Coordination behaviour of bis-terdentate N-donor ligands: Double- and single-stranded helicates, mesocates, and cyclic oligomers

Nawal K. Al-Rasbi, Harry Adams, Lindsay P. Harding, Michael D. Ward

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

Three new ligands have been prepared in which two terdentate chelating pyrazolyl-bipyridine units are connected by a central aromatic spacer via methylene "hinges": the spacers are o-phenylene (LPh), 2,6-pyridine-diyl (LPy) and 2,3-naphthalenediyl (Lnaph). The ligands act as potentially hexadentate bridging ligands, with the central pyridyl N atom of LPy not involved in coordination. The following complexes were prepared and structurally characterised: [M2(L Ph)2][ClO4]4 (M = Ni, Cu), which are dinuclear double helicates; [Ag2-(LPh)(MeCN) 2][BF4]2, a dinuclear complex with an Ag⋯Ag bond in which the ligand adopts a helical twist around the pair of metal ions; [Ni2(LPy)2][BF4] 4, an achiral "mesocate" with a box-like structure and a face-to-face arrangement of ligands; [Ag3(Lnaph) 2](BF4)3, which contains a linear trinuclear array of AgI ions with the two ligands arranged in a shallow helical twist, each ligand spanning one terminal and the central metal ion; and [Cd 6(Lnaph)6](ClO4)12, a cyclic hexanuclear helicate with a perchlorate anion in the central cavity. Both [Cu2(LPh)2][ClO4]4 and [Cd6(Lnaph)6](ClO4)12, which have architecturally similar bridging ligands, show evidence by electrospray mass spectrometry for formation of a range of cyclic oligomers in solution up to 11-mers for the CdII/Lnaph system.

Original languageEnglish
Pages (from-to)4770-4780
Number of pages11
JournalEuropean Journal of Inorganic Chemistry
Issue number30
DOIs
Publication statusPublished - 2007

Fingerprint

Oligomers
Ligands
Metal ions
Hinges
Chelation
Anions
Mass spectrometry
perchlorate
Ions
Atoms
pyridine

Keywords

  • Chelating ligands
  • Coordination chemistry
  • Helical structures
  • Self-assembly

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Coordination behaviour of bis-terdentate N-donor ligands : Double- and single-stranded helicates, mesocates, and cyclic oligomers. / Al-Rasbi, Nawal K.; Adams, Harry; Harding, Lindsay P.; Ward, Michael D.

In: European Journal of Inorganic Chemistry, No. 30, 2007, p. 4770-4780.

Research output: Contribution to journalArticle

@article{978a6375a6504dcfa68e72cb01299a93,
title = "Coordination behaviour of bis-terdentate N-donor ligands: Double- and single-stranded helicates, mesocates, and cyclic oligomers",
abstract = "Three new ligands have been prepared in which two terdentate chelating pyrazolyl-bipyridine units are connected by a central aromatic spacer via methylene {"}hinges{"}: the spacers are o-phenylene (LPh), 2,6-pyridine-diyl (LPy) and 2,3-naphthalenediyl (Lnaph). The ligands act as potentially hexadentate bridging ligands, with the central pyridyl N atom of LPy not involved in coordination. The following complexes were prepared and structurally characterised: [M2(L Ph)2][ClO4]4 (M = Ni, Cu), which are dinuclear double helicates; [Ag2-(LPh)(MeCN) 2][BF4]2, a dinuclear complex with an Ag⋯Ag bond in which the ligand adopts a helical twist around the pair of metal ions; [Ni2(LPy)2][BF4] 4, an achiral {"}mesocate{"} with a box-like structure and a face-to-face arrangement of ligands; [Ag3(Lnaph) 2](BF4)3, which contains a linear trinuclear array of AgI ions with the two ligands arranged in a shallow helical twist, each ligand spanning one terminal and the central metal ion; and [Cd 6(Lnaph)6](ClO4)12, a cyclic hexanuclear helicate with a perchlorate anion in the central cavity. Both [Cu2(LPh)2][ClO4]4 and [Cd6(Lnaph)6](ClO4)12, which have architecturally similar bridging ligands, show evidence by electrospray mass spectrometry for formation of a range of cyclic oligomers in solution up to 11-mers for the CdII/Lnaph system.",
keywords = "Chelating ligands, Coordination chemistry, Helical structures, Self-assembly",
author = "Al-Rasbi, {Nawal K.} and Harry Adams and Harding, {Lindsay P.} and Ward, {Michael D.}",
year = "2007",
doi = "10.1002/ejic.200700715",
language = "English",
pages = "4770--4780",
journal = "Chemische Berichte",
issn = "0009-2940",
publisher = "Wiley-VCH Verlag",
number = "30",

