Antiferromagnetism induced by successive protonation of terminal phenol groups of a bis(μ-phenoxide)-bridged dicopper(II,II) complex

Hiromi Saimiya, Yukinari Sunatsuki, Masaaki Kojima, Setsuo Kashino, Takashi Kambe, Masakazu Hirotsu, Haruo Akashi, Kiyohiko Nakajima, Tadashi Tokii

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

The reaction of a tripodal ligand (H2L = N,N-bis(2-hydroxybenzyl)-N′,N′-dimethylethylenediamine) with (Cu(NO3)2·3H2O and Cu(ClO4)2·6H2O in methanol yielded [Cu2(HL)2](NO3)2·H 2O (1) and [Cu2(HL)2](ClO4)2 (1′), respectively. When H2L was allowed to react with CuSO4·5H2O in the presence of triethylamine (1:1:2) in methanol, the neutral dicopper(II,II) complex [Cu2(L)2] (2) was obtained. The monopositive species [Cu2(L)(HL)]ClO4·CH3OH·H 2O (3) crystallized on mixing 1′ and 2(1:1) in methanol-dichloromethane. The crystal structures of 1,2, and 3 were determined by X-ray crystallography. All of the complexes consist of a discrete dinuclear molecule with bis(μ-phenoxide)-bridges. The tripodal ligand functions as a tetradentate ligand and one of the phenolic oxygen atoms serves as a bridging ligand. Protonation/deprotonation takes place at the terminal phenol moiety and as the phenol group is deprotonated the coordination geometry changes from a distorted square pyramid to a distorted trigonal bipyramid. The two copper ions in 1-3 are antiferromagnetically coupled with 2J = -714 (1), -19.9 (2), -277 cm-1 (3). The results clearly demonstrate that protonation/deprotonation causes a change in coordination geometry, which in turn drastically affects magnetic exchange interactions.

Original languageEnglish
Pages (from-to)3737-3742
Number of pages6
JournalJournal of the Chemical Society, Dalton Transactions
Issue number19
Publication statusPublished - 2002

Fingerprint

Antiferromagnetism
Protonation
Phenol
Ligands
Methanol
Deprotonation
Geometry
Methylene Chloride
X ray crystallography
Exchange interactions
Copper
Crystal structure
Ions
Oxygen
Atoms
Molecules
perchlorate

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Antiferromagnetism induced by successive protonation of terminal phenol groups of a bis(μ-phenoxide)-bridged dicopper(II,II) complex. / Saimiya, Hiromi; Sunatsuki, Yukinari; Kojima, Masaaki; Kashino, Setsuo; Kambe, Takashi; Hirotsu, Masakazu; Akashi, Haruo; Nakajima, Kiyohiko; Tokii, Tadashi.

In: Journal of the Chemical Society, Dalton Transactions, No. 19, 2002, p. 3737-3742.

Research output: Contribution to journalArticle

Saimiya, Hiromi ; Sunatsuki, Yukinari ; Kojima, Masaaki ; Kashino, Setsuo ; Kambe, Takashi ; Hirotsu, Masakazu ; Akashi, Haruo ; Nakajima, Kiyohiko ; Tokii, Tadashi. / Antiferromagnetism induced by successive protonation of terminal phenol groups of a bis(μ-phenoxide)-bridged dicopper(II,II) complex. In: Journal of the Chemical Society, Dalton Transactions. 2002 ; No. 19. pp. 3737-3742.
@article{01b850ac695d4f60907af42c09f883df,
title = "Antiferromagnetism induced by successive protonation of terminal phenol groups of a bis(μ-phenoxide)-bridged dicopper(II,II) complex",
abstract = "The reaction of a tripodal ligand (H2L = N,N-bis(2-hydroxybenzyl)-N′,N′-dimethylethylenediamine) with (Cu(NO3)2·3H2O and Cu(ClO4)2·6H2O in methanol yielded [Cu2(HL)2](NO3)2·H 2O (1) and [Cu2(HL)2](ClO4)2 (1′), respectively. When H2L was allowed to react with CuSO4·5H2O in the presence of triethylamine (1:1:2) in methanol, the neutral dicopper(II,II) complex [Cu2(L)2] (2) was obtained. The monopositive species [Cu2(L)(HL)]ClO4·CH3OH·H 2O (3) crystallized on mixing 1′ and 2(1:1) in methanol-dichloromethane. The crystal structures of 1,2, and 3 were determined by X-ray crystallography. All of the complexes consist of a discrete dinuclear molecule with bis(μ-phenoxide)-bridges. The tripodal ligand functions as a tetradentate ligand and one of the phenolic oxygen atoms serves as a bridging ligand. Protonation/deprotonation takes place at the terminal phenol moiety and as the phenol group is deprotonated the coordination geometry changes from a distorted square pyramid to a distorted trigonal bipyramid. The two copper ions in 1-3 are antiferromagnetically coupled with 2J = -714 (1), -19.9 (2), -277 cm-1 (3). The results clearly demonstrate that protonation/deprotonation causes a change in coordination geometry, which in turn drastically affects magnetic exchange interactions.",
author = "Hiromi Saimiya and Yukinari Sunatsuki and Masaaki Kojima and Setsuo Kashino and Takashi Kambe and Masakazu Hirotsu and Haruo Akashi and Kiyohiko Nakajima and Tadashi Tokii",
year = "2002",
language = "English",
pages = "3737--3742",
journal = "Dalton Transactions",
issn = "1477-9226",
publisher = "Royal Society of Chemistry",
number = "19",

