Electrostatic control of the formation of heteroleptic transition metal helicates

C.J. Baylies, L.P. Harding, J.C. Jeffery, R. Moon, C.R. Rice, T. Riis-Johannessen

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

The synthesis of the potentially hexadentate ditopic ligand L1, which contains both N-donor and crown ether binding units, is described. Reaction of L1 with Zn(II) results in the formation of a dinuclear double helicate ([Zn2(L1)2](ClO4)4), which has been structurally characterized. In the solid state, each ligand splits into two tridentate binding domains with two Zn(II) ions coordinated by two bridging ligands in a double helicate arrangement. This complex can further react with s-block metal ions via the crown ether unit resulting in the structurally characterized zinc-containing helicate [Zn2(L1)2Ba2](ClO4)8. Ligand recognition studies of this helicate with a ligand that does not contain the crown ether unit but does contain the same N-donor array (L2) demonstrates, via both 1H NMR and ESI-MS studies, that a ligand recognition process does occur and the major species observed are the homoleptic species ([Zn2(L1)2](ClO4)4 and [Zn2(L2)2](ClO4)4). Addition of barium ions to the mixture increases the amount of the heteroleptic species ([Zn2(L1)(L2)](ClO4)4) present, resulting in an equal amount of homoleptic and heteroleptic species. This change in ligand recognition properties is attributed to electrostatic effects.
LanguageEnglish
Pages1525-1529
Number of pages5
JournalNew Journal of Chemistry
Volume31
Issue number8
DOIs
Publication statusPublished - May 2007

Fingerprint

Transition metals
Electrostatics
Ligands
Crown Ethers
Crown ethers
Ions
Barium
Metal ions
Zinc
Nuclear magnetic resonance
perchlorate

Cite this

Baylies, C.J. ; Harding, L.P. ; Jeffery, J.C. ; Moon, R. ; Rice, C.R. ; Riis-Johannessen, T. / Electrostatic control of the formation of heteroleptic transition metal helicates. In: New Journal of Chemistry. 2007 ; Vol. 31, No. 8. pp. 1525-1529.
@article{ff0f56637593407cbe3e7dd46025331e,
title = "Electrostatic control of the formation of heteroleptic transition metal helicates",
abstract = "The synthesis of the potentially hexadentate ditopic ligand L1, which contains both N-donor and crown ether binding units, is described. Reaction of L1 with Zn(II) results in the formation of a dinuclear double helicate ([Zn2(L1)2](ClO4)4), which has been structurally characterized. In the solid state, each ligand splits into two tridentate binding domains with two Zn(II) ions coordinated by two bridging ligands in a double helicate arrangement. This complex can further react with s-block metal ions via the crown ether unit resulting in the structurally characterized zinc-containing helicate [Zn2(L1)2Ba2](ClO4)8. Ligand recognition studies of this helicate with a ligand that does not contain the crown ether unit but does contain the same N-donor array (L2) demonstrates, via both 1H NMR and ESI-MS studies, that a ligand recognition process does occur and the major species observed are the homoleptic species ([Zn2(L1)2](ClO4)4 and [Zn2(L2)2](ClO4)4). Addition of barium ions to the mixture increases the amount of the heteroleptic species ([Zn2(L1)(L2)](ClO4)4) present, resulting in an equal amount of homoleptic and heteroleptic species. This change in ligand recognition properties is attributed to electrostatic effects.",
author = "C.J. Baylies and L.P. Harding and J.C. Jeffery and R. Moon and C.R. Rice and T. Riis-Johannessen",
note = "cited By 3",
year = "2007",
month = "5",
doi = "10.1039/b702608k",
language = "English",
volume = "31",
pages = "1525--1529",
journal = "New Journal of Chemistry",
issn = "1144-0546",
publisher = "Royal Society of Chemistry",
number = "8",

}

Electrostatic control of the formation of heteroleptic transition metal helicates. / Baylies, C.J.; Harding, L.P.; Jeffery, J.C.; Moon, R.; Rice, C.R.; Riis-Johannessen, T.

In: New Journal of Chemistry, Vol. 31, No. 8, 05.2007, p. 1525-1529.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Electrostatic control of the formation of heteroleptic transition metal helicates

AU - Baylies, C.J.

AU - Harding, L.P.

AU - Jeffery, J.C.

AU - Moon, R.

AU - Rice, C.R.

AU - Riis-Johannessen, T.

N1 - cited By 3

PY - 2007/5

Y1 - 2007/5

N2 - The synthesis of the potentially hexadentate ditopic ligand L1, which contains both N-donor and crown ether binding units, is described. Reaction of L1 with Zn(II) results in the formation of a dinuclear double helicate ([Zn2(L1)2](ClO4)4), which has been structurally characterized. In the solid state, each ligand splits into two tridentate binding domains with two Zn(II) ions coordinated by two bridging ligands in a double helicate arrangement. This complex can further react with s-block metal ions via the crown ether unit resulting in the structurally characterized zinc-containing helicate [Zn2(L1)2Ba2](ClO4)8. Ligand recognition studies of this helicate with a ligand that does not contain the crown ether unit but does contain the same N-donor array (L2) demonstrates, via both 1H NMR and ESI-MS studies, that a ligand recognition process does occur and the major species observed are the homoleptic species ([Zn2(L1)2](ClO4)4 and [Zn2(L2)2](ClO4)4). Addition of barium ions to the mixture increases the amount of the heteroleptic species ([Zn2(L1)(L2)](ClO4)4) present, resulting in an equal amount of homoleptic and heteroleptic species. This change in ligand recognition properties is attributed to electrostatic effects.

AB - The synthesis of the potentially hexadentate ditopic ligand L1, which contains both N-donor and crown ether binding units, is described. Reaction of L1 with Zn(II) results in the formation of a dinuclear double helicate ([Zn2(L1)2](ClO4)4), which has been structurally characterized. In the solid state, each ligand splits into two tridentate binding domains with two Zn(II) ions coordinated by two bridging ligands in a double helicate arrangement. This complex can further react with s-block metal ions via the crown ether unit resulting in the structurally characterized zinc-containing helicate [Zn2(L1)2Ba2](ClO4)8. Ligand recognition studies of this helicate with a ligand that does not contain the crown ether unit but does contain the same N-donor array (L2) demonstrates, via both 1H NMR and ESI-MS studies, that a ligand recognition process does occur and the major species observed are the homoleptic species ([Zn2(L1)2](ClO4)4 and [Zn2(L2)2](ClO4)4). Addition of barium ions to the mixture increases the amount of the heteroleptic species ([Zn2(L1)(L2)](ClO4)4) present, resulting in an equal amount of homoleptic and heteroleptic species. This change in ligand recognition properties is attributed to electrostatic effects.

U2 - 10.1039/b702608k

DO - 10.1039/b702608k

M3 - Article

VL - 31

SP - 1525

EP - 1529

JO - New Journal of Chemistry

T2 - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

IS - 8

ER -