.",
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A family of [Cu2], [Cu4] and [Cu5] aggregates : alteration of reaction conditions, ancillary bridges and capping anions. / Das, Manisha; Craig, Gavin A.; Escudero, Daniel; Murrie, Mark; Frontera, Antonio; Ray, Debashis.

In: New Journal of Chemistry, Vol. 42, No. 17, 07.09.2018, p. 14349-14364.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A family of [Cu2], [Cu4] and [Cu5] aggregates

T2 - New Journal of Chemistry

AU - Das, Manisha

AU - Craig, Gavin A.

AU - Escudero, Daniel

AU - Murrie, Mark

AU - Frontera, Antonio

AU - Ray, Debashis

PY - 2018/9/7

Y1 - 2018/9/7

N2 - The phenoxido-bridged [Cu2] complex [Cu2(μ-H4L1)(μ-OH)(μ1,3-NO3)(NO3)(OH2)]·H2O (1) and its hierarchical [Cu4] and [Cu5] assemblies [Cu4(μ-H4L1)2(μ-OH)2(μ1,3-ClO4)(OH2)2](ClO4)3·2H2O (2) and [Cu5(μ-H4L1)2(μ3-OH)2(μ1,3-O2CCF3)2(O2CCF3)2](CF3COO)2 (3) were obtained from the reactions of H5L1 (2,6-bis-{(1,3-dihydroxy-2-methylpropan-2-ylimino)methyl}-4-methylphenol) with three copper(ii) salts. The available NO3−, ClO4− and CF3COO− ions have been trapped for ‘spontaneous’ anion-directed ‘self-assembly’ reactions. All the synthesized complexes contain the [Cu2(μ-H4L1)(μ-OH)]2+ fragment, prone to assemble and crystallize [Cu4] and [Cu5] complexes under varying reaction conditions. They were characterized by UV-vis and IR spectroscopy, X-ray diffraction analysis and magnetic studies. A change from NO3− to ClO4− and CF3COO− results in different courses of reactions based on Cu2(μ-H4L1) fragments. Binding of NO3− provided 1 as an isolated [Cu2] complex by trapping the reactive fragment. In 2 a perchlorate ligand, in the μ1,3-binding mode, has been realized as a solitary support for the condensation of two Cu2(μ-H4L1) fragments. The {Cu5(μ3-OH)2(μ1,3-O2CCF3)2}6+ constellation in 3 contains five CuII centers with a unique Z-in distorted octahedral one at the central position. Binding of different anions to the copper(ii) centers controls the nuclearity of the reaction products and tuning of the self-aggregation process within the same ligand environment (μ-H4L1−). The magnetic properties of the compounds have been studied both experimentally and using DFT calculations, revealing moderate to strong antiferromagnetic coupling in all aggregates.

AB - The phenoxido-bridged [Cu2] complex [Cu2(μ-H4L1)(μ-OH)(μ1,3-NO3)(NO3)(OH2)]·H2O (1) and its hierarchical [Cu4] and [Cu5] assemblies [Cu4(μ-H4L1)2(μ-OH)2(μ1,3-ClO4)(OH2)2](ClO4)3·2H2O (2) and [Cu5(μ-H4L1)2(μ3-OH)2(μ1,3-O2CCF3)2(O2CCF3)2](CF3COO)2 (3) were obtained from the reactions of H5L1 (2,6-bis-{(1,3-dihydroxy-2-methylpropan-2-ylimino)methyl}-4-methylphenol) with three copper(ii) salts. The available NO3−, ClO4− and CF3COO− ions have been trapped for ‘spontaneous’ anion-directed ‘self-assembly’ reactions. All the synthesized complexes contain the [Cu2(μ-H4L1)(μ-OH)]2+ fragment, prone to assemble and crystallize [Cu4] and [Cu5] complexes under varying reaction conditions. They were characterized by UV-vis and IR spectroscopy, X-ray diffraction analysis and magnetic studies. A change from NO3− to ClO4− and CF3COO− results in different courses of reactions based on Cu2(μ-H4L1) fragments. Binding of NO3− provided 1 as an isolated [Cu2] complex by trapping the reactive fragment. In 2 a perchlorate ligand, in the μ1,3-binding mode, has been realized as a solitary support for the condensation of two Cu2(μ-H4L1) fragments. The {Cu5(μ3-OH)2(μ1,3-O2CCF3)2}6+ constellation in 3 contains five CuII centers with a unique Z-in distorted octahedral one at the central position. Binding of different anions to the copper(ii) centers controls the nuclearity of the reaction products and tuning of the self-aggregation process within the same ligand environment (μ-H4L1−). The magnetic properties of the compounds have been studied both experimentally and using DFT calculations, revealing moderate to strong antiferromagnetic coupling in all aggregates.

KW - copper complex

KW - copper ion

KW - ligand

KW - nitrate

KW - phenol derivative

UR - http://eprints.gla.ac.uk/165513/

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M3 - Article

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SP - 14349

EP - 14364

JO - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

IS - 17

ER -