}

TY - JOUR

T1 - Coordination behaviour of bis-terdentate N-donor ligands

T2 - Double- and single-stranded helicates, mesocates, and cyclic oligomers

AU - Al-Rasbi, Nawal K.

AU - Adams, Harry

AU - Harding, Lindsay P.

AU - Ward, Michael D.

PY - 2007

Y1 - 2007

N2 - Three new ligands have been prepared in which two terdentate chelating pyrazolyl-bipyridine units are connected by a central aromatic spacer via methylene "hinges": the spacers are o-phenylene (LPh), 2,6-pyridine-diyl (LPy) and 2,3-naphthalenediyl (Lnaph). The ligands act as potentially hexadentate bridging ligands, with the central pyridyl N atom of LPy not involved in coordination. The following complexes were prepared and structurally characterised: [M2(L Ph)2][ClO4]4 (M = Ni, Cu), which are dinuclear double helicates; [Ag2-(LPh)(MeCN) 2][BF4]2, a dinuclear complex with an Ag⋯Ag bond in which the ligand adopts a helical twist around the pair of metal ions; [Ni2(LPy)2][BF4] 4, an achiral "mesocate" with a box-like structure and a face-to-face arrangement of ligands; [Ag3(Lnaph) 2](BF4)3, which contains a linear trinuclear array of AgI ions with the two ligands arranged in a shallow helical twist, each ligand spanning one terminal and the central metal ion; and [Cd 6(Lnaph)6](ClO4)12, a cyclic hexanuclear helicate with a perchlorate anion in the central cavity. Both [Cu2(LPh)2][ClO4]4 and [Cd6(Lnaph)6](ClO4)12, which have architecturally similar bridging ligands, show evidence by electrospray mass spectrometry for formation of a range of cyclic oligomers in solution up to 11-mers for the CdII/Lnaph system.

AB - Three new ligands have been prepared in which two terdentate chelating pyrazolyl-bipyridine units are connected by a central aromatic spacer via methylene "hinges": the spacers are o-phenylene (LPh), 2,6-pyridine-diyl (LPy) and 2,3-naphthalenediyl (Lnaph). The ligands act as potentially hexadentate bridging ligands, with the central pyridyl N atom of LPy not involved in coordination. The following complexes were prepared and structurally characterised: [M2(L Ph)2][ClO4]4 (M = Ni, Cu), which are dinuclear double helicates; [Ag2-(LPh)(MeCN) 2][BF4]2, a dinuclear complex with an Ag⋯Ag bond in which the ligand adopts a helical twist around the pair of metal ions; [Ni2(LPy)2][BF4] 4, an achiral "mesocate" with a box-like structure and a face-to-face arrangement of ligands; [Ag3(Lnaph) 2](BF4)3, which contains a linear trinuclear array of AgI ions with the two ligands arranged in a shallow helical twist, each ligand spanning one terminal and the central metal ion; and [Cd 6(Lnaph)6](ClO4)12, a cyclic hexanuclear helicate with a perchlorate anion in the central cavity. Both [Cu2(LPh)2][ClO4]4 and [Cd6(Lnaph)6](ClO4)12, which have architecturally similar bridging ligands, show evidence by electrospray mass spectrometry for formation of a range of cyclic oligomers in solution up to 11-mers for the CdII/Lnaph system.

KW - Chelating ligands

KW - Coordination chemistry

KW - Helical structures

KW - Self-assembly

UR - http://www.scopus.com/inward/record.url?scp=35848942121&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=35848942121&partnerID=8YFLogxK

U2 - 10.1002/ejic.200700715

DO - 10.1002/ejic.200700715

M3 - Article

AN - SCOPUS:35848942121

SP - 4770

EP - 4780

JO - Chemische Berichte

JF - Chemische Berichte

SN - 0009-2940

IS - 30

ER -