}

TY - JOUR

T1 - Antiferromagnetism induced by successive protonation of terminal phenol groups of a bis(μ-phenoxide)-bridged dicopper(II,II) complex

AU - Saimiya, Hiromi

AU - Sunatsuki, Yukinari

AU - Kojima, Masaaki

AU - Kashino, Setsuo

AU - Kambe, Takashi

AU - Hirotsu, Masakazu

AU - Akashi, Haruo

AU - Nakajima, Kiyohiko

AU - Tokii, Tadashi

PY - 2002

Y1 - 2002

N2 - The reaction of a tripodal ligand (H2L = N,N-bis(2-hydroxybenzyl)-N′,N′-dimethylethylenediamine) with (Cu(NO3)2·3H2O and Cu(ClO4)2·6H2O in methanol yielded [Cu2(HL)2](NO3)2·H 2O (1) and [Cu2(HL)2](ClO4)2 (1′), respectively. When H2L was allowed to react with CuSO4·5H2O in the presence of triethylamine (1:1:2) in methanol, the neutral dicopper(II,II) complex [Cu2(L)2] (2) was obtained. The monopositive species [Cu2(L)(HL)]ClO4·CH3OH·H 2O (3) crystallized on mixing 1′ and 2(1:1) in methanol-dichloromethane. The crystal structures of 1,2, and 3 were determined by X-ray crystallography. All of the complexes consist of a discrete dinuclear molecule with bis(μ-phenoxide)-bridges. The tripodal ligand functions as a tetradentate ligand and one of the phenolic oxygen atoms serves as a bridging ligand. Protonation/deprotonation takes place at the terminal phenol moiety and as the phenol group is deprotonated the coordination geometry changes from a distorted square pyramid to a distorted trigonal bipyramid. The two copper ions in 1-3 are antiferromagnetically coupled with 2J = -714 (1), -19.9 (2), -277 cm-1 (3). The results clearly demonstrate that protonation/deprotonation causes a change in coordination geometry, which in turn drastically affects magnetic exchange interactions.

AB - The reaction of a tripodal ligand (H2L = N,N-bis(2-hydroxybenzyl)-N′,N′-dimethylethylenediamine) with (Cu(NO3)2·3H2O and Cu(ClO4)2·6H2O in methanol yielded [Cu2(HL)2](NO3)2·H 2O (1) and [Cu2(HL)2](ClO4)2 (1′), respectively. When H2L was allowed to react with CuSO4·5H2O in the presence of triethylamine (1:1:2) in methanol, the neutral dicopper(II,II) complex [Cu2(L)2] (2) was obtained. The monopositive species [Cu2(L)(HL)]ClO4·CH3OH·H 2O (3) crystallized on mixing 1′ and 2(1:1) in methanol-dichloromethane. The crystal structures of 1,2, and 3 were determined by X-ray crystallography. All of the complexes consist of a discrete dinuclear molecule with bis(μ-phenoxide)-bridges. The tripodal ligand functions as a tetradentate ligand and one of the phenolic oxygen atoms serves as a bridging ligand. Protonation/deprotonation takes place at the terminal phenol moiety and as the phenol group is deprotonated the coordination geometry changes from a distorted square pyramid to a distorted trigonal bipyramid. The two copper ions in 1-3 are antiferromagnetically coupled with 2J = -714 (1), -19.9 (2), -277 cm-1 (3). The results clearly demonstrate that protonation/deprotonation causes a change in coordination geometry, which in turn drastically affects magnetic exchange interactions.

UR - http://www.scopus.com/inward/record.url?scp=0035981329&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0035981329&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0035981329

SP - 3737

EP - 3742

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 19

ER -